JP4472195B2 - Environmentally disintegrating resin molding - Google Patents

Description

【０１１４】
【実施例３】
製造例２で製造したジブロック共重合体（ＰＰ−Ｏ−ＰＬａ）を粉砕し、パウダー化した後、真空乾燥機でよく乾燥させた。この乾燥したジブロック共重合体パウダー １００重量部にイルガノックス^TM1010を０．１重量部加え、窒素雰囲気下、シリンダ温度２００℃、金型温度１０℃の条件で射出成形し、容量約３０ｍｌ、重量１０ｇのコップを成形した。
【０１１５】
得られたコップについて耐熱性および環境崩壊性を評価した。結果を表２に示す。
コップの耐熱性は、コップを２３℃の温度下に４８時間放置した後、この容器に温度７０℃のお湯を２０ｍｌ入れ、２３℃の温度下に１時間静置し、成形体が変形するか目視で評価した。
【０１１６】
コップの環境崩壊性は、コップから切りだした試料片を、実施例１と同様に、温度５８℃、水分量６０重量％の堆肥（成分；籾殻、生ゴミ、鶏糞、屎尿等）中に３ヶ月間埋設した後その変化を観察した。
【０１１７】
【実施例４】
製造例２で製造したジブロック共重合体（ＰＰ−Ｏ−ＰＬａ）を粉砕し、パウダー化したブロック共重合体パウダー １０重量部、ポリ乳酸（Ｂ１）６０重量部、プロピレン・エチレンブロック共重合体（Ｃ２）（２３０℃で測定したＭＦＲ＝２５ｇ／10分、デカン可溶部＝１１．５％）３０重量部をそれぞれを真空乾燥機でよく乾燥させた後、イルガノックス^TM1010 ０．１重量部を加え、２０ｍｍφ二軸押出機にて、窒素雰囲気下、シリンダ温度２００℃で樹脂を混合し、ペレット化した。得たペレットを真空乾燥機でよく乾燥させた後、実施例３と同様にして射出成形し、得られたコップについて耐熱性および環境崩壊性を評価した。結果を表２に示す。
【０１１８】
【比較例３】
ポリ乳酸（Ｂ１）を１００重量部およびイルガノックス^TM1010を０．１重量部用いた以外は、実施例３と同様にして射出成形し、得られたコップについて耐熱性および環境崩壊性を評価した。結果を表２に示す。
【０１１９】
【比較例４】
ポリ乳酸（Ｂ１）６７重量部、プロピレン・エチレンブロック共重合体（Ｃ２）３３重量部およびイルガノックス^TM1010 ０．１重量部を、実施例４と同様にして溶融混合しペレット化した後、実施例３と同様にして射出成形し、得られたコップについて耐熱性および環境崩壊性を評価した。結果を表２に示す。
【０１２０】
【表２】

【０１２１】
【参考例１】
製造例３で製造したジブロック共重合体（Ａ３）１００重量部を粉砕し、パウダー化した後、このパウダーにイルガノックス^TM1010 ０．１重量部をアセトンに溶かしたものをまぶし、よく撹拌し、真空乾燥機で乾燥させた。これを加熱温度２００℃、冷却温度２０℃の条件でプレス成形して、厚さ１００μｍのフィルムを得た。
【０１２２】
得られたフィルムについて耐熱性および環境崩壊性を評価した。結果を表３に示す。
フィルムの耐熱性は、フィルムから幅２ｍｍ、長さ２ｃｍの短冊状の試料を切り取り、ＴＭＡ（セイコー電子製）を用い、１０ｋｇｆ／ｃｍ²の荷重をかけ、窒素気流下、毎分２℃／分の昇温条件でクリープ試験を実施し、歪みが５％となる温度を変形温度として、この温度で耐熱性を評価した。
【０１２３】
フィルムの環境崩壊性は、フィルムから長さ５ｃｍ、幅１ｃｍの試料を切り取り、これを温度５８℃、水分量６０重量％の堆肥（成分；籾殻、生ゴミ、鶏糞、屎尿等）中に３ヶ月間埋設したのちその変化を観察した。
【０１２４】
【参考例２】
製造例３で製造したジブロック共重合体（ＨＤＰＥ−Ｏ−ＰＣＬ）を粉砕し、パウダー化したジブロック共重合体パウダー １０重量部、ポリカプロラクトン（Ｂ２）（ポリスチレン換算の重量平均分子量Ｍｗ＝１３０,０００）６０重量部、高密度ポリエチレン（Ｃ３）（１９０℃で測定するＭＦＲ＝５．２ｇ／10分、密度０．９６８ｇ／ｃｍ³）３０重量部をそれぞれ真空乾燥機でよく乾燥させた後、イルガノックス^TM1010 ０．１重量部を加え、２０ｍｍφ二軸押出機にて、窒素雰囲気下、シリンダ温度２００℃で樹脂を混合して、ペレット化した。得たペレットを真空乾燥機でよく乾燥させた後、参考例１と同様にしてプレス成形し、得られたフィルムについて耐熱性および環境崩壊性を評価した。結果を表３に示す。
【０１２５】
【比較例５】
ポリカプロラクトン（Ｂ２）を１００重量部およびイルガノックス^TM１０１０を０．１重量部用いた以外は、参考例１と同様にして、フィルムを成形し、得られたフィルムについて耐熱性および環境崩壊性を評価した。結果を表３に示す。
【０１２６】
【比較例６】
ポリカプロラクトン（Ｂ２）６７重量部、高密度ポリエチレン（Ｃ３）３３重量部およびイルガノックス^TM1010 ０．１重量部を、参考例２と同様にして溶融混合してペレット化した後、参考例１と同様にしてフィルムを成形し、得られたフィルムについて耐熱性および環境崩壊性を評価した。結果を表３に示す。
【０１２７】
【表３】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an environmentally disintegrating resin molded body, and more particularly, to an environmentally disintegrating resin molded body having an excellent balance between mechanical properties and environmental disintegrating properties.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Polyolefins such as polyethylene and polypropylene, polystyrene, polyvinyl chloride, polyester, polyamide, and the like are molded by various methods and used for various purposes. However, since these resins are chemically stable, once they are disposed in the natural environment, they remain semipermanently, thereby causing dust problems such as damage to the landscape.
[0003]
In order to solve such a problem, a resin that is broken down by biological metabolism in the environment has been developed.
As such resins, aliphatic polyesters such as polylactic acid, polyglycolic acid, poly-β-hydroxybutyric acid, poly-ε-caprolactone, polybutylene succinate, polyethylene succinate, polyvinyl alcohol, polyethylene glycol and the like are known. In view of molding processability, aliphatic polyesters have been put into practical use. However, these resins cannot be said to have sufficient heat resistance, mechanical strength, etc. in practice. For example, polylactic acid has a low crystallization rate, so it is difficult to impart heat resistance and inferior toughness. It has drawbacks such as being unsuitable for containers with practical strength. Poly-ε-caprolactone has high impact resistance, but has a low melting point and is not practical.
[0004]
OBJECT OF THE INVENTION
The present invention was made to solve such problems in the prior art, and an object of the present invention is to provide an environmentally disintegrating fat molded article excellent in practical physical properties such as heat resistance and impact resistance. It is said.
[0005]
SUMMARY OF THE INVENTION
  The environmentally disintegrating resin molded product according to the present invention is characterized by comprising an olefin-based block copolymer (A) represented by the following general formula (I);
      PO-f-R (I)
(In the formula, PO represents a polyolefin segment composed of a repeating unit derived from an olefin having 2 to 20 carbon atoms, and having a weight average molecular weight of 2,000 or more, and f represents an ether bond.TheR is obtained by a chain polymerization reaction and has a weight average molecular weight of 500 or more.PolylactideIndicates a segment. ).
[0006]
Moreover, the environmentally disintegrating resin molded body according to another aspect of the present invention is an olefin polymer composition comprising the olefin block copolymer (A) and a thermoplastic resin (B) other than the olefin block copolymer (A). It is characterized by comprising the object (C).
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the environmentally disintegrating resin molding according to the present invention will be specifically described.
The environmentally disintegrating resin molded body according to the present invention comprises an olefin-based block copolymer (A) represented by the following general formula (I).
PO-f-R (I)
In the formula, PO is a polyolefin segment composed of repeating units derived from an olefin having 2 to 20 carbon atoms, and specifically, an olefin homopolymer or copolymer selected from olefins having 2 to 20 carbon atoms. It is a polymer. When this polyolefin segment has stereoregularity, it may be either isotactic polyolefin or 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 nonconjugated 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, 1-octadecene, 1-eicosene, etc., 2 to 20, preferably 2 to 10 carbon atoms Can be mentioned.
