JP2001278930A - Production for building material and civil engineering - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production for building material and civil engineering so that it may satisfy various requirements demanded for their applications. SOLUTION: The production comprises an olefin block copolymer (A) represented by formula (I); PO-f-R [wherein PO means a polyolefin segment having weight average molecular weight of 2,000 or more, which comprises repeated units derived from a 2-20C olefin; f means an ether bond, an ester bond or an amide bond; R means a functional segment having weight average molecular weight of 500 or more obtained by chain polymerization reaction] or an olefin polymer composition (C) containing the copolymer (A) and a thermoplastic resin (B) other than copolymer (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article for building materials and civil engineering comprising an olefin-based block copolymer or an olefin-based polymer composition containing the copolymer.

[0002]

BACKGROUND ART Conventionally, various synthetic resins, for example, polyolefins, have been used as materials for building materials and molded articles for civil engineering such as flooring materials, sheets, gasket / sealing materials, and asphalt modifying materials. Of these, flooring materials are required to have impact resistance, scratch resistance, etc., sheets are required to have flexibility, pinhole resistance, puncture resistance, etc., and gasket / sealing materials are required to have flexibility. The asphalt modifier is required to have heat resistance, compatibility with asphalt, and the like.

The inventors of the present invention have studied a molded product for building materials and civil engineering which satisfies the above-mentioned requirements. Units and / or
Alternatively, an olefin-based block copolymer in which a functional segment including a repeating unit containing a hetero atom is bonded by an ether bond or the like, or an olefin-based polymer composition containing the copolymer satisfies the above requirements. To complete the present invention.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a molded product for building materials and civil engineering which satisfies various requirements required for building materials and civil engineering applications.

[0005]

SUMMARY OF THE INVENTION A molded material for building materials and civil engineering according to the present invention is represented by the following general formula (I) and has a melt flow rate (AST).
MD 1238, 230 ° C, load 2.16 kg) is 0.
PO-fR (I) (wherein PO has a carbon number of 2 to 20). Having a weight average molecular weight of 2,2.
000, wherein f is:
Shows an ether bond, an ester bond or an amide bond,
R is obtained by a chain polymerization reaction and has a weight average molecular weight of 500
The functional segment described above is shown. ).

Further, a molded article for building materials and civil engineering according to another aspect of the present invention includes the olefin-based block copolymer (A).
And an olefin polymer composition (C) containing a thermoplastic resin (B) other than (A).

[0007]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the molded article for building materials and civil engineering according to the present invention will be specifically described. Building materials according to the present invention
The molded article for civil engineering comprises the olefin-based block copolymer (A) represented by the following general formula (I). PO-fR ... (I) In the formula, PO is a polyolefin segment composed of a repeating unit derived from an olefin having 2 to 20 carbon atoms, and specifically, a polyolefin segment having 2 to 20 carbon atoms. It is a homopolymer or copolymer of the selected olefin. When this polyolefin segment has stereoregularity, it may be either an isotactic polyolefin or a syndiotactic polyolefin.

[0008] Examples of the olefin having 2 to 20 carbon atoms include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, and non-conjugated dienes. Specific examples of the linear or branched α-olefin include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -Methyl-1-pentene,
3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl
-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
2 to 2 carbon atoms such as 1-octadecene and 1-eicosene
0, preferably 2 to 10.

Examples of the cyclic olefin include those having 3 to 20, preferably 5 to 15 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and vinylcyclohexane. As the aromatic vinyl compound, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-methylstyrene Mono- or polyalkylstyrenes such as ethylstyrene are mentioned.

As the conjugated diene, for example, 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,
3-dimethylbutadiene, 4-methyl-1,3-pentadiene,
Examples thereof include those having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, such as 1,3-pentadiene, 1,3-hexadiene, and 1,3-octadiene. Non-conjugated dienes include, for example, 1,4-
Pentadiene, 1,4-hexadiene, 1,5-hexadiene,
1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6
-Methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), Dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-
Ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2- C5-20, preferably 5-1 carbon atoms such as ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.
0.

The polyolefin segment has a weight average molecular weight of usually at least 2,000, preferably at least 2,000.
10,000,000, more preferably 10,000-1
0,000,000, particularly preferably 10,000-20
It is desirable to be in the range of 0.000. The polyolefin segment includes ethylene homopolymer, ethylene / α-olefin copolymer, ethylene / propylene / vinyl norbornene copolymer, ethylene / propylene / D
MDT copolymer, ethylene / cyclic olefin / propylene / DMDT copolymer, ethylene / cyclic olefin / propylene / conjugated diene copolymer, ethylene / cyclic olefin / propylene / conjugated polyene copolymer, ethylene
Ethylene polymers such as aromatic vinyl copolymer, ethylene / aromatic vinyl / conjugated polyene copolymer; propylene homopolymer, syndiotactic propylene / ethylene copolymer, atactic propylene / ethylene copolymer, propylene -Propylene-based polymers such as α-olefin copolymers; butene-based polymers such as butene-ethylene copolymers; 4-methyl-1- such as 4-methyl-1-pentene homopolymers Pentene polymers and the like are preferred.

In the above general formula (I), f is an ether bond, an ester bond or an amide bond, and among them, an ether bond is preferable. This part f chemically bonds the above-mentioned polyolefin segment and the following functional segment. Note that f may include a part of a structure formed by the following chain polymerization reaction, for example, a radical polymerization reaction, a ring-opening polymerization reaction, or an ionic polymerization reaction.

In the above general formula (I), R is a functional segment obtained by a radical polymerization reaction, a ring-opening polymerization reaction or an ionic polymerization. It is preferably a functional segment containing a unit, and more preferably obtained by a radical polymerization reaction or a ring-opening polymerization reaction. Further, it is preferable that PO and R are segments composed of different polymers.

The repeating unit forming the functional segment is a radical polymer such as methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate, vinyl acrylate (VA), butyl acrylate (BA), styrene, acrylonitrile, and vinyl acetate. Repeating units derived from a reactive monomer; lactones, lactams, 2-oxazolines, cycloethers such as β-propiolactone, β-butyrolactone,
δ-valerolactone, glycolide, lactide, ε-caprolactone, α-pyrrolidone, γ-butyrolactam, ε-
Ring-opening polymerizable monomers such as caprolactam, ethylene oxide, propylene oxide, epichlorohydrin, oxetane, tetrahydrofuran, and octamethylcyclotetrasiloxane.

Further, as the ionic polymerizable monomer,
Anionic polymerizable monomers such as (meth) acrylates, acrylonitrile, acrylamide and the like can be mentioned. This functional segment has a weight average molecular weight (M
w) is usually 500 or more, preferably 5,000 to 1,000.
000, more preferably 2,000 to 1,000,000
0, particularly preferably in the range of 10,000 to 200,000.

Specific examples of the functional segment include styrene homopolymers, styrene polymers such as styrene / maleic anhydride copolymers, and vinyl acetate ester polymers;
Acrylic ester polymer; methacrylic ester polymer such as methyl methacrylate homopolymer; vinyl formamide polymer; acrylamide polymer, cyclic ester polymer; cyclic amide polymer; cyclic ether polymer An oxazoline-based polymer; a segment comprising a fluorine-containing polymer and the like.

The functional segment is preferably 0.01 to 9 with respect to the olefin block copolymer (A).
9.99% by weight, preferably 1 to 99% by weight, more preferably 1 to 95% by weight, particularly preferably 1 to 90% by weight
Is preferably contained in an amount of The melt flow rate (MFR; ASTM D 1238, 230 ° C., load 2.16 kg) of the olefin block copolymer (A) used in the present invention is usually 0.01 to 200 g / 10 min, preferably 0.05. -100 g / 10 min, more preferably 0.05-80 g / 10 min.

Such an olefin block copolymer (A) can be produced as follows. Olefin block copolymer (A) used in the present invention
For example, first, a polyolefin having a group 13 element bonded to a terminal is produced, and then, in the presence of the polyolefin,
It can be produced by forming an active species such as a chain polymerization reaction, for example, a radical polymerization reaction, a ring-opening polymerization reaction, or an ionic polymerization reaction, and performing these reactions.

The polyolefin having a group 13 element bonded to its terminal can be produced by coordination polymerization with a transition metal. For example, in the presence of a conventionally known catalyst for olefin polymerization, a polyolefin having 2 to 2 carbon atoms as described above is used. 20 olefins are homopolymerized or copolymerized. The polyolefin produced here becomes the polyolefin segment of the olefin-based block copolymer (A) (hereinafter sometimes referred to as “PO part”).

Conventionally known olefin polymerization catalysts include TiCl ₃ -based catalysts, MgCl ₂ -supported TiCl ₄ -based catalysts, metallocene-based catalysts, and post-metallocene-based catalysts, and the use of metallocene-based catalysts is preferred.
Examples of preferably used metallocene catalysts include conventionally known metallocene catalysts. Examples of metallocene catalysts include transition metal metallocene compounds such as titanium, vanadium, chromium, zirconium, and hafnium. The metallocene compound may be used in a liquid state or a solid state under the use conditions. Also,
These need not be a single compound, but may be supported on another compound, may be a homogeneous mixture with another compound, and may be a complex compound or a complex compound with another compound. Is also good.