[0009]
Examples of the cyclic olefin include those having 3 to 20 carbon atoms, preferably 5 to 15 such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p- Mono or polyalkyl styrenes such as ethyl styrene are mentioned.
[0010]
Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,3-hexadiene. , 1,3-octadiene and the like having 4 to 20, preferably 4 to 10 carbon atoms.
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, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene -2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2 -5 carbon atoms such as norbornadiene 0, preferably include the 5 to 10.
[0011]
The polyolefin segment has a weight average molecular weight of usually 2,000 or more, preferably 2,000 to 10,000,000, more preferably 10,000 to 10,000,000, particularly preferably 10,000 to 200,000. It is desirable to be in the range.
Examples of the polyolefin segment include ethylene homopolymers, ethylene polymers such as ethylene / α-olefin copolymers; propylene polymers such as propylene homopolymers and propylene / α-olefin copolymers; butene homopolymers, Preferred are butene polymers such as butene / ethylene copolymer; 4-methyl-1-pentene polymers such as 4-methyl-1-pentene homopolymer.
[0012]
In the general formula (I), f is an ether bond, an ester bond or an amide bond, and among these, an ether bond is preferable. The part f chemically bonds the polyolefin segment and the following functional segment.
Note that f may include a part of the structure formed by the following chain polymerization reaction, for example, radical polymerization reaction, ring-opening polymerization reaction, or ionic polymerization reaction.
[0013]
In the general formula (I), R is a functional segment obtained by radical polymerization reaction, ring-opening polymerization reaction or ionic polymerization reaction, and represents a repeating unit containing an unsaturated hydrocarbon and / or a repeating unit containing a hetero atom. The functional segment is preferably contained, and more preferably obtained by radical polymerization reaction or ring-opening polymerization reaction. The PO and R are preferably segments made of different polymers.
[0014]
The repeating unit forming the functional segment is composed of radically polymerizable monomers such as methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate, vinyl acrylate (VA), butyl acrylate (BA), styrene, acrylonitrile, vinyl acetate and the like. Derived repeating units: lactones, lactams, 2-oxazolines, cycloethers such as β-propiolactone, β-butyrolactone, δ-valerolactone, glycolide, lactide, ε-caprolactone, α-pyrrolidone, γ And ring-opening polymerizable monomers such as -butyrolactam, ε-caprolactam, ethylene oxide, propylene oxide, epichlorohydrin, oxetane, tetrahydrofuran, and octamethylcyclotetrasiloxane.
[0015]
Examples of the ion polymerizable monomer include anionic polymerizable monomers such as (meth) acrylic acid ester, acrylonitrile, and acrylamide.
This functional segment has a weight average molecular weight (Mw) of usually 500 or more, preferably 5,000 to 1,000,000, more preferably 2,000 to 1,000,000, particularly preferably 10,000 to 200. It is desirable to be in the range of 1,000.
[0016]
Specific examples of functional segments include styrene homopolymers, styrene polymers such as styrene / maleic anhydride copolymers, vinyl acetate polymers; acrylate polymers; methyl methacrylate homopolymers, etc. Methacrylic acid ester polymers; vinylformamide polymers; acrylamide polymers, cyclic ester polymers; cyclic amide polymers; cyclic ether polymers; oxazoline polymers; fluorine-containing polymers Segment.
[0017]
The functional segment is preferably 0.01 to 99.99% by weight, preferably 1 to 99% by weight, more preferably 1 to 95% by weight, particularly preferably relative to the olefinic block copolymer (A). It is preferably contained in an amount of 10 to 90% by weight.
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 minutes, preferably 0.05. It is desirable that it is -100 g / 10 min, more preferably 0.05-80 g / 10 min.
[0018]
In the olefin block copolymer (A) used in the present invention, the PO is a random copolymerization of polypropylene, polyethylene, ethylene and α-olefin having 3 or more carbon atoms, propylene and α-olefin having 4 or more carbon atoms. It is preferably a segment of a random copolymer with an olefin, particularly a polypropylene having a comonomer content of less than 10 mol% selected from ethylene and an α-olefin having 4 or more carbon atoms, and an α-olefin having 3 or more carbon atoms. Polyethylene having a comonomer content of less than 10 mol%, a random copolymer having an ethylene content of 10 to 90 mol%, an α-olefin content of 3 or more carbon atoms of 90 to 10 mol%, and a propylene content of 10 to 90 mol %, A random copolymer segment having a content of α-olefin having 4 or more carbon atoms of 90 to 10 mol% Preferably, f is an ether bond or an ester bond, and R is a functional segment obtained by ring-opening polymerization such as polylactic acid, polyglycolic acid, ε-polycaprolactone, polyethylene glycol, etc. It is preferable.
[0019]
Such an olefin type block copolymer (A) can be manufactured as follows.
The olefin block copolymer (A) used in the present invention, for example, first produces a polyolefin having a terminal group 13 element bonded thereto, and then in the presence of the polyolefin, a chain polymerization reaction such as a radical polymerization reaction, It can manufacture by forming active species, such as a ring polymerization reaction and an ionic polymerization reaction, and performing these reactions.
[0020]
A polyolefin having a group 13 element bonded to the terminal can be produced by coordination polymerization with a transition metal. For example, an olefin having 2 to 20 carbon atoms as described above in the presence of a conventionally known olefin polymerization catalyst. Is produced by homopolymerization or copolymerization. The polyolefin produced here becomes a polyolefin segment of the olefin-based block copolymer (A) (hereinafter sometimes referred to as “PO part”).
[0021]
Conventionally known olefin polymerization catalysts include TiCl._ThreeCatalyst, MgCl₂Supported TiCl_FourAnd a metallocene catalyst, and a metallocene catalyst is preferably used.
Examples of the metallocene catalyst preferably used include conventionally known metallocene catalysts. Examples of metallocene catalysts include metallocene compounds of transition metals such as titanium, vanadium, chromium, zirconium and hafnium. The metallocene compound can be used in a liquid or solid form under the use conditions. Moreover, these do not need to be a single compound, may be supported on other compounds, may be a homogeneous mixture with other compounds, and may be complex compounds or compound compounds with other compounds. There may be.
[0022]
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 chiral metallocene compounds having C2 symmetry include rac-ethylene-bis (indenyl) zirconium dichloride, rac-ethylene-bis (tetrahydroindenyl) zirconium dichloride, 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-dimethylsilylene-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 Lido, 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, rac-dimethylsilylene-bis {1- [2-n-propyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilylene Preferred examples include -bis {1- [2-n-propyl-4- (9-phenanthryl) indenyl]} zirconium dichloride and the like.
[0023]
Metallocene compounds having a chiral structure having C1 symmetry include ethylene [2-methyl-4- (9-phenanthryl) -1-indenyl] (9-fluorenyl) zirconium dichloride, 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) ( Preferred examples include 3-t-butylcyclopentadienyl) zirconium dichloride and the like.
[0024]
Examples of the metallocene compound that is preferably used among conventionally known metallocene compounds include metallocene compounds having only one substituted cyclopentadienyl group.
For example, (tertiary butyramide) (tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (tertiary butylamide) (tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (methylamide) (tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide) (tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamide) (tetramethyl-η^Five-Cyclopentadienyl) methylene titanium dichloride, (tertiary butylamide) dimethyl (tetramethyl-η^Five-Cyclopentadienyl) silane titanium dichloride, (tertiary butylamido) dimethyl (tetramethyl-η^Five-Cyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η^Five-Cyclopentadienyl) silane titanium dichloride, (phenylphosphide) dimethyl (tetramethyl-η^Five-Cyclopentadienyl) silane zirconium dibenzyl and the like.
[0025]
Further, among the conventionally known metallocene compounds, the metallocene compound preferably used has two substituted cyclopentadienyl groups, and these two cyclopentadienyl groups are (substituted) alkylene, (substituted) silylene, etc. Also included are metallocene compounds that are not bonded by the bonding group.
For example, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfo 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 Clopentadienyl) zirconium bis (methanesulfonate), bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis ( (Hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, and the like.
[0026]
The above metallocene compounds may be used alone or in combination of two or more._ThreeCatalyst, MgCl₂Supported TiCl_FourThe catalyst may be used in combination with other olefin polymerization catalysts such as a system catalyst and a post metallocene catalyst.
In the production of polyolefin, the metallocene compound is used in combination with the following organometallic catalyst component. TiCl_ThreeCatalyst, MgCl₂Supported TiCl_FourAlso when a system catalyst or a postmetallocene catalyst is used, it is used in combination with the following organometallic catalyst component.