For the production of polyolefin, it is preferable to use a metallocene compound having a chiral structure having C2 symmetry or C1 symmetry among conventionally known metallocene catalysts. Examples of the metallocene compound having a chiral structure having C2 symmetry include rac-ethylene-bis (indenyl) zirconium dichloride, rac-ethylene-bis (tetrahydroindenyl) zirconium dichloride, and rac-dimethylsilylene-bis (2,3,5- (Trimethylcyclopentadienyl)
Zirconium dichloride, rac-dimethylsilylene-bis [1- (4-phenylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, rac-dimethyl Silylene-bis {1- [2-methyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilylene-bis {1- [2-methyl-4- (2-naphthyl) indenyl]} zirconium dichloride , Rac-dimethylsilylene
-Bis {1- [2-methyl-4- (1-anthracenyl) indenyl]} zirconium dichloride, rac-dimethylsilylene
-Bis {1- [2-methyl-4- (9-anthryl) indenyl]}
Zirconium dichloride, rac-dimethylsilylene-bis {1- [2-methyl-4- (9-phenanthryl) indenyl]}
Zirconium dichloride, rac-dimethylsilylene-bis {1- [2-methyl-4- (o-chlorophenyl) indenyl]}
Zirconium dichloride, rac-dimethylsilylene-bis {1- [2-methyl-4- (pentafluorophenyl) indenyl]} zirconium dichloride, rac-dimethylsilylene
-Bis [1- (2-ethyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis {1- [2-
Ethyl-4- (1-naphthyl) indenyl] {zirconium dichloride, rac-dimethylsilylene-bis} 1- [2-ethyl-
4- (9-phenanthryl) indenyl] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-n-propyl
-4-phenylindenyl)] zirconium dichloride, ra
c-dimethylsilylene-bis {1- [2-n-propyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-
Dimethylsilylene-bis {1- [2-n-propyl-4- (9-phenanthryl) indenyl]} zirconium dichloride is a preferred example.

Examples of the metallocene compound having a C1 symmetry and having a chiral structure include ethylene [2-methyl-4- (9-phenanthryl) -1-indenyl] (9-fluorenyl) zirconium dichloride and ethylene [2-methyl-4- (9-phenanthryl) -1-indenyl] (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (9-fluorenyl) (3-t-butylcyclopentadienyl) zirconium dichloride, diphenylsilylene (9- Fluorenyl) (3-t
-Butylcyclopentadienyl) zirconium dichloride and the like can be mentioned as preferred examples.

The metallocene compound preferably used among the conventionally known metallocene compounds also includes a metallocene compound having only one substituted cyclopentadienyl group. For example, (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1, 2-ethanediyl titanium dichloride, (methyl amide) (tetramethyl
-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide) (tetramethyl-η ⁵
-Cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl) methylene titanium dichloride, (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclo (Pentadienyl) silanetitanium dichloride, (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanezirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane Titanium dichloride, (phenylphosphido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanezirconium dibenzyl and the like.

Further, among the conventionally known metallocene compounds, the metallocene compound preferably used has two substituted cyclopentadienyl groups, and the two cyclopentadienyl are (substituted) alkylene, (substituted) ) Metallocene compounds that are not bonded by a bonding group such as silylene are also included. For example, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate) Nato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (Butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutyl Cyclopentadienyl)
Zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride,
Bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, and the like.

The above metallocene compounds may be used alone.
Two or more kinds may be used in combination._Threesystem
Catalyst, MgCl_TwoSupported TiCl_FourBased catalyst, post metallo
Combination with other olefin polymerization catalysts such as styrene catalysts
They may be used together. In the production of polyolefin,
Metallocene compounds are combined with the following organometallic catalyst components
Used. Also, TiCl_ThreeSystem catalyst, MgCl_TwoResponsible
Holding type TiCl _Four-Based catalyst or post-metallocene-based catalyst
Also used in combination with the following organometallic catalyst components
used.

The post-metallocene catalyst is a transition metal complex containing a nitrogen atom or an oxygen atom in a ligand, and a conventionally known transition metal complex is preferably used. Examples of post-metallocene catalysts include transition metal complexes as described in the following references. 1) M. Brookhart et al., J. Am. Chem. Soc. 1995, 117, 6414-
6415 2) M. Brookhart et al., J. Am. Chem. Soc. 1996, 118, 267-2
68 3) DHMcConville et al., Macromolecules 1996, 29, 52
41-5243 4) RFJordan et al., Organometallics 1997,16,3282-
3302 5) RHGrubbs et al., Organometallics 1998, 17, 3149-
3151 6) S. Collins et al., Organometallics 1999, 18, 2731-2
733 7) MSEisen et al., Organometallics 1998, 17, 3155-3
157 8) MSEisen et al., J. Am. Chem. Soc. 1998, 120, 8640-86
36 9) RFJordan et al., J. Am. Chem. Soc. 1997, 119, 8125-8
126 10) K. Hakala et al., Macromol. Rapid Commun. 18, 634-6
38 (1997) The organometallic catalyst component preferably contains an element selected from Group 13 of the periodic table. Among them, an organoaluminum compound, an organic boron compound, a complex alkyl compound of aluminum or boron with a Group 1 element of the periodic table And the like.

As the organoaluminum compound, for example, compounds represented by the following general formula can be exemplified. R ^a _n AlX _3-n (wherein, R ^a represents a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen or hydrogen, n represents a 0 to 3.) R ^a is a carbon atom A hydrocarbon group of Formulas 1 to 12, such as an alkyl group, a cycloalkyl group or an aryl group,
Specific examples include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and the like.

Specific examples of such an organoaluminum compound include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-aluminum and the like.
Trialkylaluminums such as ethylhexylaluminum; trialkenylaluminums such as triisoprenylaluminum; dimethylaluminum chloride;
Diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride,
Dialkyl aluminum halides such as dimethyl aluminum bromide, methyl aluminum sesquichloride,
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide; diethyl Alkyl aluminum hydrides such as aluminum hydride, diisobutyl aluminum hydride and ethyl aluminum dihydride are exemplified.

Further, as the organoaluminum compound,
A compound represented by the general formula can also be used. R^a _nAlY_3-n In the above formula, R^aIs the same as above, and Y is -O
R^bGroup, -OSiR^c _ThreeGroup, -OAlR^d _TwoGroup, -NR
^e _TwoGroup, -SiR^f _ThreeGroup or -N (R^g) AlR^h _TwoIn the base
And n is 1-2, R^b, R^c, R^dAnd R^hIs
Chill, ethyl, isopropyl, isobutyl, cyclohexyl
Sil, phenyl and the like;^eIs a hydrogen atom, methyl,
Ethyl, isopropyl, phenyl, trimethylsilyl
Which is R^fAnd R^gIs methyl, ethyl and the like.

Specific examples of such an organoaluminum compound include the following compounds. (I) ^a compound represented by R ^a _n Al (OR ^b ) _3-n , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (ii) R ^a n Al (OSiR ^c ) _3- n _n , for example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂
Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc., and (iii) compounds represented by R ^a _n Al (OAlR ^d ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-Bu) ) ₂ AlOAl
(Iso-Bu) _{2, ^{etc., (iv) R a n Al}} (NR e 2) a compound represented by _3-n, e.g., Me ₂ AlNEt _2, Et ₂ AlNHM
e, Me ₂ AlNHEt, Et ₂ AlN (Me ₃ Si) ₂ , (iso-B
u) ₂ AlN (Me ₃ Si) ₂ and (v) R ^a _n Al (Si
R ^f ₃ ) A compound represented by _3-n , for example, (iso-Bu) ₂ Al
Such as ^{_{SiMe 3, (vi) R a}} n Al [N (R ^g) -Al
R ^h ₂ ] _3-n , for example, Et ₂ AlN (M
e) -AlEt ₂ (iso-Bu) ₂ , AlN (Et) Al (iso-Bu)
₂ etc.

Similar compounds such as oxygen
, Two or more aluminum atoms are bonded via a nitrogen atom
Organic aluminum compounds can be mentioned. concrete
Contains (C_TwoH_Five)_TwoAlOAl (C_TwoH_Five)_Two, (C_FourH₉)_TwoAl
OAl (C_FourH₉) _Two, (C_TwoH_Five)_TwoAlN (C_TwoH_Five) Al (C_Two
H_Five)_Two Such. Furthermore, methyl aluminoxane, ethyl alcohol
Minoxane, propylaluminoxane, butylalumino
Aluminoxanes such as xane can be mentioned.

Further, an organoaluminum compound represented by the following general formula can also be used. R ^a AlXY (where R ^a , X and Y are the same as above) Examples of the organic boron compound include triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, Tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, texylborane, dicyclohexylborane, Disiamyl borane, diisopinocan phenyl borane, 9-borabicyclo
[3.3.1] Nonane, dimethylborane, dichloroborane, catecholborane, B-bromo-9-borabicyclo [3.3.1] nonane, borane-triethylamine complex, borane-methylsulfide complex and the like.

Further, an ionic boron compound may be used as the organic boron compound. Such compounds include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) boron Ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl)
Ammonium tetra (p-trifluoromethylphenyl)
Boron, N, N-dimethylanilinium tetra (phenyl)
Boron, dicyclohexylammonium tetra (phenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, bis [tri (n-butyl) ammonium] nonaborate, Bis [tri (n-butyl) ammonium] decaborate and the like can be mentioned.

Examples of the complex alkylated product of Group 1 element of the periodic table and aluminum include compounds represented by the following general formula. M ¹ AlR ^j ₄ (wherein, M ¹ represents Li, Na or K, and R ^j represents a hydrocarbon group having 1 to 15 carbon atoms.) Specifically, LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ )
_{4 and the} like.

Examples of the organic boron compound and the complex alkylated product of boron with the Group 1 element in the periodic table include the above-mentioned organic aluminum compound and the complex alkylated product of aluminum with the Group 1 element in the periodic table in which aluminum is substituted with boron. Can be mentioned. The organometallic catalyst components can be used alone or in combination of two or more.

The organometallic catalyst component is preferably used in combination with a compound having a hydrogen-13 group element bond and a trialkylaluminum, an aluminoxane or an ionic boron compound. The compound is preferably a compound having a hydrogen-boron bond. These compounds may be used for polymerization after mixing, or after starting polymerization using only trialkylaluminum or aluminoxane or ionic boron compound, a compound having a hydrogen-13 group element bond may be added to the polymerization system. preferable.

Examples of the compound having a hydrogen-13 group element bond include diethyl aluminum hydride, diisobutyl aluminum hydride and ethyl aluminum dihydride among the organic aluminum compounds; and 9-borabicyclo [3.
3.1] Nonane, dimethylborane, dichloroborane, catecholborane and the like.

The olefin polymerization catalyst as described above may be preliminarily polymerized. There is no particular limitation on the method of performing the prepolymerization, for example, can be performed in the presence of an inert solvent,
It is preferable to add the olefin and each catalyst component to the inert solvent and carry out prepolymerization under relatively mild conditions. At this time, the reaction may be performed under the condition that the produced prepolymer is dissolved in the polymerization medium, or may be performed under the condition that the prepolymer is not dissolved.
It is preferably performed under conditions that do not dissolve.

Examples of the olefin used for the prepolymerization include α-olefins having 2 or more carbon atoms. Specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-olefin. 1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4,
4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1
-Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. These may be used in combination of two or more. The α-olefin used in the prepolymerization may be the same as or different from the α-olefin used in the olefin polymerization described below, but is preferably the same as the olefin used in the olefin polymerization.

Specific examples of the inert solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene;
Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride and chlorobenzene. These may be used in combination.

Among these inert solvents, it is particularly preferable to use an aliphatic hydrocarbon. The prepolymerization is α-
The reaction can be carried out in a state in which the olefin is in a liquid state, or under gas phase conditions. The prepolymerization can be performed in any of a batch system, a semi-continuous system, and a continuous system. Further, in the preliminary polymerization, it is preferable to use a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization.

The above olefin block copolymer (A)
The polyolefin to be the PO portion of the olefin is a homopolymerization or copolymerization of the olefin having 2 to 20 carbon atoms as described above in the presence of the olefin polymerization catalyst as described above (hereinafter, referred to as “Polyolefin”).
Sometimes simply referred to as “olefin polymerization”. ). The olefin polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. As the reaction solvent for suspension polymerization, the above-mentioned inert solvent can be used, or an olefin that is liquid at the reaction temperature can be used. The reaction temperature is
Usually, it is in the range of -50 ° C to 200 ° C, preferably 0 ° C to 150 ° C. The polymerization pressure is usually 0.1 to 100 atm,
Preferably it is 1 to 50 atm. The olefin polymerization can be performed in any of a batch system, a semi-continuous system, and a continuous system. When the olefin polymerization is performed in two or more stages, the reaction conditions may be the same or different.

In the olefin polymerization, the weight average molecular weight is usually 2,000 or more, preferably 2,000 to 1,000,000.
00 polyolefin is produced. In this case, it is preferable that molecular hydrogen, which is a general molecular weight regulator, is not present in the polymerization system. It is preferable to control by controlling one or more kinds. Specifically, as a method for adjusting the molecular weight, for example, in suspension polymerization in which molecular hydrogen is substantially absent, increasing the concentration of the organometallic catalyst component can reduce the molecular weight of the obtained polyolefin, Also, in suspension polymerization in which molecular hydrogen is substantially absent, raising the polymerization temperature can lower the molecular weight of the resulting polyolefin.

One end of the polyolefin obtained as described above is a terminal to which a group 13 element is bonded or an unsaturated terminal. Whether one end of the polyolefin is a group 13 element-bonded terminal or an unsaturated bond terminal depends on polymerization conditions such as the type and / or amount of the organometallic catalyst component used and the polymerization temperature. When one terminal of the polyolefin is an unsaturated bond terminal, a compound containing a Group 13 element is reacted to convert the compound into a terminal to which a Group 13 element is bonded.
In addition, when the obtained polyolefin is a mixture of one having a group 13 element bonded to one end and one having an unsaturated bond terminal at one end, if necessary, one end may have an unsaturated bond. You may convert the terminal of the polyolefin which is a terminal into the terminal which group 13 element couple | bonded.

The compound containing a Group 13 element used in the reaction is selected from the compounds exemplified as the organic compound catalyst component, and the compounds exemplified as the organic aluminum compound or the organic boron compound are preferably used.
Among them, a trialkylaluminum, a dialkylaluminum hydride or a boron compound having one or more hydrogen-boron bonds is more preferable, and a boron compound having one or more hydrogen-boron bonds is particularly preferable. Most preferred compounds include 9-borabicyclo [3.3.1] nonane, which may be a monomer or a dimer.

The reaction between a polyolefin having an unsaturated bond terminal at one end and a compound containing a Group 13 element is carried out, for example, as follows. A mixture of 0.1 to 50 g of a polypropylene having a vinylidene group at the end and 5 to 1000 ml of a 0.01 to 5 mol / l-octane solution of diisobutylaluminum hydride was added.
Reflux for 5-6 hours. 0.1-50 g of polypropylene terminated with vinylidene group, 5-1000 ml of anhydrous tetrahydrofuran, and 0.05-50 ml of 0.1-50 ml of 9-borabicyclo [3.3.1] nonane.
Mix with 10 mol / l-tetrahydrofuran solution and stir at 20-65 ° C for 0.5-24 hours.

As described above, a polyolefin to be the PO portion of the olefin block copolymer (A) is produced. A group 13 element is bonded to one end of the obtained polyolefin. Preferably, the Group 13 element is boron. Next, in the presence of a polyolefin having a Group 13 element bonded to one end, chain polymerization active species such as a radical polymerization reaction, a ring-opening polymerization reaction, and an ionic polymerization reaction are formed, and these reactions are performed to perform olefin block copolymerization. A polymer (A) is produced. By this reaction, the 1
An f-part is formed between the group III element and the polyolefin segment, and a polymer produced by a chain polymerization reaction such as a radical polymerization reaction, a ring-opening polymerization reaction, or an ionic polymerization reaction has a functional segment (hereinafter referred to as “R part”). "). The part f may include a part of a structure formed by a chain polymerization reaction such as a radical polymerization reaction, a ring-opening polymerization reaction, and an ionic polymerization reaction.

This polymerization reaction is carried out, for example, as follows. (1) When the group 13 element bonded to one end of the polyolefin is boron, a radical is generated by oxidizing a carbon-boron bond with molecular oxygen in the presence of a radical polymerizable monomer to cause a radical polymerization reaction. Do.

Specifically, a polyolefin having boron bonded to one end is oxidized with molecular oxygen in the presence of a radically polymerizable monomer. This converts the terminal boron to peroxyborane (-OOB). The peroxyborane is stirred in the presence of a radically polymerizable monomer, whereby the O—O bond is cleaved to generate a radical, and the generated alkoxy radical (—O ^* ) serves as an initiator to perform radical polymerization. Radical polymerization of the reactive monomer proceeds.

The radical polymerizable monomers include methyl methacrylate (MMA) and ethyl methacrylate (E
MA), butyl methacrylate, vinyl acrylate (VA), butyl acrylate (BA), styrene, acrylonitrile, vinyl acetate, and the like.
These radically polymerizable monomers can be used alone,
It may be used in combination of more than one kind.

The termination of the radical polymerization can be carried out by precipitating the polymer in methanol. As described above, the olefin block copolymer (A) in which the f portion is an ether bond or an ester bond and the R portion is a radical polymer can be produced. (2) When the group 13 element bonded to one end of the polyolefin is aluminum, a carbon-aluminum bond is oxidized with molecular oxygen to generate an active species to perform a ring-opening polymerization reaction.