[0027]
The post metallocene catalyst is a transition metal complex containing a nitrogen atom or an oxygen atom in the ligand, and a conventionally known one is preferably used as the transition metal complex. Examples of the post metallocene catalyst catalyst include transition metal complexes as described in the following documents.
1) M. Brookhart et al., J. Am. Chem. Soc. 1995, 117, 6414-6415
2) M. Brookhart et al., J. Am. Chem. Soc. 1996, 118, 267-268
3) D.H.McConville et al., Macromolecules 1996, 29, 5241-5243
4) R.F.Jordan et al., Organanometallics 1997, 16, 3282-3302
5) R.H.Grubbs et al., Organanometallics 1998,17,3149-3151
6) S. Collins et al., Organometallics 1999, 18, 2731-2733
7) M.S.Eisen et al., Organanometallics 1998, 17, 3155-3157
8) M.S.Eisen et al., J.Am.Chem.Soc. 1998,120,8640-8636
9) R.F.Jordan et al., J.Am.Chem.Soc. 1997,119,8125-8126
10) K. Hakala et al., Macromol. Rapid Commun. 18, 634-638 (1997)
The organometallic catalyst component preferably includes an element selected from Group 13 of the periodic table. Among them, an organoaluminum compound, an organic boron compound, a complex alkyl compound of Group 1 element of the periodic table and aluminum or boron, and the like are preferable. It is done.
[0028]
As an organoaluminum compound, the compound shown with the following general formula can be illustrated, for example.
R^a _nAlX_3-n
(Wherein R^aRepresents a hydrocarbon group having 1 to 12 carbon atoms, X represents halogen or hydrogen, and n is 0 to 3. )
R^aIs a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, Such as cyclopentyl, cyclohexyl, phenyl, tolyl.
[0029]
Specifically, as such an organoaluminum compound,
Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum;
Trialkenyl aluminum such as triisoprenyl aluminum;
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, etc. Alkyl aluminum sesquihalides;
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide;
Examples include alkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride, and ethylaluminum dihydride.
[0030]
As the organoaluminum compound, a compound represented by the following general formula can also be used.
R^a _nAlY_3-n
In the above formula, R^aIs the same as above,
Y is -OR^bGroup, -OSiR^c _ThreeGroup, -OAlR^d ₂Group, -NR^e ₂Group, -SiR^f _ThreeGroup or -N (R^g) AlR^h ₂A group, n is 1-2, R^b, R^c, R^dAnd R^hAre methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, and the like, and R^eIs a hydrogen atom, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., and R^fAnd R^gAre methyl, ethyl and the like.
[0031]
Specific examples of such an organoaluminum compound include the following compounds.
(I) R^a _nAl (OR^b)_3-n  A compound represented by, for example,
Dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc.
(Ii) R^an Al (OSiR^c)_3-n  A compound represented by, for example,
Et₂Al (OSiMe_Three), (Iso-Bu)₂Al (OSiMe_Three), (Iso-Bu)₂Al (OSiEt_Three)Such,
(Iii) R^a _nAl (OAR)^d ₂)_3-n  A compound represented by, for example,
Et₂AlOAlEt₂, (Iso-Bu)₂AlOAl (iso-Bu)₂ Such,
(Iv) R^a _nAl (NR^e ₂)_3-n  A compound represented by, for example,
Me₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt, Et₂AlN (Me_ThreeSi)₂, (Iso-Bu)₂AlN (Me_ThreeSi)₂Such,
(V) R^a _nAl (SiR^f _Three)_3-n  A compound represented by, for example,
(Iso-Bu)₂AlSiMe_ThreeSuch,
(Vi) R^a _nAl [N (R^g) -AlR^h ₂]_3-n  A compound represented by, for example,
Et₂AlN (Me) -AlEt₂(Iso-Bu)₂, AlN (Et) Al (iso-Bu)₂Such.
[0032]
In addition, similar compounds, for example, an organoaluminum compound in which two or more aluminums are bonded via an oxygen atom or a nitrogen atom can be given.
Specifically, (C₂H_Five)₂AlOAl (C₂H_Five)₂, (C_FourH₉)₂AlOAl (C_FourH₉)₂, (C₂H_Five)₂AlN (C₂H_Five) Al (C₂H_Five)₂ Such.
Furthermore, aluminoxanes such as methylaluminoxane, ethylaluminoxane, propylaluminoxane, and butylaluminoxane can be exemplified.
[0033]
Moreover, the organoaluminum compound represented by the following general formula can also be used.
R^aAlXY
(Wherein R^a, X and Y are the same as above)
Organic boron compounds 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, dicyamilborane, diisopinocanphenylborane, 9-borabicyclo [3.3.1] nonane, dimethyl Examples thereof include borane, dichloroborane, catecholborane, B-bromo-9-borabicyclo [3.3.1] nonane, borane-triethylamine complex, and borane-methyl sulfide complex.
[0034]
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) 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-dimethylanilinium tetrakis (pentafluorophenyl) borate, bis [ And tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and the like.
[0035]
Examples of complex alkylated products of Group 1 elements of the periodic table and aluminum include compounds represented by the following general formula.
M¹AlR^j _Four
(Where M¹Represents Li, Na or K, R^jRepresents a hydrocarbon group having 1 to 15 carbon atoms. )
Specifically, LiAl (C₂H_Five)_Four, LiAl (C₇H₁₅)_FourEtc.
[0036]
The organoboron compound and the complex alkylated product of Group 1 element of the periodic table and boron are compounds of the above-described organoaluminum compound and the complex alkylated product of Group 1 element of the periodic table and aluminum substituted with boron. Can be mentioned.
The said organometallic catalyst component can be used individually by 1 type or in combination of 2 or more types.
[0037]
The organometallic catalyst component is preferably used in combination with a compound having a hydrogen-13 group element bond and a trialkylaluminum or aluminoxane or an ionic boron compound. A compound having a hydrogen-boron bond is preferred. These compounds may be used for polymerization after mixing, or may be added to a polymerization system after having initiated polymerization using only trialkylaluminum, aluminoxane or ionic boron compound, and then having a hydrogen-13 group element bond. preferable.
[0038]
Examples of the compound having a hydrogen-13 group element bond include diethylaluminum hydride, diisobutylaluminum hydride, ethylaluminum dihydride, etc. among organoaluminum compounds; 9-borabicyclo [3.3.1] nonane among organoboron compounds, Examples thereof include dimethylborane, dichloroborane, and catecholborane.
[0039]
The olefin polymerization catalyst as described above may be preliminarily polymerized. There is no particular limitation on the method for carrying out the prepolymerization. For example, the prepolymerization can be carried out in the presence of an inert solvent, and the prepolymerization can be carried out under relatively mild conditions by adding an olefin and each catalyst component to the inert solvent. preferable. At this time, it may be carried out under the condition that the produced prepolymer is dissolved in the polymerization medium, or may be carried out under the condition where it is not dissolved, but it is preferably carried out under the condition where it is not dissolved.
[0040]
Examples of the olefin used for the prepolymerization include α-olefins having 2 or more carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-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, etc. . Two or more of these may be used in combination. The α-olefin used in the prepolymerization may be the same as or different from the α-olefin used in the olefin polymerization described later, but the same olefin as used in the olefin polymerization is preferable.
[0041]
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; halogenated hydrocarbons such as ethylene chloride and chlorobenzene. These may be used in combination.
[0042]
Of these inert solvents, it is particularly preferable to use an aliphatic hydrocarbon. The prepolymerization can be performed in a state where the α-olefin is in a liquid state, or can be performed under a gas phase condition. The prepolymerization can be performed in any of a batch type, a semi-continuous type, and a continuous type. Further, in the prepolymerization, it is preferable to use a catalyst having a concentration higher than the catalyst concentration in the system in the main polymerization.
[0043]
The polyolefin to be the PO part of the olefin block copolymer (A) is homopolymerized or copolymerized with an olefin having 2 to 20 carbon atoms as described above in the presence of the above olefin polymerization catalyst ( Hereinafter, it may be simply referred to as “olefin polymerization”.
The olefin polymerization can be carried out in any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods. As the reaction solvent for the suspension polymerization, the above-mentioned inert solvent can be used, or a liquid olefin can be used at the reaction temperature. The reaction temperature is usually 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 1 to 50 atm. Olefin polymerization can be carried out in any of batch, semi-continuous, and continuous methods, and when it is carried out in two or more stages, the reaction conditions may be the same or different.