Specifically, the carbon-aluminum bond is oxidized with molecular oxygen, thereby converting the aluminum at the terminal of the PO portion to aluminum oxide (-O-Al). The ring-opening polymerizable monomer is subjected to ring-opening polymerization using the thus obtained aluminum oxide as an active species. As ring-opening polymerizable monomers, lactones, lactams, 2-
Oxazolines, cycloethers and the like, specifically, β-propiolactone, β-butyrolactone, δ-valerolactone, glycolide, lactide, ε-caprolactone, α-pyrrolidone, γ-butyrolactam, ε-caprolactam, Examples include ethylene oxide, propylene oxide, epichlorohydrin, oxetane, tetrahydrofuran, and octamethylcyclotetrasiloxane. These ring-opening polymerizable monomers may be used alone or in combination of two or more.

The ring-opening polymerization reaction is carried out usually at a temperature of 0 to 100 ° C. for 30 minutes to 12 hours, preferably for 1 hour to 6 hours. The ring-opening polymerization reaction can be stopped by precipitating the polymer in methanol. As described above, the olefin block copolymer (A) in which the f portion is an ether bond or an ester bond and the R portion is a ring-opening polymer can be produced. (3) After converting a Group 13 element bonded to one end of the polyolefin into a hydroxyl group, an amino group, an aldehyde group or a halogen, a ring-opening polymerization reaction is performed by generating a ring-opening polymerization active species.

The ring-opening polymerization active species is produced, for example, by adding a sodium hydroxide solution and a hydrogen peroxide solution to a polyolefin having one end bonded to boron at 40 to 50 ° C.
The reaction can be performed by converting boron into a hydroxyl group by reacting for up to 5 hours, reacting butyllithium with this, and then reacting with diethylaluminum chloride to convert the hydroxyl group into aluminum oxide.

The above ring-opening polymerizable monomer is subjected to a ring-opening polymerization reaction using the aluminum oxide obtained as described above as an active species. The ring-opening polymerization reaction is performed in the same manner as in the above method (2). Further, instead of aluminum oxide, another metal alkoxide, metal halide or metal amine may be bonded to one end of the polyolefin to be an active species for the ring-opening polymerization reaction. Active species other than aluminum oxide are generated using a hydroxyl group, an amino group, an aldehyde group or a halogen bonded to one end of the polyolefin. Among these, it is preferable to use aluminum oxide as the active species. As described above, the olefin block copolymer (A) in which the f portion is an ether bond, an ester bond, or an amide bond and the R portion is a ring-opening polymer can be produced.

As an example of the ionic polymerization reaction, for example, in the case of performing an anionic polymerization reaction, after converting the above-mentioned polyolefin having a hydroxyl group at the terminal to a polyolefin having a lithium, potassium, sodium, phosphorus-containing group or the like at the terminal, It can be obtained by polymerizing a monomer capable of anion polymerization. As an example, a method for producing a block copolymer having a (meth) acrylic acid ester as an example of a segment in which the R portion is an anionic polymer using a polyolefin having a terminal lithium is described.

Of a polyolefin having a terminal lithium
The prepared polyolefin having a terminal lithium is obtained by reacting the polyolefin having a terminal hydroxyl group with an organic lithium compound. The reaction between the polyolefin having a hydroxyl group at the terminal and the organolithium compound is usually performed in a solvent.

Examples of the organic lithium compound include alkyl lithium such as butyl lithium, propyl lithium, ethyl lithium and methyl lithium; and alkoxy lithium such as butoxy lithium, propoxy lithium, ethoxy lithium and methoxy lithium. In the present invention, alkyl lithium is more preferably used.

Examples of the solvent used in the reaction include the same hydrocarbons as those exemplified as the inert hydrocarbon medium. When reacting a polyolefin having a hydroxyl group at an end with an organolithium compound, the organolithium compound is added in an amount of 0.1 to 1 mol of the hydroxyl group at the end of the polyolefin.
To 100 mol, preferably 0.2 to 10 mol. The reaction temperature is generally -100 to 100C, preferably 0 to 80C, and the reaction time is usually 0.1 to 48.
Hours, preferably 0.5 to 12 hours.

Thus, a polyolefin having a terminal lithium represented by the following general formula (II) is produced. PO—O—Li (II) wherein PO has a weight average molecular weight of 1,000 to 10,000.
0,000, preferably 3,000 to 1,000,000,
More preferably, the polyolefin segment has a molecular weight of 5,000 to 500,000. The terminal Li polyolefin has Mw / Mn of 2 or more, preferably 3 to 15,
More preferably, it is desirable to be in the range of 4 to 14.

Production of Block Copolymer Next, for example, (meth) acrylate is anionically polymerized in the presence of the above-mentioned terminal Li polyolefin to form a polyolefin block copolymer comprising a polyolefin segment and a (meth) acrylate segment. Obtain a polymer. The polymerization is carried out by mixing a solvent, a terminal Li polyolefin and a (meth) acrylate, or
It is performed by mixing i-polyolefin and liquid (meth) acrylate. The anionic polymerization active species can be formed by mixing the terminal Li polyolefin, the solvent, and the (meth) acrylate.

Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; diethyl ether, dioxane, tetrahydrofuran (THF), Ether solvents such as monoglyme and diglyme are used. These solvents are 1
Species can be used alone or in combination of two or more. Among them, aromatic hydrocarbons and ether solvents are preferably used.

Examples of the (meth) acrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, vinyl acrylate, and methacrylic acid. 2-methoxyethyl acid, 2- (N, N-diethylamino) ethyl methacrylate and the like. These (meth) acrylic acid esters can be used alone or in combination of two or more. As the combination of the (meth) acrylic ester, two or more selected from acrylic esters, two or more selected from methacrylic esters, one or more selected from acrylic esters, and one or more selected from methacrylic esters In combination with

In the polymerization, compounds useful for forming anionic polymerization active species such as triphenylphosphine, α, α'-dipyridyl, hexamethylphosphoramide (HMPA), titanium tetrachloride, alkyllithium, and alkoxylithium are added. May be. Polymerization is usually -100 ° C
At a polymerization temperature of 100 ° C, preferably -80 ° C to 80 ° C, more preferably -70 ° C to 70 ° C, for 1 minute to 500 hours, preferably 10 minutes to 300 hours, more preferably 15 minutes to 150 hours. Will be implemented. In this polymerization, the terminal Li polyolefin is 0.001 to 10
0 mol / liter, preferably 0.005 to 50 mol /
Liter, more preferably 0.01 to 10 mol / l, even more preferably 0.1 to 5 mol / l. The (meth) acrylic acid ester is usually used in an amount of 0.001 to 500 mol / l, preferably 0.1 to 500 mol / l.
005-300 mol / l, more preferably 0.0
It is used at a concentration of 1-150 mol / l.

It is preferable to produce a poly (meth) acrylate segment having stereoregularity by the above polymerization. That is, a stereoregular poly (substituted acrylate) having a triad syndiotacticity (rr) of 70% or more or a triad isotacticity (mm) of 70% or more is preferable. Rr
For and mm, the sample was dissolved in nitrobenzene-d5, and ¹ H-NMR was measured.
Rr, mr, mm detected near 5, 1.25 ppm
Peak area of rr to the sum of peak areas of
It is determined from the ratio of the peak area of m.

As described above, a polymer containing a block copolymer in which the polyolefin segment (PO) and the poly (meth) acrylate segment are chemically bonded can be produced. Whether or not the polymer containing the (meth) acrylate segment is chemically bonded can be determined by, for example, the molecular weight of the obtained polymer, the solubility in an organic solvent, or spectroscopic analysis. That is, the molecular weight of the polymer obtained by the method of the present invention shows a high value with respect to the molecular weight of PO of the terminal Li polyolefin, and corresponds to the polyolefin segment of the olefin-based block copolymer polymer obtained by the method of the present invention. The dissolution behavior in an organic solvent of a mixture of a polymer and a polymer corresponding to a segment of a polymer produced by anionic polymerization of the polymer indicates that the olefin-based block copolymer obtained by the method of the present invention is soluble in an organic solvent. Behave differently, or
The terminal structure of the olefin-based block copolymer obtained by the method of the present invention is analyzed by ¹³ C-NMR to determine the chemical bond between the polyolefin segment and the poly (meth) acrylate segment of the polymer produced by anionic polymerization. It can be determined that the target block copolymer has been produced by detecting the derived peak.

In the above chain polymerization reactions such as radical polymerization reaction, ring opening polymerization reaction and ionic polymerization reaction, the weight average molecular weight is usually 500 or more, preferably 5000 to 1,
Produce 1,000,000 polymers. The molded article for building materials and civil engineering according to the present invention is formed from the olefin-based block copolymer (A) as described above. The olefin-based block copolymer (A) may contain an additive which is conventionally used as a filler, a core material, and other resins in an arbitrary ratio.

Further, the molded article for building materials and civil engineering according to the present invention
The olefin-based block copolymer (A);
It may be formed from an olefin polymer composition (C) containing a thermoplastic resin (B) other than the above. Examples of the thermoplastic resin (B) include polyolefin, polyamide, polyester, polyacetal, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate, polyphenylene oxide, polyacrylate, and polyvinyl chloride.

Specific examples of the polyolefin include ethylene polymers such as ethylene homopolymer, ethylene / α-olefin copolymer, and ethylene / polar group-containing vinyl copolymer; propylene homopolymer, propylene / α-olefin Propylene-based polymers such as copolymers; butene-based polymers such as butene homopolymer; 4-methyl-1-pentene-based polymers such as 4-methyl-1-pentene homopolymer; 3-methyl-
3-methyl-1-butene polymers such as 1-butene homopolymer; hexene polymers such as hexene homopolymer; Among them, ethylene-based polymers, propylene-based polymers, and 4-methyl-1-pentene-based polymerizations are preferable, and in the case of ethylene-based polymers, ethylene / polar group-containing vinyl copolymers are preferable.

Specific examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate;
Polycaprolactone, polyhydroxybutyrate and the like can be mentioned. Among them, polyethylene terephthalate is particularly preferred. Specifically, as a polyamide, nylon-
6, Nylon-66, Nylon-10, Nylon-1
2, aliphatic polyamides such as nylon-46; and aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines. Among them, nylon-6 is particularly preferred.

Specific examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, and polybutyraldehyde. Among them, polyformaldehyde is particularly preferred. The polystyrene may be a homopolymer of styrene or a binary copolymer of styrene and acrylonitrile, methyl methacrylate, α-methylstyrene, or the like.

The ABS contains a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and is derived from styrene. Structural unit 40 ~
ABS containing 60 mol% is preferably used. Examples of polycarbonate include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane,
Examples include polymers obtained from 2-bis (4-hydroxyphenyl) butane and the like. Among them, polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

As the polyphenylene oxide, it is preferable to use poly (2,6-dimethyl-1,4-phenylene oxide). As the polyacrylate, it is preferable to use polymethyl methacrylate and polybutyl acrylate. Thermoplastic resin (B) as described above
May be used alone or in combination of two or more.

The olefin polymer composition (C) used in the present invention contains the olefin block copolymer (A) in an amount of 1 to 99% by weight, preferably 50 to 99% by weight.
99 to 1% by weight, preferably 5% by weight of the thermoplastic resin (B)
Desirably, it is contained in an amount of 0 to 1% by weight. The olefin polymer composition (C) further includes a crosslinking agent, a crosslinking accelerator, a crosslinking aid, a softener, a tackifier, an antioxidant, a foaming agent, a processing aid, an adhesion promoter, and an inorganic filler. , An organic filler, a crystal nucleating agent, a heat stabilizer, a weather stabilizer, an antistatic agent, a coloring agent, a lubricant, a flame retardant, a blooming inhibitor and the like. Further, the olefin polymer composition (C) may contain a thermosetting resin.

Crosslinking Agents Crosslinking agents include sulfur, sulfur compounds and organic peroxides. 1 minute half-life temperature is 130 ℃ ～ 2
Organic peroxides at 00 ° C. are preferred, specifically dicumyl peroxide, di-t-butyl peroxide, di-t-
Butylperoxy-3,3,5-trimethylcyclohexane, t
-Butylcumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-
2,5-di- (t-butylperoxy) -hexane and the like are preferred. In addition, when using an organic peroxide as a crosslinking agent, it is preferable to use a crosslinking assistant together.

Of the various cross-linking agents as described above, it is preferable to use sulfur or a sulfur-based compound, particularly sulfur, since a cross-linked product having excellent properties can be obtained. However, organic peroxides are particularly excellent in cross-linking efficiency. Is more preferable. As a crosslinking accelerator , specifically, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene
2-Benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole and the like are used.

Crosslinking Aids Crosslinking aids are used in crosslinking organic peroxides. Specific examples of the crosslinking aid include sulfur; p-quinonedioxime,
quinone dioxime compounds such as p, p'-dibenzoylquinone dioxime; and polyfunctional monomers such as (meth) acrylate compounds such as trimethylolpropane triacrylate and polyethylene glycol dimethacrylate; diallyl phthalate, triallylcia Allyl compounds such as nurate; maleimide compounds such as N, N'-m-phenylenebismaleimide; divinylbenzene and the like.

As the softening agent, a softening agent conventionally compounded in rubber is widely used, and specifically, a petroleum softening agent such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and petrolatum. Coal tar softeners such as coal tar and coal tar pitch; fatty oil softeners such as castor oil, linseed oil, rapeseed oil and coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax and lanolin; Fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; and synthetic high molecular substances such as petroleum resins, atactic polypropylene, and coumarone indene resins. Among them, a petroleum softener is preferably used, and particularly, a process oil is preferably used.

As the foaming agent, a foaming agent generally used for foaming rubber can be widely used.
Inorganic blowing agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine Azo compounds such as nitroso compounds, azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonyl Hydrazide), diphenylsulfone-3,3'-
Sulfonyl hydrazide compounds such as disulfonyl hydrazide; and azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide, and p-toluenesulfonyl azide. Of these, nitroso compounds, azo compounds and azide compounds are preferred.

[0080] with foaming aid also blowing agents can also be used a foaming aid, if used in combination foaming aid, lowering of the decomposition temperature of the foaming agent, decomposition accelerator, an effect such as uniform bubble. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and derivatives thereof.

Processing aids Examples of processing aids include acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid, salts of these higher fatty acids, for example, barium stearate, zinc stearate, and the like.
Examples include calcium stearate or esters. The adhesion-imparting agent improves the adhesion between the crosslinked product and a decorative layer such as a coating film. Examples of the adhesion-imparting agent include an organotin compound, a tertiary amine compound, a hydroxyl group-containing (co) polymer, Metal hydroxide and the like.

Inorganic fillers : 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, titanic acid Calcium, barium sulfate, calcium sulfite, talc,
Clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder,
Molybdenum sulfide and the like can be mentioned.

Among these, a layered compound is preferable, and a clay mineral having swelling and cleavage properties with respect to a dispersion medium is particularly preferably used. Such clay minerals are generally of a type having a two-layer structure having an octahedral layer having aluminum or magnesium as a central metal on the top of a tetrahedral layer of silica, and a type having a tetrahedral layer of silica containing aluminum or magnesium. It is classified into a type having a three-layer structure in which an octahedral layer serving as a central metal is narrowed from both sides. The former two-layer structure type includes kaolinite group and antigolite group, and the latter three-layer structure type includes smectite group, vermiculite group and mica group depending on the number of interlayer cations. Can be.

More specifically, these clay minerals include kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectite. Light, tetrasilicyl mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, zansophyllite, chlorite and the like can be mentioned.

A clay mineral treated with an organic material (hereinafter sometimes referred to as an organically modified clay mineral) can also be used as an inorganic layered compound. (Note that clay minerals treated with an organic material are described in Asakura Shoten, See Clay Encyclopedia). Among the above clay minerals, smectites, vermiculites, and micas are preferable, and smectites are more preferable, from the viewpoint of swelling or cleavage. Examples of the smectite group include montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, and hectorite.

The dispersion medium for swelling or cleaving the inorganic layered compound is, for example, in the case of a natural swelling clay mineral, water, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, dimethylformamide, dimethyl sulfoxide, Acetone and the like are mentioned, and alcohols such as water and methanol are more preferable.

In the case of organically modified clay minerals, aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as ethyl ether and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; n-pentane; aliphatic hydrocarbons such as n-hexane and n-octane; halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and perchloroethylene;
Examples include ethyl acetate, methyl methacrylate (MMA), dioctyl phthalate (DOP), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, and silicone oil.

Crystal nucleating agent As the crystal nucleating agent, various conventionally known nucleating agents can be used without any particular limitation. Examples of the crystal nucleating agent include the following aromatic phosphate ester salts, benzylidene sorbitol, aromatic carboxylic acids, and rosin-based nucleating agents. As the aromatic phosphate salt, the following formula (III)
Can be mentioned.

[0089]

Embedded image

Wherein R ¹ is an oxygen atom, a sulfur atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R ² and R ³ may be the same or different, may be R ² , R ^3, or R ² and R ³ may be bonded to form a ring; Represents a trivalent metal atom, and n is an integer of 1 to 3.) As the compound represented by the formula (III), specifically, sodium-2,2'-methylene-bis (4,6 -Di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium
-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis (4,6-di-
(t-butylphenyl) phosphate, sodium-2,2'-
Ethylidene-bis (4-i-propyl-6-t-butylphenyl)
Phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-
2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium -Bis [2,2'-thiobis (4-ethyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis
-(4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-thiobis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2 '-Thiobis- (4-t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis (4,6-di-methylphenyl)
Phosphate, sodium-2,2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl ) Phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis- (2,2'-methylene-bis (4,6- Di-t
-Butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4 ,
6-di-t-butylphenyl) phosphate], sodium-
2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium ( (4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl)
Phosphate, calcium-bis [(4,4'-dimethyl-
6,6'-di-t-butyl-2,2'-biphenyl) phosphate],
Sodium-2,2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate,
Sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium- Bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phospho Fate], barium-bis [2,2'-ethylidene-bis (4,6-di-t
-Butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylfell) phosphate] and aluminum-tris [2,2'-ethylidene-bis (4, 6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof. In particular, sodium-2,2'-methylene-bis (4,6-di-
(t-butylphenyl) phosphate is preferred.