[0044]
In the olefin polymerization, a polyolefin having a weight average molecular weight of usually 2,000 or more, preferably 2,000 to 1,000,000 is produced. At this time, it is preferable that molecular hydrogen which is a general molecular weight regulator is not present in the polymerization system, and the molecular weight is adjusted by any of the above-mentioned organometallic catalyst component concentration, polymerization temperature, and olefin concentration (polymerization pressure). It is preferable to carry out by controlling one or more kinds. Specifically, as a method for preparing the molecular weight, for example, in suspension polymerization in which molecular hydrogen is not substantially present, increasing the concentration of the organometallic catalyst component can reduce the molecular weight of the resulting polyolefin, In suspension polymerization in which molecular hydrogen is not substantially present, the molecular weight of the resulting polyolefin can be lowered by increasing the polymerization temperature.
[0045]
One end of the polyolefin obtained as described above is an end bonded with a group 13 element or an unsaturated bond end. Whether one end of the polyolefin is a terminal to which a group 13 element is bonded or an unsaturated bond terminal depends on the polymerization conditions such as the type and / or amount of the organometallic catalyst component used and the polymerization temperature.
When one end of the polyolefin is an unsaturated bond end, a compound containing a group 13 element is reacted to convert the end to a group 13 element bonded. In addition, even when the obtained polyolefin is a mixture of one having a group 13 element bonded to one end and one having an unsaturated bond end on one end, the one end is unsaturated bond, if necessary. You may convert the terminal of polyolefin which is a terminal into the terminal which group 13 element combined.
[0046]
The compound containing a group 13 element used in the reaction is selected from the compounds exemplified as the organic compound catalyst component described above, and the compounds exemplified as the organoaluminum compound or the organoboron compound are preferably used. Among these, 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.
[0047]
The reaction of a polyolefin having one end of an unsaturated bond and a compound containing a group 13 element is performed, for example, as follows.
(1) 0.1 to 50 g of polypropylene having a vinylidene group at the end and 0.01 to 5 mol / liter-octane solution of diisobutylaluminum hydride in an amount of 5 to 1000 ml are mixed and refluxed for 0.5 to 6 hours. .
(2) 0.1 to 50 g of polypropylene having a terminal vinylidene group, 5 to 1000 ml of anhydrous tetrahydrofuran, and 0.05 to 10 mol of 0.1 to 50 ml of 9-borabicyclo [3.3.1] nonane The liter-tetrahydrofuran solution is mixed and stirred at 20-65 ° C. for 0.5-24 hours.
[0048]
The polyolefin used as the PO part of an olefin type block copolymer (A) is manufactured as mentioned above. A group 13 element is bonded to one end of the obtained polyolefin. The group 13 element is preferably boron.
Next, chain polymerization active species such as radical polymerization reaction, ring-opening polymerization reaction, and ionic polymerization reaction are formed in the presence of the polyolefin having a group 13 element bonded to one end, and these reactions are performed to carry out the olefin block copolymer. A polymer (A) is manufactured. By this reaction, the f part is formed between the group 13 element bonded to the terminal and the polyolefin segment, and a polymer produced by a chain polymerization reaction such as radical polymerization reaction, ring-opening polymerization reaction, ionic polymerization reaction, It becomes a functional segment (hereinafter sometimes referred to as “R portion”). 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, or an ionic polymerization reaction.
[0049]
This polymerization reaction is performed, 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. Do.
Specifically, a polyolefin having boron bonded to one end is oxidized with molecular oxygen in the presence of a radical polymerizable monomer. This converts the terminal boron into peroxyborane (—O—O—B). When the peroxyborane is stirred in the presence of a radical polymerizable monomer, the O—O bond is cleaved to generate a radical, and the generated alkoxy radical (—O^*) Serves as an initiator, and radical polymerization of the radical polymerizable monomer proceeds.
[0050]
Examples of the radical polymerizable monomer include methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate, vinyl acrylate (VA), butyl acrylate (BA), styrene, acrylonitrile, vinyl acetate and the like. These radically polymerizable monomers may be used alone or in combination of two or more.
[0051]
Termination of radical polymerization can be performed by precipitating the polymer in methanol. As described above, an olefin block copolymer (A) in which the f part is an ether bond or an ester bond and the R part is a radical polymer can be produced.
(2) When the group 13 element bonded to one end of the polyolefin is aluminum, active species are generated by oxidizing the carbon-aluminum bond with molecular oxygen to perform a ring-opening polymerization reaction.
[0052]
Specifically, the carbon-aluminum bond is oxidized with molecular oxygen, thereby converting the aluminum at the end of the PO moiety into aluminum oxide (—O—Al). The ring-opening polymerizable monomer is subjected to ring-opening polymerization using the obtained aluminum oxide as an active species.
Examples of the ring-opening polymerizable monomer include lactones, lactams, 2-oxazolines, cycloethers, and the like. Specifically, β-propiolactone, β-butyrolactone, δ-valerolactone, glycolide, lactide, Examples include ε-caprolactone, α-pyrrolidone, γ-butyrolactam, ε-caprolactam, 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.
[0053]
The ring-opening polymerization reaction is usually performed at a temperature of 0 to 100 ° C. for 30 minutes to 12 hours, preferably 1 hour to 6 hours. The ring-opening polymerization reaction can be stopped by precipitating the polymer in methanol. As described above, an olefin block copolymer (A) in which the f part is an ether bond or an ester bond and the R part is a ring-opening polymer can be produced.
(3) A group 13 element bonded to one end of the polyolefin is converted into a hydroxyl group, an amino group, an aldehyde group, or a halogen, and then a ring-opening polymerization active species is generated to perform a ring-opening polymerization reaction.
[0054]
For example, a ring-opening polymerization active species is produced by adding a sodium hydroxide solution and a hydrogen peroxide solution to a polyolefin bonded with boron at one end and reacting at 40 ° C. to 50 ° C. for 3 to 5 hours to form boron into a hydroxyl group. This can be carried out by reacting butyllithium with this and then reacting with diethylaluminum chloride to convert the hydroxyl group into aluminum oxide.
[0055]
The ring-opening polymerizable monomer is subjected to a ring-opening polymerization reaction using the aluminum oxide obtained by such a method 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 as an active species for the ring-opening polymerization reaction. Active species other than aluminum oxide are generated using a hydroxyl group, amino group, aldehyde group or halogen bonded to one end of the polyolefin. Among these, it is preferable to use aluminum oxide as an active species. As described above, an olefin block copolymer (A) in which the f part is an ether bond, an ester bond or an amide bond and the R part is a ring-opening polymer can be produced.
[0056]
As an example of an ionic polymerization reaction, for example, when an anionic polymerization reaction is performed, an anionic polymerization can be performed after converting a 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 various monomers. 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 lithium at the terminal will be described.
[0057]
Preparation of polyolefin with terminal lithium
A polyolefin having lithium at the terminal can be obtained by reacting the polyolefin having a hydroxyl group at the terminal with an organic lithium compound. The reaction between the polyolefin having a hydroxyl group at the terminal and the organolithium compound is usually carried out in a solvent.
[0058]
Examples of the organic lithium compound include alkyl lithium such as butyl lithium, propyl lithium, ethyl lithium, and methyl lithium; alkoxy lithium such as butoxy lithium, propoxy lithium, ethoxy lithium, and methoxy lithium. In the present invention, alkyl lithium is more preferably used.
[0059]
Examples of the solvent used for the reaction include the same hydrocarbons as exemplified as the inert hydrocarbon medium.
When the polyolefin having a terminal hydroxyl group is reacted with the organolithium compound, the organolithium compound is used in an amount of 0.1 to 100 mol, preferably 0.2 to 10 mol, per 1 mol of the hydroxyl group of the polyolefin end. . The reaction temperature is usually −100 to 100 ° C., preferably 0 to 80 ° C., and the reaction time is usually 0.1 to 48 hours, preferably 0.5 to 12 hours.
[0060]
In this way, a polyolefin having lithium at the terminal represented by the following general formula (II) is produced.
PO-O-Li (II)
In the formula, PO represents a polyolefin segment having a weight average molecular weight of 1,000 to 10,000,000, preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000. The terminal Li polyolefin preferably has Mw / Mn of 2 or more, preferably 3 to 15, more preferably 4 to 14.
[0061]
Production of block copolymers
Next, for example, (meth) acrylic acid ester is anionically polymerized in the presence of the terminal Li polyolefin to obtain a polyolefin block copolymer comprising a polyolefin segment and a (meth) acrylic acid ester segment.
The polymerization is carried out by mixing the solvent, the terminal Li polyolefin and the (meth) acrylic acid ester, or by mixing the terminal Li polyolefin and a liquid (meth) acrylic acid ester. An anionic polymerization active species can be formed by mixing the terminal Li polyolefin, the solvent, and the (meth) acrylic acid ester.
[0062]
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), monoglyme, and diglyme. An ether solvent such as is used. These solvents can be used singly or in combination of two or more. Of these, aromatic hydrocarbons and ether solvents are preferably used.
[0063]
Examples of (meth) acrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, vinyl acrylate, 2-methacrylic acid 2- Examples include methoxyethyl and 2- (N, N-diethylamino) ethyl methacrylate. These (meth) acrylic acid esters can be used singly or in combination of two or more. As a combination of (meth) acrylic acid esters, 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. And combinations thereof.
[0064]
In addition, compounds useful for the formation of anionic polymerization active species such as triphenylphosphine, α, α′-dipyridyl, hexamethylphosphoramide (HMPA), titanium tetrachloride, alkyllithium, and alkoxylithium may be added during polymerization. Good.
The polymerization is usually performed at a polymerization temperature of −100 ° C. to 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. Is carried out over 15 minutes to 150 hours. In this polymerization, the terminal Li polyolefin is 0.001 to 100 mol / liter, preferably 0.005 to 50 mol / liter, more preferably 0.01 to 10 mol / liter, and further preferably 0.1 to 5 mol. Used at a concentration of mol / liter. The (meth) acrylic acid ester is usually used at a concentration of 0.001 to 500 mol / liter, preferably 0.005 to 300 mol / liter, more preferably 0.01 to 150 mol / liter.
[0065]
It is preferable to produce a poly (meth) acrylic acid ester segment having stereoregularity by polymerization as described above. 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 and mm are obtained by dissolving the sample in nitrobenzene-d5.¹H-NMR is measured and determined by the ratio of the peak area of rr or the peak area of mm to the sum of the peak areas of rr, mr, and mm detected in the vicinity of 0.85, 1.05, and 1.25 ppm, respectively.
[0066]
As described above, a polymer containing a block copolymer in which a polyolefin segment (PO) and a poly (meth) acrylic ester segment are chemically bonded can be produced. Whether or not the polymer includes a chemically bonded polymer with an acrylate segment can be determined by, for example, the molecular weight of the obtained polymer, 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, corresponding to the polyolefin segment of the olefin block copolymer polymer obtained by the method of the present invention. The dissolution behavior in the organic solvent of the mixture of the polymer and the polymer corresponding to the segment of the polymer produced by anionic polymerization of the polymer indicates that the olefin block copolymer obtained by the method of the present invention is dissolved in the organic solvent. The terminal structure of the olefinic block copolymer obtained by the method of the present invention is different from that of the behavior.¹³The target block copolymer can be produced by detecting peaks derived from chemical bonds between the polyolefin segment and the poly (meth) acrylate segment of the polymer produced by anionic polymerization as analyzed by C-NMR. Can be judged.
[0067]
In the chain polymerization reaction such as the above radical polymerization reaction, ring-opening polymerization reaction, and ionic polymerization reaction, a polymer having a weight average molecular weight of usually 500 or more, preferably 5,000 to 1,000,000 is produced.
The environmentally disintegrating resin molding according to the present invention is formed from the olefin block copolymer (A) as described above. The olefin block copolymer (A) may contain an additive known in the art in any proportion as it is used for fillers, core materials, and other resins.
[0068]
Moreover, the environmentally disintegrating resin molded product according to the present invention is an olefin polymer composition (C) containing the olefin block copolymer (A) and a thermoplastic resin (B) other than the olefin block copolymer (A). It may be formed. The olefin polymer composition (C) may contain two or more olefin block copolymers (A).
In addition to the olefin block copolymer (A) and the thermoplastic resin (B), the olefin polymer composition (C) includes a crosslinking agent, a crosslinking accelerator, a crosslinking aid, a softener, and an adhesive. Imparting agent, anti-aging agent, foaming agent, processing aid, adhesion imparting agent, inorganic filler, organic filler, crystal nucleating agent, heat stabilizer, weathering stabilizer, antistatic agent, colorant, lubricant, flame retardant, An additive such as an anti-blooming agent may be included. Further, secondary modification such as crosslinking and foaming may be performed.
[0069]
As the thermoplastic resin (B), polyolefin, polyamide, polyester, polyacetal, polystyrene, acrylonitrile / butadiene / styrene copolymer (ABS), polycarbonate, polyphenylene oxide, polyacrylate, polyvinyl chloride and the like are used.
Specific examples of polyolefins include ethylene polymers such as ethylene homopolymers and ethylene / α-olefin copolymers; propylene polymers such as propylene homopolymers and propylene / α-olefin copolymers; Butene polymers such as polymers; 4-methyl-1-pentene polymers such as 4-methyl-1-pentene homopolymer; 3-methyl-1-butenes such as 3-methyl-1-butene homopolymer Hexene polymers such as hexene homopolymers. Of these, ethylene polymers, propylene polymers, and 4-methyl-1-pentene polymerization are preferable.
[0070]
Specific examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; aliphatics such as polylactic acid, polyglycolic acid, poly-ε-caprolactone, polybutylene succinate, and polyhydroxybutyrate. Examples include polyester. Among these, polyethylene terephthalate is particularly preferable.
[0071]
Specific examples of polyamides include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon-46; aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines, and the like. It is done. Among these, nylon-6 is particularly preferable.
Specific examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde and the like. Among these, polyformaldehyde is particularly preferable.
[0072]
Polystyrene may be a homopolymer of styrene, or a binary copolymer of styrene and acrylonitrile, methyl methacrylate, or α-methylstyrene.
ABS includes 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 a structural unit derived from styrene. ABS contained in an amount of 40 to 60 mol% is preferably used.
[0073]
Polycarbonates include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl) Examples thereof include polymers obtained from butane and the like. Of these, polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.
[0074]
As the polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene oxide) is preferably used.
As the polyacrylate, polymethyl methacrylate or polybutyl acrylate is preferably used.
The thermoplastic resins (B) as described above may be used alone or in combination of two or more.
[0075]
Among these thermoplastic resins (B), polyolefins (b-1) such as polyethylene, polypropylene, and ethylene / propylene copolymers, and polylactic acid, polyglycolic acid, poly-ε-caprolactone, polybutylene succinate, etc. It is preferable to use in combination with aliphatic polyester (b-2).
For example, as the polyolefin (b-1), at least one kind of polyolefin (Mw: 5,000 to 1,000,000) selected from polyethylene, isotactic polypropylene, isotactic block polypropylene and the like and having a high crystallization rate is used. And at least one aliphatic polyester (Mw: 2,000 to 1,000,000) selected from polylactic acid, polyglycolic acid and the like as the aliphatic polyester (b-2) and having a relatively slow crystallization rate. Is preferred. At this time, the PO part of the olefinic block copolymer (A) is the same kind of polyolefin as the polyolefin (b-1), and the R part is the same kind of aliphatic polyester as the aliphatic polyester (b-2). preferable.
[0076]
Further, as polyolefin (b-1), ethylene / α-olefin copolymer such as ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / octene copolymer (α-olefin content: 2 to 98 mol%) , Mw: 5,000 to 1,000,000); propylene / ethylene copolymer, propylene / butene copolymer (ethylene or C4 or higher α-olefin content: 2-98 mol%, Mw: 2,000- High-rigidity aliphatic polyester (Mw: 2,000 to 1,000,000) selected from polylactic acid, polyglycolic acid and the like as a soft polyolefin such as 1,000,000) and aliphatic polyester (b-2) It is also preferable to use At this time, the PO part of the olefinic block copolymer (A) is the same kind of polyolefin as the polyolefin (b-1), and the R part is the same kind of aliphatic polyester as the aliphatic polyester (b-2). preferable.
[0077]
Further, as the polyolefin (b-1), a high melting point polyolefin such as high density polyethylene, medium density polyethylene, isotactic polypropylene, poly-4-methyl-1-pentene (Mw: 5,000 to 1,000,000) and As the aliphatic polyester (b-2), a flexible aliphatic polyester (Mw: 2,000 to 1,000,000) such as polyε-caprolactone or a hydrophilic polyether (Mw: 2,000 to 1) such as polyethylene glycol , 000,000). At this time, the PO part of the olefinic block copolymer (A) is the same kind of polyolefin as the polyolefin (b-1), and the R part is the same kind of aliphatic polyester as the aliphatic polyester (b-2). preferable.
[0078]
When such a combination is used, it is possible to provide an environmentally disintegrating resin molded body having practical properties such as environmental disintegration and excellent heat resistance and mechanical strength.
When the olefin polymer composition (C) used in the present invention contains the olefin block copolymer (A), the polyolefin (b-1), and the aliphatic polyester (b-2). 1 to 98 parts by weight of the olefin block copolymer (A), 1 to 70 parts by weight of the polyolefin (b-1), and 98 to 1 part by weight of the aliphatic polyester (b-2) ((A ) + (B-1) + (b-2) is preferably contained in an amount of 100 parts by weight), 5 to 50 parts by weight of the olefin block copolymer (A), the polyolefin (b-1) 5 to 50 parts by weight, and the aliphatic polyester (b-2) in an amount of 90 to 45 parts by weight ((A) + (b-1) + (b-2) is 100 parts by weight). Particularly preferred.
[0079]
As a method for adjusting such an olefin polymer composition (C), any known method can be employed. For example, the olefin block copolymer (A), the thermoplastic resin (B), and the above additives. Can be melt kneaded using an extruder, a kneader, or the like.
The environmentally disintegrating resin molding according to the present invention is disintegrated by biological metabolism, heat, light, etc. in the natural environment and does not retain its shape. Even if the molded body is collapsed, a part of the resin forming the molded body remains in the environment.
[0080]
Molding method
The environmentally disintegrating resin molding according to the present invention is formed from the olefin block copolymer (A) or the olefin polymer composition (C).
The molding method of the environmentally disintegrating resin molding according to the present invention is not particularly limited, and can be manufactured by a method such as calendar molding, extrusion molding, injection molding, blow molding, press molding, stamping molding, or the like.
[0081]
When extruding the olefin-based block copolymer (A) or the olefin-based polymer composition (C), conventionally known extruding equipment and molding conditions can be employed, such as a single screw extruder, By using a kneading extruder, a ram extruder, a gear extruder, etc., the molten olefin block copolymer (A) or olefin polymer composition (C) is extruded from a T die or the like (sheet or film). Unstretched) and the like.
[0082]
The stretched film is obtained by stretching an extruded sheet or an extruded film (unstretched) as described above, for example, by a tenter method (longitudinal and transverse stretching or transverse and longitudinal stretching), a simultaneous biaxial stretching method, or a uniaxial stretching method. An inflation film can also be produced from the olefin block copolymer (A) or the olefin polymer composition (C) according to the present invention.
[0083]
Filaments can be made, for example, by extruding the molten composition through a spinneret. Further, it may be prepared by a melt blown method.
The injection-molded body can be manufactured by injection molding into various shapes using a known injection molding apparatus under known conditions.
The blow-molded product can be manufactured by adopting known conditions using a conventionally known blow molding apparatus.
[0084]
In injection blow molding, the above composition is injected into a parison mold at a resin temperature of 100 ° C. to 250 ° C. to form a parison, and then the parison is held in a mold having a desired shape, and then air is blown into the mold. A hollow molded body can be manufactured by wearing on.
An example of the press-molded body is a mold stamping molded body.
[0085]
Application
The environmentally disintegrating resin molded body according to the present invention is easily disintegrated in the environment and is excellent in rigidity, heat resistance, impact resistance and the like, and can be used in a wide range of fields such as outdoor goods and disposable containers.
For example, fresh food containers such as fish, vegetables and eggs sold in supermarkets; take-out food containers such as bento and prepared dishes; containers for noodles such as beverage cups and ramen; containers such as disposable dishes used outdoors ; Food packaging bags, plastic bags in supermarkets, bags such as garbage bags, garbage bags for garbage It can be used as a cloth for outdoor goods such as a tent, and also as a water retaining material or film that easily collapses in the environment.
[0086]
【The invention's effect】
The environmentally disintegrating resin molded body according to the present invention is excellent in mechanical strength and heat resistance such as elastic modulus and impact resistance, and easily disintegrates in the environment. It can be applied to a certain field.
In addition, the environmentally disintegrating resin molded body according to the present invention is superior in balance of physical properties such as strength and transparency as compared with a molded body made of a composition of a conventional biodegradable polymer and a polyolefin resin.
[0087]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[0088]
[Production Example 1]
[Preparation of catalyst solution]
Methylaluminoxane and rac-dimethylsilylenebis (2-ethyl-4-naphthylindenyl) zirconium dichloride in toluene having a zirconium concentration of 0.00011 mmol / liter and a molar ratio of aluminum to zirconium (Al / Zr) of 350 (A suitable amount of toluene was added if necessary), and the mixture was stirred for 15 minutes for preactivation treatment to prepare catalyst solution (1).
[0089]
[Olefin polymerization]
A glass reactor with an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of purified toluene, ethylene was circulated at a rate of 80 liters per hour, and propylene was circulated at a rate of 120 liters per hour, and stirred at 600 rpm with a magnetic stirrer While maintaining at 45 ° C. for 10 minutes. Next, 6.7 mg of triisobutylaluminum was charged to the reactor in terms of aluminum atoms. Furthermore, 0.045 mg (0.0005 mmol) of the catalyst solution (1) was charged in terms of zirconium atom. After polymerization at 50 ° C. and normal pressure for 20 minutes, a small amount of isopropanol (IPA) was added to terminate the polymerization. After completion of the polymerization, the reaction solution was poured into 2 liters of dilute hydrochloric acid in methanol to precipitate the polymer. The precipitated polymer was washed twice with methanol, and the obtained polymer was dried at 130 ° C. under reduced pressure overnight.
[0090]
The obtained ethylene / propylene random copolymer (EPR) was 28.8 g, and the catalyst activity was 172.8 kg / mmol-Zr · hr. The ethylene content determined from IR analysis was 81.7 mol%, and an unsaturated bond was present at the polymer terminal. Mw was 55,000.
[Hydroboration]
20 g of the EPR suspended in 100 ml of degassed dry tetrahydrofuran (THF) in a dry box filled with argon was placed in a glass flask equipped with a magnetic stir bar and further 9-borabicyclo [3.3.1] nonane (9 -BBN) in THF (0.5 mol) (5.8 ml) was added. The slurry was stirred at 55 ° C. for 5 hours in a dry box and then filtered. The obtained residue was washed with degassed dry IPA and then dried under reduced pressure to obtain EPR (EPR-B) having boron at the terminal. Obtained.
[0091]
[Hydroxylation]
10 g of the EPR-B was suspended in 50 ml of degassed dry THF, and 2.3 ml of an aqueous solution containing 0.5 g of NaOH and 0.6 ml of methanol were added under a nitrogen atmosphere. The suspension is cooled to 0 ° C. and H₂O₂After adding 1.8 ml of a (30%) aqueous solution and reacting at 40 ° C. for 6 hours, 100 ml of methanol was added to stop the reaction. The obtained polymer was filtered off, and the obtained filtrate was heated to reflux in 100 ml of methanol for 2 hours and then filtered again. The obtained residue was dried under reduced pressure at 50 ° C. for 8 hours to obtain EPR (EPR-OH) containing an OH group at the terminal.
[0092]
[Lactide polymerization]
3.5 g of the EPR-OH was suspended with dry toluene in a dry box. Excess n-butyllithium was added thereto, and the mixture was stirred for 12 hours. Then, filtration and toluene washing were repeated to obtain an EPR having a lithium oxide at the terminal. The EPR having lithium oxide at the terminal is suspended in toluene, and 3 equivalents of diethylaluminum chloride is added and reacted for 12 hours to react with EPR having an aluminum oxide at the terminal (EPR-OAlEt).₂) This EPR-OAlEt₂Was washed with toluene and hexane, filtered, resuspended in 80 ml of toluene, 156.2 g of purified lactide was added, and the mixture was reacted at room temperature for 64 hours. After stopping the reaction by adding 100 ml of methanol, the polymer was precipitated in acidic methanol, and the unnecessary part was extracted and removed with acetone using a Soxhlet extractor, whereby an ethylene / propylene random copolymer-O-polylactide diblock was obtained. A copolymer (EPR-O-PLa) was obtained.
[0093]
The weight average molecular weight (Mw) of the PLa portion of this diblock copolymer calculated by the following formula:₂) Was 150,000.
Mw₂= Mw₁・ (W₂-W₁) / W₁
In the above formula
Mw₁: Mw of EPR section
Mw₂: Mw of PLa part
W₁: EPR-OAlEt used for lactide polymerization₂Weight of
W₂: Yield of diblock copolymer
Respectively.
[0094]
[Production Example 2]
[Preparation of catalyst solution]
Methylaluminoxane and dimethylsilylenebis (indenyl) zirconium dichloride are mixed in toluene at a ratio such that the zirconium concentration is 0.00011 mmol / liter and the molar ratio of aluminum to zirconium (Al / Zr) is 350 (appropriate if necessary An amount of toluene was added.), And the mixture was stirred for 15 minutes for preactivation treatment to prepare a catalyst solution (2).
[0095]
[polymerization]
750 ml of purified heptane was charged into a 2 liter stainless steel autoclave thoroughly purged with nitrogen, and the system was replaced with propylene. Next, the system was heated to 40 ° C., and 0.20050 mmol of triisobutylaluminum and 0.00050 mmol of the catalyst solution (2) were added in terms of zirconium atoms. Thereafter, the temperature was raised while being pressurized with propylene. The polymerization was started when the total pressure became 0.8 MPa and the temperature reached 70 ° C., and polymerization was carried out for 30 minutes while maintaining this pressure and temperature. After 30 minutes, the supply of propylene was stopped to complete the polymerization reaction. After depressurization and cooling, the slurry was taken out, and the solid part was collected by filtration, and dried under reduced pressure at 80 ° C. and 500 mmHg for 12 hours under a nitrogen flow.
[0096]
Polypropylene (PP) obtained as described above was 39.8 g, and the activity was 161 kg / mmol-Zr · hr. The Mw measured by GPC of this polypropylene was 69,000. The melting point (Tm) measured by DSC is 139.1 ° C.¹³The mesopentad fraction (mmmm) measured by C-NMR was 90.8%. As a result of IR analysis, it was confirmed that an unsaturated bond was present at the polymer terminal.
[0097]
[Hydroboration]
In a dry box filled with argon, 20 g of the above end-unsaturated polypropylene suspended in 100 ml of degassed and dried THF was placed in a glass flask equipped with a magnetic stirring bar, and a THF solution of 9-BBN (0.5 Mol) 4.6 ml was added. This slurry was stirred at 55 ° C. for 5 hours in a dry box, filtered, washed with degassed dry IPA, and then dried under reduced pressure to obtain polypropylene having a terminal boron (PP-B).
[0098]
[Hydroxylation]
10 g of the PP-B was suspended in 50 ml of degassed dry THF, and 1.8 ml of an aqueous solution containing 0.4 g of NaOH and 0.5 ml of methanol were added under a nitrogen atmosphere. The suspension is cooled to 0 ° C. and H₂O₂After adding 1.5 ml of a (30%) aqueous solution and reacting at 40 ° C. for 6 hours, 100 ml of methanol was added to stop the reaction. The obtained polymer was filtered off, and the obtained filtrate was heated to reflux in 100 ml of methanol for 2 hours and then filtered again. The obtained residue was dried under reduced pressure at 50 ° C. for 8 hours to obtain PP (PP-OH) containing an OH group at the terminal.
[0099]
[Lactide polymerization]
The PP-OH (3.5 g) was suspended with dry toluene in a dry box. Excess n-butyllithium was added thereto and stirred for 12 hours, and then filtration and toluene washing were repeated to obtain PP having a lithium oxide at the terminal. PP (PP-OAlEt) having aluminum oxide at its terminal is prepared by suspending PP having lithium oxide at its terminal with toluene, adding 3 equivalents of diethylaluminum chloride and reacting for 12 hours.₂) This PP-OAlEt₂After washing with toluene and hexane and filtering, the obtained filtrate was resuspended in 80 ml of toluene, and 124.1 g of purified lactide was added and reacted at room temperature for 64 hours. After the reaction was stopped by adding 100 ml of methanol, the polymer was precipitated in acidic methanol, and unnecessary portions were extracted and removed with acetone using a Soxhlet extractor to obtain a polypropylene-O-polylactide diblock copolymer (PP- O-PLa) was obtained.
[0100]
The weight average molecular weight (Mw) of the PLa portion calculated from the following formula of this diblock copolymer:₂) Was 150,000.
Mw₂= Mw₁・ (W₂-W₁) / W₁
In the above formula
Mw₁: Mw of PP part
Mw₂: Mw of PLa part
W₁: PP-OAlEt used for lactide polymerization₂Weight of
W₂: Yield of diblock copolymer
Respectively.
[0101]
[Production Example 3]
[Preparation of catalyst solution]
In a glass container thoroughly substituted with nitrogen, bis (pentamethyl-η^Five-Cyclopentadienyl) dimethylzirconium was weighed so that the zirconium atom became 0.23 mmol, and a toluene solution of tris (pentafluorophenyl) borane was added thereto so that the boron atom became 0.92 mmol. An appropriate amount of toluene was added thereto to make a total amount of 50 ml, and a catalyst solution (3) having a zirconium concentration of 0.0046 mmol / ml was prepared.
[0102]
[Olefin polymerization]
225 ml of purified toluene was charged into a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, and ethylene was circulated at a rate of 200 liters per hour, and stirred at 45 ° C. with stirring at 600 rpm using a magnetic stirring bar. Hold for a minute. Next, 7.5 mmol of triisobutylaluminum in terms of aluminum atoms was charged into the reactor. Furthermore, 9 mmol of 9-BBN was charged, and then 0.075 mmol of the catalyst solution (3) was charged in terms of zirconium atoms. Polymerization was carried out at 50 ° C. and normal pressure for 5 minutes, and then a small amount of anhydrous methanol was added to terminate the polymerization. After completion of the polymerization, the polymer was washed with anhydrous THF, and the resulting polymer was dried at 50 ° C. under reduced pressure overnight. The obtained polyethylene was 5.1 g, and the catalytic activity was 816 g / mmol-Zr · hr.
[0103]
[Molecular weight and confirmation of polymer ends]
Of the obtained polyethylene, 1.0 g was added to 25 ml of anhydrous THF. To this was added 1 ml of an aqueous solution containing 0.2 g of NaOH and 0.25 ml of methanol under a nitrogen atmosphere at room temperature. Then 0.8 ml of 30% H₂O₂Was added dropwise at 0 ° C. After reacting this at 40 ° C. for 6 hours, the reaction solution was poured into 2 liters of methanol solution to precipitate a polymer. The obtained polymer was refluxed with 50 ml of methanol for 2 hours, and then dried under reduced pressure at 50 ° C. for 8 hours. The Mw determined from GPC analysis was 52,400. Moreover, since it confirmed that the polymer terminal was modified by the hydroxyl group and there was no unsaturated bond from IR analysis, it was judged that the terminal of the polyethylene was modified with boron.
[0104]
[Hydroxylation]
20 g of polyethylene having boron at the end was suspended in 50 ml of degassed dry THF, and 2.4 ml of an aqueous solution containing 0.5 g of NaOH and 0.6 ml of methanol were added under a nitrogen atmosphere. The suspension is cooled to 0 ° C. and H₂O₂1.9 ml of a (30%) aqueous solution was added dropwise and reacted at 40 ° C. for 6 hours, and then 100 ml of methanol was added to stop the reaction. The resulting polymer was filtered off, and the filtrate was heated to reflux in 100 ml of methanol for 2 hours and then filtered again. The obtained filtrate was dried under reduced pressure at 50 ° C. for 8 hours to obtain homopolyethylene (HDPE-OH) containing an OH group at the terminal.
[0105]
[Caprolactone polymerization]
The HDPE-OH (3.5 g) was suspended with dry toluene in a dry box. Excess n-butyllithium was added thereto and stirred for 12 hours, followed by repeated filtration and toluene washing to obtain HDPE having a lithium oxide at the terminal. HDPE having lithium oxide at the terminal is suspended in toluene, 3 equivalents of diethylaluminum chloride is added and reacted for 12 hours to react with HDPE having aluminum oxide at the terminal (HDPE-OAlEt₂) This HDPE-OAlEt₂After washing with toluene and hexane and filtering, the obtained filtrate was resuspended in 80 ml of toluene, and 127.2 g of purified caprolactone was added and reacted at room temperature for 76 hours. After stopping the reaction by adding 100 ml of methanol, the polymer was precipitated in acidic methanol, and the precipitated polymer was extracted and removed with acetone using a Soxhlet extractor, so that the polyethylene-O-polycaprolactone diblock was co-polymerized. A polymer (HDPE-O-PCL) was obtained.
[0106]
The Mw (Mw of the PCL part) calculated by the following formula of this diblock copolymer₂) Was 150,000.
Mw₂= Mw₁・ (W₂-W₁) / W₁
In the above formula
Mw₁: Mw of HDPE
Mw₂: Mw of PCL part
W₁: HDPE-OAlEt used for caprolactone polymerization₂Weight of
W₂: Yield of diblock copolymer
Respectively.
[0107]
[Example 1]
The diblock copolymer (EPR-O-PLa) produced in Production Example 1 was pulverized and powdered, and then thoroughly dried with a vacuum dryer. 0.1 parts by weight of Irganox 1010 (trade name, manufactured by Ciba Specialty Chemicals) was added to 100 parts by weight of the dried diblock copolymer powder, and the conditions were a cylinder temperature of 200 ° C and a mold temperature of 10 ° C under a nitrogen atmosphere. A small blow container having a capacity of 50 ml and a weight of 15 g was manufactured by direct blow molding.
[0108]
The resulting small blow container was evaluated for drop test, transparency and environmental disintegration. The results are shown in Table 1.
The small blow container drop test was conducted by leaving a closed small blow container filled with 40 ml of water at a temperature of 23 ° C. for 48 hours, then dropping it at 23 ° C. from a height of 1 m onto a concrete surface, The bottle was observed for rupture or not.
[0109]
The transparency of the small blow container was measured by the Haze value of the side surface (thickness: about 200 μm) of the small blow container.
The environment-disintegrating property of a small blow container is a sample of 5 cm long and 1 cm wide cut from the side of the small blow container, and composted at a temperature of 58 ° C and a moisture content of 60% by weight (components: rice husk, raw garbage, chicken manure, manure) Etc.) and the change was observed after being buried for 3 months.
[0110]
[Example 2]
10 parts by weight of diblock copolymer powder pulverized and powdered from the diblock copolymer (EPR-O-PLa) produced in Production Example 1, polylactic acid (B1) (polystyrene equivalent Mw = 150,000) 60 parts by weight, 30 parts by weight of ethylene / propylene random copolymer (C1) (MFR measured at 190 ° C. = 5.2 g / 10 min, propylene content = 20 mol%) were each well dried in a vacuum dryer. After, Irganox^TM0.110 parts by weight of 1010 was added, and the resin was mixed and pelletized in a 20 mmφ twin screw extruder at a cylinder temperature of 200 ° C. in a nitrogen atmosphere. The obtained pellets were thoroughly dried with a vacuum dryer and then blow-molded in the same manner as in Example 1. The resulting small blow container was measured for drop test, transparency and environmental disintegration. The results are shown in Table 1.
[0111]
[Comparative Example 1]
100 parts by weight of polylactic acid (B1) and Irganox^TMExcept for using 10 parts by weight of 1010, blow molding was performed in the same manner as in Example 1, and the resulting small blow container was measured for drop test, transparency, and environmental disintegration. The results are shown in Table 1.
[0112]
[Comparative Example 2]
67 parts by weight of polylactic acid (B1), 33 parts by weight of ethylene / propylene copolymer (C1) and Irganox^TM1010 0.1 parts by weight were melt-mixed and pelletized in the same manner as in Example 2 and then blow-molded in the same manner as in Example 1. The resulting small blow container had a drop test, transparency and environmental disintegration. It was measured. The results are shown in Table 1.
[0113]
[Table 1]

[0114]
[Example 3]
The diblock copolymer (PP-O-PLa) produced in Production Example 2 was pulverized and powdered, and then thoroughly dried with a vacuum dryer. Irganox was added to 100 parts by weight of the dried diblock copolymer powder.^TM0.110 parts by weight of 1010 was added, and injection molding was performed under conditions of a cylinder temperature of 200 ° C. and a mold temperature of 10 ° C. in a nitrogen atmosphere to form a cup having a capacity of about 30 ml and a weight of 10 g.
[0115]
The obtained cup was evaluated for heat resistance and environmental disintegration. The results are shown in Table 2.
As for the heat resistance of the cup, after leaving the cup at 23 ° C. for 48 hours, put 20 ml of hot water of 70 ° C. in this container and leave it at 23 ° C. for 1 hour to deform the molded body. Visually evaluated.
[0116]
The environmental disintegration property of the cup was measured in the same manner as in Example 1 except that the sample piece was placed in compost (component: rice husk, raw garbage, chicken manure, manure, etc.) at a temperature of 58 ° C. and a water content of 60% by weight. The changes were observed after being buried for months.
[0117]
[Example 4]
10 parts by weight of block copolymer powder obtained by pulverizing and powdering the diblock copolymer (PP-O-PLa) produced in Production Example 2, 60 parts by weight of polylactic acid (B1), propylene / ethylene block copolymer (C2) 30 parts by weight (MFR measured at 230 ° C. = 25 g / 10 min, decane-soluble part = 11.5%) were each well dried in a vacuum dryer, and then Irganox^TM1010 0.1 part by weight was added, and the resin was mixed at a cylinder temperature of 200 ° C. in a nitrogen atmosphere in a 20 mmφ twin screw extruder to be pelletized. The obtained pellets were thoroughly dried with a vacuum dryer, and then injection-molded in the same manner as in Example 3. The resulting cups were evaluated for heat resistance and environmental disintegration. The results are shown in Table 2.
[0118]
[Comparative Example 3]
100 parts by weight of polylactic acid (B1) and Irganox^TMExcept that 0.1 part by weight of 1010 was used, injection molding was carried out in the same manner as in Example 3, and the obtained cup was evaluated for heat resistance and environmental disintegration. The results are shown in Table 2.
[0119]
[Comparative Example 4]
67 parts by weight of polylactic acid (B1), 33 parts by weight of propylene / ethylene block copolymer (C2) and Irganox^TM1010 0.1 parts by weight were melt-mixed and pelletized in the same manner as in Example 4, and then injection-molded in the same manner as in Example 3. The resulting cup was evaluated for heat resistance and environmental disintegration. The results are shown in Table 2.
[0120]
[Table 2]

[0121]
[Reference example 1]
  After 100 parts by weight of the diblock copolymer (A3) produced in Production Example 3 was pulverized and powdered, Irganox was added to the powder.^TM1010 0.1 parts by weight dissolved in acetone was sprayed, stirred well, and dried with a vacuum dryer. This was press-molded under the conditions of a heating temperature of 200 ° C. and a cooling temperature of 20 ° C. to obtain a film having a thickness of 100 μm.
[0122]
The obtained film was evaluated for heat resistance and environmental disintegration. The results are shown in Table 3.
As for the heat resistance of the film, a strip-shaped sample having a width of 2 mm and a length of 2 cm is cut from the film, and TMA (manufactured by Seiko Electronics) is used, and 10 kgf / cm.²A creep test was carried out under a temperature increase condition of 2 ° C./min under a nitrogen stream, and the temperature at which the strain became 5% was defined as the deformation temperature, and the heat resistance was evaluated at this temperature.
[0123]
The environmental disintegration of the film is 3 months in a compost (component: rice husk, raw garbage, chicken manure, manure, etc.) with a temperature of 58 ° C. and a moisture content of 60% by cutting a sample 5 cm long and 1 cm wide from the film. The change was observed after burying.
[0124]
[Reference example 2]
  10 parts by weight of diblock copolymer powder (HDPE-O-PCL) produced in Production Example 3 and pulverized to form powder, polycaprolactone (B2) (polystyrene converted weight average molecular weight Mw = 130) , 000) 60 parts by weight, high density polyethylene (C3) (MFR measured at 190 ° C. = 5.2 g / 10 min, density 0.968 g / cm^Three) After thoroughly drying 30 parts by weight with a vacuum dryer, Irganox^TM1010 0.1 part by weight was added, and the resin was mixed in a 20 mmφ twin screw extruder at a cylinder temperature of 200 ° C. in a nitrogen atmosphere and pelletized. After drying the obtained pellets well in a vacuum dryer,Reference example 1The film thus obtained was press-molded, and the obtained film was evaluated for heat resistance and environmental disintegration. The results are shown in Table 3.
[0125]
[Comparative Example 5]
  100 parts by weight of polycaprolactone (B2) and Irganox^TMExcept for using 0.1 part by weight of 1010,Reference example 1In the same manner as above, a film was formed, and the obtained film was evaluated for heat resistance and environmental disintegration. The results are shown in Table 3.
[0126]
[Comparative Example 6]
  67 parts by weight of polycaprolactone (B2), 33 parts by weight of high-density polyethylene (C3) and Irganox^TM1010 0.1 parts by weightReference example 2In the same manner as above, after melt mixing and pelletizing,Reference example 1Films were molded in the same manner as described above, and the obtained films were evaluated for heat resistance and environmental disintegration. The results are shown in Table 3.
[0127]
[Table 3]

Claims (2)

An environmentally disintegrating resin molded product comprising the olefin block copolymer (A) represented by the following general formula (I);
PO-f-R (I)
(In the formula, PO represents a polyolefin segment composed of a repeating unit derived from an olefin having 2 to 20 carbon atoms, and has a weight average molecular weight of 2,000 or more, f represents an ether bond , and R represents A polylactide segment obtained by a chain polymerization reaction and having a weight average molecular weight of 500 or more is shown.).   An environmental disruption characterized by comprising an olefin polymer composition (C) comprising the olefin block copolymer (A) according to claim 1 and a thermoplastic resin (B) other than the (A). Resin molding.