As the aromatic phosphate salt, there can be mentioned a compound represented by the following formula (IV).

[0092]

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(In the formula, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, M represents a 1 to 3 valent metal atom, and n represents an integer of 1 to 3.) Specific examples of the compound represented by the formula (IV) include sodium-bis (4-t-butylphenyl) phosphate,
Sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-octylphenyl) phosphate Phosphate, potassium-bis (4-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium-bis (4-t-
Butylphenyl) phosphate, lithium-bis (4-t
-Butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate, and mixtures of two or more thereof. Particularly, sodium-bis (4-t-butylphenyl) phosphate is preferred.

Examples of the benzylidene sorbitol include compounds represented by the following formula (V).

[0095]

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(In the formula, R ⁵ may be the same or different, and represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and m and n are each an integer of 0 to ^5. ) As the compound represented by the formula (V), specifically, 1,3,
2,4-dibenzylidene sorbitol, 1,3-benzylidene-
2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-
Methylbenzylidene-2,4-benzylidene sorbitol,
1,3-p-ethylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-p
-Methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn -Propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-
Butylbenzylidene) sorbitol, 1,3,2,4-di (ps-
Butylbenzylidene) sorbitol, 1,3,2,4-di (pt-
Butylbenzylidene) sorbitol, 1,3,2,4-di (2 ',
4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2- 4-p-chlorobenzylidene sorbitol, 1,3-p
-Chlorbenzylidene-2,4-benzylidene sorbitol,
1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p-methylbenzylidene-2,4 -P-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof In particular, 1,3,2,4-dibenzylidenesorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p
-Ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol,
Preferred are 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof.

Among the benzylidene sorbitols described above, a compound represented by the following formula (VI) can be mentioned as a preferred example.

[0098]

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(In the formula, R ⁵ may be the same or different and each represents a methyl group or an ethyl group.) As the aromatic carboxylic acid, aluminum hydroxydiparat-t- represented by the following formula (VII) is used. Butyl benzoate and the like can be mentioned.

[0100]

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The rosin-based nucleating agent includes, for example, a metal salt of rosin acid. The metal salt of rosin acid refers to a reaction product of rosin acid and a metal compound. Examples of rosin acids include natural rosins such as gum rosin, tall oil rosin, and wood rosin; various modifications such as disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, and α, β-ethylenically unsaturated carboxylic acid-modified rosin Rosin; a purified product of the natural rosin and a purified product of the modified rosin can be exemplified. The unsaturated carboxylic acids used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin include, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid And methacrylic acid. Among these, at least one rosin acid selected from the group consisting of natural rosin, modified rosin, a purified product of natural rosin, and a purified product of modified rosin is preferable. Here, rosin acid is pimaric acid, sandaracopimaric acid, parastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid,
It contains a plurality of resin acids selected from tetrahydroabietic acid and the like.

Examples of the metal compound which reacts with rosin acid to form a metal salt include compounds having a metal element such as sodium, potassium and magnesium and forming a salt with the rosin acid. Specific examples include chlorides, nitrates, acetates, sulfates, carbonates, oxides, hydroxides, and the like of the above metals. Examples of other crystal nucleating agents include high melting point polymers, metal salts of aromatic carboxylic acids and aliphatic carboxylic acids, and inorganic compounds.

As the high melting point polymer, polyvinyl cycloalkane such as polyvinyl cyclohexane and polyvinyl cyclopentane, poly 3-methyl-1-pentene, poly 3-
Examples thereof include methyl-1-butene and polyalkenylsilane. Examples of the metal salts of aromatic carboxylic acids and aliphatic carboxylic acids include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrrolecarboxylate.

The olefin polymer composition (C) can be prepared by subjecting each component to various methods known in the art, for example, a Henschel mixer,
It can be manufactured by a method of mixing with a blender, a ribbon blender, a tumbler blender, or the like, or a method of melting and kneading with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like, followed by granulation or pulverization. it can.

Molded Article The molded article for building materials and civil engineering according to the present invention is formed from the olefin block copolymer (A) or the olefin polymer composition (C) containing the (A). Molded articles include, for example, building materials such as flooring materials, floor tiles, floor sheets, sound insulation sheets, heat insulation panels, vibration damping materials, decorative sheets, baseboards, asphalt modifiers, gasket / sealing materials, roofing sheets, and waterproof sheets. -Useful in a wide range of fields for civil engineering.

These molded products for building materials and civil engineering can be produced by, for example, calender molding, extrusion molding, injection molding, blow molding, press molding, stamping molding and the like. When the olefin-based block copolymer (A) or the olefin-based polymer composition (C) is extrusion-molded, a conventionally known extrusion apparatus and molding conditions can be employed. For example, a single screw extruder, Using a kneading extruder, a ram extruder, a gear extruder, or the like, extruding the molten olefin block copolymer (A) or olefin polymer composition (C) from a T-die or the like to form a sheet or film ( (Unstretched).

The stretched film is obtained by stretching the above-mentioned extruded sheet or extruded film (unstretched) by, for example, a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method and a uniaxial stretching method. . Further, an inflation film can be produced from the olefin-based block copolymer (A) or the olefin-based polymer composition (C) according to the present invention.

The injection molded article is prepared by injecting the olefin block copolymer (A) or the olefin polymer composition (C) into various shapes using a conventionally known injection molding apparatus under known conditions. It can be manufactured by molding. The blow molded article can be manufactured using a conventionally known blow molding apparatus under a known condition.

In the injection blow molding, the olefin block copolymer (A) or the olefin polymer composition (C) is injected into a parison mold at a resin temperature of 100 ° C. to 300 ° C. to form a parison. Next, after holding the parison in a mold having a desired shape, air is blown therein, and the parison is mounted on the mold, whereby a hollow molded body can be manufactured. Examples of the press molded body include a mold stamping molded body.

Hereinafter, the present invention will be described in more detail with reference to several examples of preferred embodiments of the molded article for building materials and civil engineering according to the present invention. When the molded material for building materials and civil engineering according to the present invention is a wallpaper, a floor material (floor sheet, floor tile), a sound insulation sheet, a decorative sheet, a gasket / sealing material, a thermoplastic resin (B), an inorganic filler, It is preferably formed from an olefin polymer composition (C) containing a tackifier and the like.
Further, the olefin polymer composition (C) may be foamed or cross-linked. Foaming and cross-linking foaming may be performed after shaping or may be performed simultaneously with molding.

As the olefin block copolymer (A) used here, the PO portion is an ethylene / cyclic olefin copolymer (ethylene content: 1 to 99% by weight, M
w: 5 × 10 ^{3 to} 5 × 10 ⁶ ), syndiotactic propylene / ethylene copolymer (propylene content: 50 to
99 mol%, Mw: 5 × 10 ^{3 to} 5 × 10 ⁶ ), atactic propylene / ethylene copolymer (propylene content: 50 to 99 mol%, Mw: 5 × 10 ^{3 to} 5 × 1)
0 ^6), ethylene · alpha-olefin copolymer (ethylene content: 99) ^{mol%, Mw: 5 × 10 3} ~5 × 1
0 ^6), ethylene-propylene-vinyl norbornene copolymer (ethylene content: 50 to 99 mol%, propylene content: 50 ^{mol%, Mw: 5 × 10 3} ~5 × 1
0 ^6), ethylene-propylene-DMDT copolymer (ethylene content: 50 to 98 mol%, propylene content: 1
50 mol%, Mw: 5 × 10 ^{3 to} 5 × 10 ⁶ ), ethylene / cyclic olefin / propylene / DMDT copolymer (ethylene content: 40 to 97 mol%, cyclic olefin content:
1 to 20 mol%, propylene content: 1 to 39 mol%, M
w: 5 × 10 ^{3 to} 5 × 10 ⁶ ), or an ethylene / aromatic vinyl copolymer (ethylene content: 1 to 99) mol%, M
w: 5 × 10 ^{3 to} 5 × 10 ⁶ ), the f portion is an ether bond, and the R portion is a styrene homopolymer (Mw: 2 × 10 3).
^{3 to} 5 × 10 ⁶ ), methyl methacrylate homopolymer (Mw: 2 × 10 ^{3 to} 5 × 10 ⁶ ), or styrene / maleic anhydride copolymer (styrene content: 50 to 99 mol%, Mw: 2) × 10 ^{3 to} 5 × 10 ⁶ ) are preferable.

When the PO portion is as described above, the molded article is excellent in flexibility, impact resistance and scratch resistance. Further, when the R portion is as described above, the molded product is:
Excellent heat resistance, compatibility with fillers, etc. Further, when the R portion is a homo- or copolymer of a hydrophilic compound such as ethylene oxide, hydroxyethyl methacrylate, or acrylamide, a moist touch is obtained.

When the building material or civil engineering molded article is a wallpaper, a sound-insulating sheet, a decorative sheet, or the like, the sheet or film obtained by calendering or extrusion molding is stretched to form a perforated film to form a breathable film. In some cases. When the building material / civil engineering product according to the present invention is a vibration damping material, a thermoplastic resin (B), an inorganic filler,
Olefin polymer composition (C) containing a tackifier and the like
It is preferred that The olefin polymer composition (C) is preferably used after crosslinking.
Crosslinking improves strength, oil resistance, and the like.

As the olefin block copolymer (A) used herein, the PO portion is an ethylene / cyclic olefin / propylene / conjugated diene copolymer (ethylene content: 50 to 97 mol%, cyclic olefin content: 1 to 1). 35
Mol%, propylene content: 1 to 45 mol%, Mw: 5 ×
10 ^{3 to} 5 × 10 ⁶ ), ethylene / cyclic olefin / propylene / conjugated polyene copolymer (ethylene content 50 to 9)
7 mol%, cyclic olefin content: 1 to 35 mol%, propylene content: 1 to 45 mol%, Mw: 5 × 10 ^{3 to} 5 ×
10 ⁶ ), ethylene homopolymer (Mw: 5 × 10 ^{3 to} 5 ×)
10 ⁶ ) Ethylene / α-olefin copolymer (ethylene content: 1
Mol% or more and less than 100 mol%, Mw: 5 × 10 ^{3 to} 5 ×
10 ⁶ ) or an ethylene / aromatic vinyl / conjugated polyene copolymer (ethylene content: 2 to 98 mol%, aromatic vinyl content: 1 to 98 mol%, Mw: 5 × 10 ^{3 to} 5 × 1)
0 ⁶ ), the f portion is an ether bond or an amide bond, and the R portion is preferably a homopolymer or a copolymer of styrene, methyl methacrylate, maleic anhydride, ε-caprolactam and the like.

The R part is preferably contained in an amount of 1 to 99% by weight based on the olefin block copolymer (A). When the PO portion is as described above, the tan δ at room temperature measured by dynamic viscoelasticity measurement becomes 0.2 or more and the vibration absorption is excellent by appropriately adjusting the composition, and the toughness and the strength are also improved. An excellent molded body is obtained. When the R portion is as described above, the olefin polymer composition (C) has excellent affinity with the filler and the like, and the molded article has excellent heat resistance and the like.

In the case where the molded product for building materials and civil engineering according to the present invention is an asphalt modifying material, the olefin-based block copolymer (A) has a PO portion of ethylene / cyclic olefin / propylene / conjugated diene copolymer. Copolymer, ethylene / cyclic olefin / propylene / conjugated polyene copolymer (ethylene content: 50 to 97 mol%, cyclic olefin content:
1 to 30 mol%, propylene content: 1 to 40 mol%, M
w: 5 × 10 ^{3 to} 5 × 10 ⁶ ) or an ethylene / α-olefin copolymer (ethylene content: 1 to 99 mol%, M
w: 5 × 10 ^{3 to} 5 × 10 ⁶ ), the f portion is an ether bond or an amide bond, and the R portion is a homopolymer or copolymer such as styrene, methyl methacrylate, maleic anhydride, and ε-caprolactam. It is preferable to use the following.

The R part is preferably contained in an amount of 1 to 99% by weight based on the olefin block copolymer (A). When the PO portion is as described above, it is excellent in heat stability when melt blended with asphalt. When the R portion is as described above, the olefin-based block copolymer (A) has excellent compatibility with asphalt. Furthermore, the strength and heat resistance after asphalt is solidified are improved.

In the case where the molded material for building materials and civil engineering according to the present invention is a gasket / sealing, a roofing sheet or a waterproof sheet, an olefin polymer composition containing a thermoplastic resin (B), an inorganic filler and the like. It is preferably formed from (C). In the case of a fining sheet and a water-stop sheet, the olefin polymer composition (C) is preferably used after being crosslinked. Crosslinking improves strength, oil resistance, etc., and also improves pinhole resistance and piercing resistance. In the case of gasket sealing, the olefin polymer composition (C) is preferably used by crosslinking and foaming.
Further, these olefin-based polymer compositions (C) are
After impregnating a cloth or the like as a solution, the solvent can be evaporated off and used as a gasket / sealing, roofing sheet, or waterproof sheet.

As the olefin block copolymer (A) used herein, the PO portion is an ethylene / α-olefin / conjugated diene copolymer or an ethylene / α-olefin / conjugated polyene copolymer (ethylene content: 50 ~ 98 mol%, α-olefin content: 1-48 mol%, Mw: 5
× 10 ^{3 to} 5 × 10 ⁶ ), an ethylene / cyclic olefin / propylene / conjugated polyene copolymer (ethylene content: 50
~ 97 mol%, cyclic olefin content: 1 ~ 30 mol%,
Propylene content: 1 to 40 mol%, Mw: 5 × 10 ³ to
5 × 10 ⁶ ) or an ethylene / aromatic vinyl / conjugated diene copolymer (ethylene content: 50 to 98 mol%, aromatic vinyl content: 1 to 30 mol%, Mw: 5 × 10 ^{3 to} 5)
× 10 ⁶ ), wherein the f portion is an ether bond or an amide bond, and the R portion is a homopolymer or a copolymer such as styrene, methyl methacrylate, maleic anhydride, and ε-caprolactam.

The R part is preferably contained in an amount of 1 to 99% by weight based on the olefin block copolymer (A).

[0121]

The molded product for building materials and civil engineering according to the present invention satisfies various requirements required for building materials and civil engineering applications.

[0122]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0123]

[Preparation Example 1] [Pre-activation of catalyst] 10.0 mg of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was weighed into a glass container sufficiently purged with nitrogen.
To this, a toluene solution of methylaluminoxane was added so as to be 17.2 mmol in terms of aluminum atoms, and 2
Ultrasonic irradiation was performed at 3 ° C. for 15 minutes. Next, an appropriate amount of toluene was added to make the whole 50 ml, which was used as a catalyst solution (1).

[Ethylene / Norbornene Copolymerization] 20 g of norbornene at room temperature under a nitrogen atmosphere was placed in a 1-liter stainless steel autoclave sufficiently purged with nitrogen.
600 ml of a cyclohexane solution was charged. Next, 0.6 mmol of triisobutylaluminum was added, and the inside of the system was replaced with ethylene. The system was pressurized with ethylene and further heated to 70 ° C. in the system and 0.7 MPa in total pressure. Then, 12.8 ml of the above-mentioned catalyst solution (1) was injected into the reactor using pressurized nitrogen to initiate polymerization. After the initiation of the polymerization, only ethylene is supplied, and the total pressure is 0.7 MPa, 70
Polymerization was carried out at a temperature of 5 ° C for 5 minutes. Five minutes after the start of the polymerization, 5 ml of isopanol was injected into the reactor using pressurized nitrogen to terminate the polymerization reaction. After depressurization, the polymer solution was taken out, and an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the polymer solution were brought into contact with each other with vigorous stirring at a ratio of 1: 1 using a homomixer. Moved to. After allowing this contact mixture to stand, the aqueous phase is separated and removed,
Further, washing with water was performed twice, and the polymerization liquid phase was purified and separated. Next, the polymer solution purified and separated was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a copolymer, and then a solid portion (copolymer) was collected by filtration and washed sufficiently with acetone. Further, in order to extract unreacted norbornene remaining in the polymer, this solid portion was poured into acetone so that the solid portion became 40 g / liter, and the extraction operation was performed at 60 ° C. for 2 hours.
Time went. After the extraction treatment, a solid portion was collected by filtration, and dried under reduced pressure at 130 ° C. and 350 mmHg for 12 hours under a nitrogen flow.

The thus obtained ethylene / norbornene random copolymer (C2 / NBR) had a yield of 2
It was 5.7 g. Therefore, the catalyst activity is 41.8 kg
/ Mmol-Zr · hr. As a result of IR analysis, the norbornene content was 8.5 mol%, and an unsaturated bond was present at the polymer terminal. Further, as a result of GPC measurement, Mw was 140,000.

[Hydroboration] The terminally unsaturated C2 / NBR 20 suspended in 100 ml of degassed and dried THF in a dry box filled with argon.
g was placed in a glass flask equipped with a magnetic stirrer, and 2.3 ml of a solution of 9-borabicyclo [3.3.1] nonane (9-BBN) in tetrahydrofuran (THF) (0.5 M) was added. The slurry was stirred in a dry box at 55 ° C. for 5 hours, filtered, washed with deaerated and dried isopropyl alcohol (IPA), and dried under reduced pressure to obtain a boron-terminated ethylene-norbornene random copolymer (C
2 / NBR-B).

[Styrene polymerization] 20 g of the C2 / NBR-B was placed in a closed flask, and dried styrene (S
t) After adding and suspending 11.4 g and 80 ml of THF, 1.5 ml of dry oxygen was blown to start the reaction. Then, after stirring at room temperature for 14 hours, 100 ml of methanol was added to stop the reaction. The precipitated polymer was extracted and fractionated with acetone and heptane over 24 hours by a Soxhlet extractor under a nitrogen atmosphere, and a C2 / NBR-O-polystyrene diblock copolymer (C2 / NBR-O-PSt) was used as an insoluble component. Obtained.

The weight average molecular weight (Mw ₂ ) of the PSt part of this diblock copolymer calculated by the following equation was 5,000.
Met. Mw ₂ = Mw ₁ · (W ₂ −W ₁ ) / Mw _{1 In the} above formula, Mw ₁ : Mw of C2 / NBR part, Mw ₂ : Mw of PSt part W ₁ : C2 / NBR-B used for styrene polymerization Weight W ₂ : Yield of diblock copolymer is shown.

[0129]

[Production Example 2] [Ethylene / propylene / triene copolymerization] Purified heptane (651 ml), 4,8-dimethyl-1,4,8 at room temperature under a nitrogen atmosphere in a 2-liter stainless steel autoclave sufficiently purged with nitrogen. -Decatriene (D
MDT) 24 ml, a solution of triisobutylaluminum in heptane 0.75 mmol per aluminum atom,
A toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added in an amount of 0.021 mmol per boron atom.

Next, after adding 9 liters of propylene, the temperature inside the reactor was raised. When the temperature in the system reached 60 ° C., the supply of ethylene was started, and the pressure was increased to 0.9 MPa.
When the temperature in the system reached 70 ° C. and the total pressure reached 0.9 MPa, the toluene solution of (Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilanetitanium dichloride was converted to titanium atom to give 0.1%. The polymerization was initiated by pressurizing the reactor with pressurized nitrogen into the 00105 mmol reactor. The polymerization was carried out for 30 minutes while maintaining the total pressure at 0.9 MPa and 70 ° C. Thirty minutes after the start of the polymerization, 50 ml of methanol was added to stop the polymerization reaction. After cooling and depressurization, the polymer solution was taken out and poured into about 3 liters of methanol to precipitate a polymer. Next, the mixture was cut with a mixer, washed with about 2 liters of methanol, and dried under reduced pressure at 400 ° C. and 400 mmHg for 12 hours under nitrogen flow.

The yield of the ethylene / propylene / triene copolymer (EPT) thus obtained was 31.6 g.
Met. Therefore, the catalytic activity is 60.2 kg / mmo.
1-Ti · hr. As a result of IR analysis, the ethylene content was 69 mol%, the DMDT content was 3 mol%, and the Mw was 180,200. [Hydroboration] The above EP suspended in 100 ml of degassed and dried THF in a dry box filled with argon.
20 g of T was placed in a glass flask equipped with a magnetic stirrer, and 1.8 ml of a 9-BBN THF solution (0.5 M) was added. This slurry was stirred in a dry box at 55 ° C. for 5 hours, then filtered, washed with degassed and dried IPA, and dried under reduced pressure to obtain a boron-terminated ethylene-propylene-triene copolymer (EPT-B). I got

[Methyl methacrylate polymerization] 20 g of the EPT-B was placed in a closed flask, 8.5 g of dry methyl methacrylate (MMA) and 80 ml of THF were added to suspend the mixture, and then 1.1 ml of dry oxygen was blown therein. The reaction was started. Then, after stirring at room temperature for 2 hours, 100
The reaction was stopped by adding ml of methanol. The precipitated polymer was subjected to a Soxhlet extraction under nitrogen atmosphere.
Extraction and fractionation were performed with a mixed solvent of acetone and heptane over 4 hours to obtain an EPT-O-polymethyl methacrylate diblock copolymer (EPT-O-PMMA) as an insoluble component.

The weight average molecular weight (Mw ₂ ) of the PMMA portion of this diblock copolymer calculated by the following equation was 5,000.
It was 0. Mw ₂ = Mw ₁ · (W ₂ −W ₁ ) / Mw _{1 In the} above formula, Mw ₁ : Mw of EPT part, Mw ₂ : Mw of PMMA part W ₁ : Weight of EPT-B used for MMA polymerization W ₂ : The yield of the diblock copolymer is shown.

[0134]

Example 1 100 parts of the diblock copolymer polymerized in Production Example 1, 200 parts of magnesium hydroxide, 10 parts of calcium stearate and 3 parts of titanium white were blended in an open roll (front roll). / Roll: 12
(0/120 ° C., 16/18 rpm) to obtain a blend. This was press-formed at 200 ° C. to obtain a test piece. Roll kneading property, surface hardness, heat resistance and scratch resistance of this test piece were evaluated as follows. Table 1 shows the results.

Roll kneading property rating: Roll kneadable without problems ○ Good that cannot be adhered to the roll Ｓ S that does not adhere to the roll and is not sufficiently kneaded Ｎ NS TMA (penetration temperature: heat resistance) 2 kg / cm ² using 8 mmφ indenter, heating rate 5
The penetration temperature was determined under the conditions of ° C / min.

Surface hardness Shore A hardness was measured according to ASTM D676. Using a martens hardness scratch hardness tester manufactured by Tokyo Ikki,
A load of 20 g of a scratching indenter was applied to a 3 mm-thick test piece, the groove width generated when the sample was scratched was measured, and the reciprocal thereof was calculated.

[0137]

Comparative Example 1 Ethylene / butene random copolymer (ethylene content: 88 mol%, density: 885 kg / m ³ , M
w: 155000, Mw / Mn: 1.87), except that a test piece was produced in the same manner as in Example 1 and the roll kneading property, surface hardness, heat resistance and scratch resistance of this test piece were measured. Evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

[0138]

[Table 1]

The use of the diblock copolymer according to the present invention was superior in heat resistance, flexibility, scratch resistance and roll kneading property.

[0140]

Example 2 Diblock copolymer polymerized in Production Example 2, zinc white, stearic acid, FEF carbon black,
A naphthenic oil, a vulcanization accelerator and sulfur were compounded according to Table 2, and an open roll (front roll / rear roll: 70 /
The mixture was kneaded at 70 ° C and 16/18 rpm to obtain an unvulcanized compounded rubber.

The unvulcanized compounded rubber thus obtained was heated by a press heated to 160 ° C. for 20 minutes to produce a vulcanized sheet, and the following tests were performed. Table 2 shows the results. Tensile test Tensile strength (TB) and elongation (EB) were measured according to JIS K6301.

Hardness test JIS A hardness (HS) was measured according to JIS K6301. Ozone resistance test The ozone resistance test was performed in an ozone test tank. The conditions were as follows: ozone concentration: 80 ppm, elongation: 80%, temperature: 40 ° C.
A 96 hour static test. The evaluation of the ozone resistance was performed in accordance with JIS K6301 based on the state of deterioration of the surface. The evaluation criteria for the surface state are as follows,
For example, it is displayed as “C-5”. (Number of cracks) A: A small number of cracks B: A large number of cracks C: Infinite number of cracks (Size and depth of cracks) 1: Not visible to the naked eye but can be confirmed with a magnifying glass of 10 times magnification 2 ... the ... what crack is relatively large deep (less than 1mm) 4 ... that crack larger deep (less than 1mm or 3 mm) 5 ... 3 mm or more cracks or cut-and-raised likely that vibration damping properties Rheometric Co. RDSII 2.5 rad
The dynamic viscoelasticity at 25 ° C. was measured at a frequency of / sec, and the attenuation rate (tan δ) was measured. The larger the tan δ, the better the vibration damping property.

[0143]

Comparative Example 2 In Example 2, ethylene-propylene / 5- was used in place of the diblock copolymer polymerized in Production Example 2.
Ethylidene-2-norbornene copolymer (ethylene / propylene (molar ratio); 68/32), intrinsic viscosity [η];
A vulcanized sheet was prepared and tested in the same manner as in Example 2, except that 1.7 dl / g and an iodine value of 12) were used and the composition of each component was changed as described in Table 2. . Table 2 shows the results.

[0144]

[Table 2]

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Taku Kanda 6-1-2 Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Ryo Mori Inventor 6-Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture -1-2 Inside Mitsui Chemicals Co., Ltd. (72) Junji Tanji Inventor 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Chemicals Co., Ltd. (72) Hideyuki Kaneko 580 Nagaura, Sodegaura City, Chiba Prefecture −32 Mitsui Chemicals Co., Ltd. (72) Inventor Shunichi Hama 3-8-1 -106, Makuhari Hongo, Hanamigawa-ku, Chiba City, Chiba Prefecture (72) Inventor Shinichi Furushiro 580-32, Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals (72) Inventor Norio Kashiwa 580-32 Nagaura, Sodegaura-shi, Chiba Prefecture Mitsui Chemicals, Inc.

Claims (2)

[Claims] 1. A resin having a melt flow rate (ASTMD 1238, 230 ° C., load 2.
PO-fR ... (I) (16 kg) comprising the olefin-based block copolymer (A) in the range of 0.01 to 200 g / 10 min. , PO is composed of a repeating unit derived from an olefin having 2 to 20 carbon atoms, and has a weight average molecular weight of 2,2.
Represents a polyolefin segment having a molecular weight of not less than 000, f represents an ether bond, an ester bond or an amide bond, R represents a chain polymerization reaction, and has a weight average molecular weight of 500
The functional segment described above is shown. ). 2. The olefin block copolymer (A) according to claim 1, and a thermoplastic resin (B) other than (A).
A molded article for building materials and civil engineering, comprising an olefin polymer composition (C) containing: