JP2002275217A - ETHYLENE-alpha-OLEFIN COPOLYMER FOR MODIFYING BIODEGRADABLE RESIN, COMPOSITION THEREOF AND FORMED PRODUCT THEREOF - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene-α-olefin copolymer for modifying biodegradable resin, excellent in flexibility, extrusion processability and calendering workability and generating little heat in incinerating the final products. SOLUTION: This ethylene-α-olefin copolymer for modifying biodegradable resin is made from ethylene and a 3-12C α-olefin and satisfies the following (a) to (d) conditions; (a) α-olefin content is 5-95 wt.%, (b) Mooney viscosity: M1+4 100 deg.C is 5-150, (c) tensile stress M100 is <=8 MPa measured in accordance with JIS-K-6251 and (d) Q value (the ratio of weight-average chain length to number-average chain length) is >=4 measured by GPC.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene-α-olefin copolymer for modifying a biodegradable resin, a composition thereof, and a molded product thereof. More specifically, the present invention, by blending with a biodegradable resin, is excellent in flexibility, extrudability and calender moldability, and can reduce damage to an incinerator due to little heat generation when the final product is incinerated. Ethylene-α-olefin copolymer for biodegradable resin modification, its biodegradable resin composition, and an extruded product obtained by extruding the biodegradable resin composition or obtained by calendering. The present invention relates to a calender molded body to be obtained.

[0002]

2. Description of the Related Art Conventionally, polyethylene, polypropylene,
BACKGROUND ART Thermoplastic resins such as polystyrene, polyethylene terephthalate, and polyvinyl chloride are widely used for packaging materials, food containers, sundries, household appliances, and the like. After use, these products are discarded from homes and factories, but are ultimately discarded on land for refuse disposal and burial, or incinerated at incineration plants.

In recent years, the amount of use of these thermoplastic resins has been greatly increased, and accordingly, the amount discarded from homes and factories has been rapidly increasing, and the shortage of land to be buried around large cities is a serious problem. It has become. Further, when these thermoplastic resins are disposed of in the environment, these thermoplastic resins remain without being decomposed due to their chemical stability,
It causes problems such as spoiling the landscape and polluting the living environment of marine life, and has become a major social problem.
On the other hand, when these thermoplastic resins are incinerated, the generation of harmful outgas can be suppressed by a method of incineration at a high temperature, but this method may shorten the durability of the incinerator due to the generated combustion heat.

In order to solve these problems, biodegradable polymers have attracted attention in recent years. However, since the melt tension at the time of molding is low, the roll release property during calendering,
The shape retention during extrusion was poor, and molding was difficult.

[0005]

Under these circumstances, the problems to be solved by the present invention are excellent in flexibility, extrudability and calendering formability, and the heat generated by incineration of the final product is small. An object of the present invention is to provide a biodegradable resin-modifying ethylene-α-olefin copolymer for obtaining a biodegradable resin composition capable of reducing damage to a furnace, a composition thereof, and a molded article thereof.

[0006]

That is, a first aspect of the present invention is a biodegradable composition comprising ethylene and an α-olefin having 3 to 12 carbon atoms and satisfying the following conditions (a) to (d). It relates to an ethylene-α-olefin copolymer for modifying a reactive resin. (A) α-olefin content is 5 to 95% by weight (b) Mooney viscosity: ML _{1 + 4} 100 ° C. is 5 to 150 (c) Tensile measured according to JIS-K-6251 it can stress M ₁₀₀ is equal to or less than 8 MPa (d) GPC Q value in the measurement (weight average molecular chain length / number average molecular chain length) is 4 or more a second aspect of the present invention, the above-mentioned The present invention relates to a biodegradable resin composition obtained by adding a biodegradable resin to an ethylene-α-olefin copolymer for biodegradable resin modification. Further, the third invention of the present invention relates to an extruded product and a calendered product obtained by extruding or calendering the biodegradable resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of the α-olefin having 3 to 12 carbon atoms of the present invention include propylene, 1-butene,
3-methyl-1-butene, 4-methyl-1-pentene,
Examples include 1-hexene, 1-octene, 1-decene and the like. When the carbon number of the α-olefin is 13 or more, the monomer cost of the α-olefin becomes high, which is inconvenient from the viewpoint of industrial production. 3-12 carbon atoms
Α-olefin may be used singly,
Alternatively, two or more thereof may be used in combination. The α-olefin content in the copolymer of the present invention needs to be 5 to 95% by weight, and preferably, the α-olefin has 3 carbon atoms.
When the carbon number of the α-olefin is 6 to 12, the content is 25 to 40% by weight.
If the α-olefin content is too small, the flexibility of the final product using the copolymer is poor. On the other hand, if the α-olefin content is excessive, the strength of the final product using the copolymer is poor.

The Mooney viscosity (ML) of the copolymer of the present invention
_{(1 + 4} 100 ° C.) must be 5 to 150, preferably 20 to 80. If the Mooney viscosity is too low, bleed will occur on the surface of the final product using the copolymer.
On the other hand, if the Mooney viscosity is too high, the processability of the composition using the copolymer deteriorates.

JIS-K-6251 of the copolymer of the present invention
And tensile stress M ₁₀₀ measured by the compliant must be less than 8 MPa, preferably not more than 4 MPa, more preferably not more than 2.5 MPa, more preferably not more than 2.0 MPa. If the value is excessive, the flexibility of the final product using the copolymer is poor.

In the GPC measurement of the copolymer of the present invention, Q
The value (weight average molecular chain length / number average molecular chain length) needs to be 4 or more, and preferably 6 or more. If the Q value is too small, the extrudability and calenderability of the composition using the obtained copolymer will deteriorate. Further, as long as the constitutional requirements of the present invention are met, it is preferable that the Q value is large in terms of extrusion workability and calenderability. The Q value is measured by a gel permeation chromatography (GPC) method (for example, 150C / GPC apparatus manufactured by Waters). The elution temperature is 140 ° C., and the column used is, for example, Shodex Packed Column manufactured by Showa Denko KK
A-80M, a molecular weight standard substance uses polystyrene (for example, Tosoh Corporation, molecular weight 68-8,400,000). The obtained polystyrene equivalent weight average molecular weight (M
w), the number average molecular weight (Mn), and this ratio (Q value) are defined as the molecular weight distribution. The measurement sample contains about 5 mg of polymer 5
dissolved in o-dichlorobenzene of about 1 mg / ml
Concentration. 400 μl of the obtained sample solution was injected, and the elution solvent flow rate was 1.0 ml / min.
And it is detected by the refractive index detector.

[0011] The copolymer of the present invention comprises the above (a) to (d)
And an ethylene-α-olefin copolymer satisfying the following condition (e):
-More preferably, it is an olefin copolymer. (E) The molecular weight distribution curve shows two or more peaks

When the molecular weight distribution curve of the copolymer of the present invention has one peak, the broadening of the molecular weight distribution is insufficient, and a molded article molded using the obtained composition using the copolymer is used. Extrudability, especially extruded skin, and calenderability may deteriorate. Examples of the number of peaks in the molecular weight distribution curve of the copolymer of the present invention include two (bimodal), three (trimodal), and four (tetramodal).

From the viewpoint of improving the flexibility of a molded article molded using the obtained biodegradable composition, the density of the copolymer of the present invention at 23 ° C. should be 0.90 g / cm ³ or less. Is preferable, and more preferably 0.89 / cm
³ or less, more preferably 0.88 / cm ³ or less, and particularly preferably 0.87 g / cm ³ or less.

The copolymer of the present invention comprises the following component (A):
(C) In the presence of a catalyst system obtained by combining the components as described below, ethylene and α
-It can be produced by subjecting an olefin to polymerization. In addition, it is also possible to use three or more polymerization tanks as long as they meet the constitutional requirements of the present invention.

The component (A) is represented by the general formula VO (OR)
_n X _3-n (where R is a hydrocarbon group, X is a halogen, 0 ≦ n
≦ 3) can be used, and VOCl ₃ , VO (OCH ₃ ) Cl ₂ , VO (OC
H ₃ ) ₂ Cl, VO (OCH ₃ ) ₃ , VO (OC ₂ H ₅ ) Cl
₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (OC ₂ H ₅ ) ₃ , VO
(OC ₃ H ₇ ) Cl ₂ , VO (OC ₃ H ₇ ) ₂ Cl, VO (O
_{C 3 H 7) 3, VO} (Oiso-C 3 H 7) Cl 2, VO (O
_{iso-C 3 H 7) 2} Cl, VO (Oiso-C 3 H 7) 3,
_{VO (On-C 4 H 9} ) Cl 2, VO (On-C 4 H 9) 2 C
_{l, VO (On-C 4} H 9) 3, or it can be exemplified mixtures thereof. Among these, those other than VOCl ₃ can be easily obtained by reacting VOCl ₃ with alcohol or reacting VOCl ₃ with VO (OR) ₃ .

The component (B) is represented by the general formula R '_mAlX
_3-m(Where R ′ is a hydrocarbon group, X is a halogen, 0 ≦ m
≦ 3)
And (C_TwoH_Five)_TwoAlCl, (C_FourH₉)_TwoAlC
l, (C₆H₁₃)_TwoAlCl, (C _TwoH_Five)_1.5AlC
l_1.5, (C_FourH₉)_1.5AlCl_1.5, (C₆H₁₃)_1.5A
lCl_{1. Five}, C_TwoH_FiveAlCl_Two, C_FourH₉AlCl_Two, C₆H
₁₃AlCl_TwoEtc. can be exemplified.

Although it is possible to obtain the copolymer of the present invention by using a catalyst system comprising only the components (A) and (B), the following will be described in order to further reduce the amount of low molecular weight components that bleed. The component (C) may be used in combination.

As the component (C), a halogenated ester compound represented by the following general formula can be used. (However, R ″ is an organic group having 1 to 20 carbon atoms and is partially or completely halogen-substituted, and R ′ ″ is a hydrocarbon group having 1 to 20 carbon atoms). Compounds, more preferably perchlorcrotonates, are very effective. Specifically, ethyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, methyl dichlorophenyl acetate, ethyl dichlorophenyl acetate, methyl perchlorocrotonate, ethyl perchlorcrotonate,
Examples thereof include propyl perchlor crotonate, isopropyl perchlor crotonate, butyl perchlor crotonate, cyclopropyl perchlor crotonate, and phenyl perchlor crotonate.

The molar ratio of the organoaluminum compound (B) to the vanadium compound (A) in the polymerization reaction is 2.5 or more, and the molar ratio of the halogenated ester compound (C) to the vanadium compound (A) is Must be at least 1.5.

The copolymer of the present invention may use a known Ziegler-Natta type catalyst or a known single-site catalyst (such as a metallocene catalyst) alone or in combination with a plurality of the above catalyst systems,
In addition, it can be produced using one or two or more polymerization tanks. From the viewpoint of uniformity of the composition distribution of the obtained polymer, known single-site catalysts (such as metallocene-based catalysts) are preferable. Examples of the site catalyst include, for example, JP-A-58-19309 and JP-A-6-19309.
0-35005, JP-A-60-35006, JP-A-60-35007, JP-A-60-35
008, JP-A-61-130314, JP-A-3-1630088, JP-A-4-268307, JP-A-9-12790, and JP-A-9-873
No. 13, JP-A-10-508055, JP-A-11-80233, JP-T-10-508055, etc., metallocene-based catalysts, JP-A-10-31
6710, JP-A-11-100394, JP-A-11-80228, JP-A-11-80227
JP-A-10-513489, JP-A-10-513489
Non-metallocene complex catalysts described in JP-A-338706 and JP-A No. 11-71420 can be exemplified. Among these, metallocene catalysts are generally used, and among them, preferred metallocene catalysts are exemplified. Examples include a cyclopentadiene-type anion skeleton having at least one
From the viewpoint of the flexibility of the obtained polymer, a transition metal complex of Groups 3 to 12 of the periodic table having a C ₁ symmetric structure is preferred. Further, as an example of a preferable production method using a metallocene catalyst for obtaining a polymer having a high molecular weight, an olefin polymerization catalyst using the following (α) and the following (β) and / or (γ) In the presence of
A method obtained by copolymerizing ethylene and an α-olefin can be exemplified. (Α): at least one of transition metal complexes represented by the following general formulas [I] to [III] (In the above general formulas [I] to [III], M 1 represents a transition metal atom of Group 4 of the periodic table of the element, A represents an atom of Group 16 of the periodic table of the element, and J represents Xp represents an atom belonging to the 14th group of the periodic table of elements, and Cp1 represents a group having a cyclopentadiene-type anion skeleton.
1, R2, R3, R4, R5 and R6 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a disubstituted amino group. Is shown. X
3 represents an atom belonging to Group 16 of the periodic table of the elements. R1, R
2, R3, R4, R5 and R6 may be arbitrarily combined to form a ring. Two M1, A, J, Cp1, X1, X2, X
3, R1, R2, R3, R4, R5 and R6 may be the same or different. (Β): One or more aluminum compounds selected from the following (β1) to (β3) (β1) Organoaluminum compound represented by general formula E1aAlZ3-a (β2) General formula ｛-Al (E2) -O- Cyclic aluminoxane having a structure represented by｝ b (β3) General formula E3 ｛-Al (E3) -O-｝ cAlE3
Linear aluminoxane having a structure represented by 2 (provided that E1, E2 and E3 are each a hydrocarbon group, and all E1, all E2 and all E3 may be the same or different Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more, and c is 1 (Γ): boron compound of any of the following (γ1) to (γ3): (γ1) boron compound represented by general formula BQ1Q2Q3, (γ2) general formula G + (BQ1Q2Q3Q4)- A boron compound represented by (γ3) a boron compound represented by the general formula (LH) + (BQ1Q2Q3Q4)-(where B is a boron atom in a trivalent valence state;
1 to Q4 are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different.
G + is an inorganic or organic cation, L is a neutral Lewis base, and (LH) + is a Bronsted acid. )

Examples of the inert hydrocarbon medium used for preparing the catalyst include propane, butane, pentane, and the like.
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; ethylene chloride and chlorin Examples thereof include halogenated hydrocarbons such as benzene and dichloromethane, and mixtures thereof. The preparation temperature is usually -100 to
The temperature is preferably in the range of 250 ° C., and the pressure and time can be arbitrarily set.

The polymerization of the copolymer of the present invention is carried out in a hydrocarbon solvent. As the hydrocarbon solvent, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclohexane, methylcyclopentane, cycloaliphatic hydrocarbons such as methylcyclohexane, benzene, toluene, Examples include aromatic hydrocarbons such as xylene. Further, α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene and the like can be used as a part or all of the solvent. The polymerization temperature is preferably from 40 to 160 ° C.,
40-80 degreeC is more preferable from a viewpoint of molecular weight control.

The polymerization is carried out at atmospheric pressure or under pressure using one polymerization tank or two polymerization tanks in series.
It is preferably carried out at 1 to 5 MPa, particularly 0.1 to 2 MPa.
Preferably between MPa. The average residence time of the reaction liquid per polymerization tank is preferably 2 to 180 minutes, more preferably 20 to 120 minutes. The polymer concentration is preferably 15% by weight or less, more preferably 12% by weight or less, from the viewpoint of reducing the viscosity of the reaction solution.

The control of the molecular weight of the copolymer of the present invention is exemplified by hydrogen, diethylamine, aryl chloride pyridine-N-oxide and the like, and hydrogen is particularly preferred.

When two polymerization tanks are used, the temperature and molecular weight regulator of the first and second polymerization tanks can be arbitrarily set so as to satisfy the constitutional requirements of the present invention. It is preferable to synthesize the polymer and polymerize the low molecular weight polymer in the second tank, and the polymerization temperature in the first tank is preferably 40 to 60 ° C, and the polymerization temperature in the second tank is preferably 50 to 80 ° C. If the polymerization temperature in the first tank is too high, the molecular weight of the high molecular weight polymer may be insufficient, and if the polymerization temperature in the second tank is too low, it becomes necessary to use a large amount of the molecular weight regulator, which is not preferable. .

On the other hand, the molecular weight regulator can be added to either or both of the first and second tanks. However, by reducing the amount used in the first tank and increasing the amount used in the second tank, it is sufficient. It is preferable because a high molecular weight polymer and a low molecular weight polymer can be polymerized.

The ratio of the amount of copolymer produced in the first and second tanks is preferably in the range of 2.0 / 0.05 to 1 / 2.5. Furthermore, more preferable results can be obtained by performing the process in the range of 2.0 / 0.1 to 2 / 1.5.

A method is also conceivable in which a copolymer satisfying the same structural requirements as the copolymer obtained by the above-described method is synthesized by blending separately synthesized polymers.

However, it is possible to simultaneously polymerize and blend a high molecular weight polymer and a low molecular weight polymer by using the above-mentioned catalyst system consisting of a known Ziegler-Natta type catalyst or a known single-site catalyst in combination (hybrid). It is a method suitable for mass production. In this case, a plurality of polymerization tanks are not necessarily required, and there is no problem even if one polymerization tank is used.

When the copolymer of the present invention is used as a polyolefin-based resin modifier, it is preferably in the form of pellets.

The shape of the copolymer pellet is spherical,
Examples include a columnar shape, a lens shape, and a cubic shape.
These can be produced by a known pelletizing method.For example, after the copolymer is uniformly melt-mixed and extruded by an extruder, a spherical shape is obtained by hot cutting or strand cutting.
A columnar or lenticular pellet is obtained. In this case, the cutting may be performed underwater or in an air stream such as air. The cubic pellets can be obtained, for example, by uniformly mixing, molding into a sheet by a roll or the like, and using a sheet pelletizing machine. As the size, the length of the longest part of the pellet is preferably 3 cm or less. In the case of pellets having a size exceeding this, the weighing error may increase.

The copolymer pellets are obtained by powdering one or more of calcium stearate, calcium carbonate, barium sulfate, silica, talc, stearic acid and polyolefin powder on the surface of the pellets. This is preferable from the viewpoint of further suppressing cohesion or suppressing the bridging phenomenon of the pellet when the pellet is taken out from a silo or the like. The powdered amount may be added in a required amount according to the size and shape of the pellet, but it is usually preferable to add 0.05 to 3 parts by weight to the copolymer pellet. If the addition amount is too small, the effect of further suppressing cohesion cannot be exerted, and if it is too large, physical properties and the like are lowered and production costs are increased. In particular, when transparency of the end product to be obtained is important, it is preferable to use polyolefin powder. Examples of polyolefin powder include polyethylene resin and polypropylene resin powder.

The average particle size of the polyolefin powder is preferably not more than 500 μm, particularly preferably not more than 300 μm. If the particle size is too large, it may not be able to adhere to the pellet surface, and the effect of improving cohesion may not be obtained.

At the time of producing the copolymer pellets, a nucleating agent, a clarifying agent, a heat stabilizer, an ultraviolet stabilizer,
A weathering stabilizer, a foaming agent, an antifogging agent, an antirust agent, an ion trapping agent, a flame retardant, a flame retardant auxiliary, an inorganic filler, an organic pigment, an inorganic pigment, a lubricant, and the like can be added. Furthermore, polyethylene resins, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, -Vinyl acetate copolymer, ethylene-styrene copolymer, polypropylene resin, polybutene-1, petroleum resin, ethylene-propylene-nonconjugated diene copolymer rubber, polybutadiene, styrene-butadiene block copolymer rubber, styrene- Butadiene-styrene block copolymer rubber, styrene-butadiene random copolymer rubber, partially hydrogenated styrene-butadiene-styrene block copolymer rubber, partially hydrogenated styrene-butadiene random copolymer rubber, styrene-isoprene block copolymer Combined rubber, partially hydrogenated styrene-isoprene blow It can be added a resin or rubber such as click copolymer rubber.

Next, the biodegradable resin composition derived from the novel ethylene-α-olefin copolymer for modifying biodegradable resin in the present invention will be described. The biodegradable resin composition of the present invention comprises (a) 5 to 95 parts by weight of the ethylene-α-olefin copolymer for modifying the biodegradable resin of the present invention and (b) 5 to 95 parts by weight of the biodegradable resin. And a biodegradable resin composition comprising: More preferably, (a) 10
To 90 parts by weight and (b) 10 to 90% by weight, and more preferably (a) 20
It is a biodegradable resin composition comprising from 80 to 80 parts by weight and (b) from 20 to 80% by weight. (A) is too large ((b) is too small)
In some cases, the resulting biodegradable resin composition may be inferior in biodegradability and low heat build-up during incineration, while the biodegradable resin obtained when (b) is excessive ((a) is too small) The effect of improving the extrusion processability and calenderability of the composition may be insufficient.

The component (b) used in the biodegradable resin composition of the present invention is a biodegradable resin. (B) can be selected from a wide variety of known biodegradable resins, starch biodegradable resins, corn starch biodegradable resins,
Selected from microbial biodegradable resin, succinic polyester biodegradable resin, polyesteramide biodegradable resin, polycaprolactone biodegradable resin, cellulose acetate biodegradable resin, polylactic acid biodegradable resin It is preferable to contain at least one or more components.

In the present invention, additives such as antioxidants, antistatic agents, weathering agents, ultraviolet absorbers, coloring agents, dispersants, lubricants, etc. Colorants such as glass fiber, carbon fiber, metal fiber, aramid fiber, glass beads, filler such as asbestos, mica, calcium carbonate, potassium titanate whisker, talc, barium sulfate, glass flake, or other rubbery materials A united material, a thermoplastic resin, or the like can be appropriately blended.

Examples of the lubricant include waxes, higher alcohols, fatty acids, fatty acid metal salts, fatty acid amides, carboxylic acid esters, phosphoric acid esters, sulfonic acid metal salts, acid ester metal salts, acrylic resins, fluorine-containing resins, and silicones. And the like, and two or more kinds may be used in combination.

Examples of waxes include petroleum wax such as paraffin wax and microcrystalline wax, vegetable wax such as rice wax, mineral wax such as montan wax, polyethylene wax,
Examples include synthetic waxes such as low molecular weight polypropylene.

As higher alcohols, lauryl alcohol, myristyl alcohol, palmityl alcohol,
Examples include stearyl alcohol, behenyl alcohol, oleyl alcohol, erucyl alcohol, and 12 hydroxystearyl alcohol.

Examples of the fatty acid include lauric acid, palmitic acid, stearic acid, behenic acid, oleic acid, erucic acid, linoleic acid and ricinoleic acid.

Examples of the metal salts of fatty acids include fatty acids such as lauric acid, palmitic acid, stearic acid, behenic acid, oleic acid, erucic acid, linoleic acid, and ricinoleic acid.
Salts of metals such as a, Mg, Al, K, Ca, Zn, Ba, and Pb, specifically, lithium stearate, sodium stearate, calcium stearate, and zinc stearate can be exemplified.

Examples of the fatty acid amide include lauric amide, palmitic amide, stearic amide, oleic amide, erucamide, methylenebisstearic amide, ethylenebisstearic amide, ethylenebisoleic amide, stearyldiethanolamide and the like. Can be exemplified.

Examples of the carboxylic acid esters include aliphatic carboxylic acids such as acrylic acid, crotonic acid, isocrotonic acid, fumaric acid, maleic acid, succinic acid, and aconitic acid.
Fatty acids such as lauric acid, palmitic acid, stearic acid, behenic acid, oleic acid, erucic acid, linoleic acid, ricinoleic acid, carboxylic acids such as lactic acid, malic acid, tartaric acid, oxycarboxylic acids such as citric acid, and myristyl alcohol; Aliphatic alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol and 12 hydroxystearyl alcohol, aromatic alcohols such as benzyl alcohol, β-phenylethyl alcohol and phthalyl alcohol, glycerin, diglycerin, polyglycerin, sorbitan, sorbitol, propylene Glycol, polypropylene glycol, polyethylene glycol, pentaerythritol, esters with alcohols such as polyhydric alcohols such as trimethylolpropane, etc. Glycerol monooleate, glycerol dioleate, polyethylene glycol monostearate, distearate and citric acid can be exemplified in the.

Examples of the phosphoric acid ester include a monoalkyl ester, a dialkyl ester and a trialkyl ester of phosphoric acid and a higher alcohol, and specific examples thereof include AX-1 manufactured by Asahi Denka Kogyo.

As the acrylic resin, acrylic acid, methyl acrylate, ethyl acrylate butyl acrylate,
Specific examples include acrylates such as acrylate-2-ethylhexyl, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and polymers mainly containing methacrylates such as methacrylate-2-ethylhexyl. Examples include Metabrene manufactured by Mitsubishi Rayon and Kane Ace manufactured by Kanegafuchi Chemical Industry.

Examples of the metal sulfonic acid salt include sodium stearyl sulfonate, sodium lauryl sulfonate,
Sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate, potassium stearylsulfonate, potassium laurylsulfonate, dibutylsodium sulfosuccinate, di-2-ethylhexylsodium sulfosuccinate, disodium lauryl sulfosuccinate, disodium lauryl polyoxyethylene sulfosuccinate And the like.

Examples of the acid ester metal salts include sulfates such as sodium lauryl sulfate and potassium lauryl sulfate, and phosphates such as sodium lauryl phosphate and potassium lauryl phosphate.

Examples of the fluorine-containing resins include fluorine-containing olefins such as tetrafluoroethylene, hexafluoropropylene, fluoroalkylethylene and perfluoroalkylvinyl ether, and fluorine-containing alkyl acrylates such as perfluoroalkylene acrylate and perfluoromethalkylene acrylate. Examples of a polymer having a main unit of a fluorinated monomer such as a fluorine alkyl methacrylate, specifically, polytetrafluoroethylene, perfluoro (polyoxypropylene ethyl ether) and the like can be given.

Examples of the silicones include polymers having a siloxane derivative such as dimethylsiloxane, methylphenylsiloxane and diphenylsiloxane as a main unit.
Specific examples include polydimethylsiloxane and polymethylphenylsiloxane.

Other rubbery polymers or thermoplastic resins include polyethylene resins, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, and ethylene- (meth) acrylate copolymers. , Saponified ethylene-vinyl acetate copolymer, ethylene-styrene copolymer, polypropylene resin, polybutene-1, petroleum resin, ethylene-propylene-nonconjugated diene copolymer rubber, polybutadiene, styrene-butadiene block copolymer Rubber, styrene-butadiene-styrene block copolymer rubber, styrene-butadiene random copolymer rubber, partially hydrogenated styrene-butadiene-styrene block copolymer rubber, partially hydrogenated styrene-butadiene random copolymer rubber, styrene Isoprene block copolymer rubber, partially hydrogenated polystyrene - it can be exemplified isoprene block copolymer rubber.

Among them, from the viewpoint of improving the compatibility between the copolymer according to the present invention and the biodegradable resin, a polar group-containing rubbery polymer or a thermoplastic resin is used as another rubbery polymer or a thermoplastic resin. Preferably, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene-styrene copolymer, Examples include petroleum resins.

The biodegradable resin composition of the present invention comprises (a)
(B) and other additional components may be kneaded using a conventional kneading apparatus, for example, a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a twin-screw extruder, or the like. The kneading device may be any of a closed type and an open type, but a closed type device which can be replaced with an inert gas is preferable. The kneading temperature is a temperature at which all of the mixed components are melted, and usually,
It is 80-250 degreeC, Preferably it is 100-240 degreeC. The kneading time depends on the type and amount of the constituent components mixed and the type of the kneading device, and is therefore not generally discussed.However, when using a kneading device such as a pressure kneader or a Banbury mixer, the mixing time is usually , About 3 to 10 minutes. In the kneading step, each component may be kneaded at a time. Alternatively, after kneading some components, the remaining components are added to continue the kneading. A kneading method can also be adopted.

The biodegradable resin composition of the present invention is particularly excellent as a material for extrusion molding, and is melt-extruded from an extruder in which a mold in the shape of a molded product is attached to the tip of the extruder, and cooled.
By cutting, a shaped extruded product can be obtained. In addition, a sheet or film-like extruded body can be obtained by inflation processing or T-die casting processing.

Further, the biodegradable resin composition of the present invention is particularly excellent as a material for calender molding, and is a sheeting process for continuously producing a smooth sheet having high thickness accuracy.
A doubling process for continuously producing sheets having high thickness accuracy without pinholes in laminating the same or different thermoplastic elastomer compositions and thermoplastic resin compositions,
A topping process of laminating a cloth or the like on a sheet to continuously form a composite, a friction process of rubbing a thermoplastic elastomer composition into a cloth for the purpose of improving adhesiveness, applying an engraving pattern to the roll surface, and applying that pattern to the sheet surface A calender molded body can be obtained by a profiling process in which the calender molding is performed.

The molded article obtained from the biodegradable resin composition of the present invention can be used for packaging materials (film, sheet, bottle,
Cups, trays, can carriers, etc.), agricultural materials (agricultural films, binding tapes, etc.), consumer materials (diaper backsheets, shopping bags, garbage bags, etc.), as well as toners and inks used in copying machines, etc. Containers and hoses, tubes, gaskets for transportation and storage of cosmetics, paints, foodstuffs, etc.
It can be used for various uses such as packing, mats and labels.

[0057]

The following examples further illustrate the present invention, but are by way of illustration and should not be construed as limiting the invention. [I] Production and evaluation of component (a) The measurement was performed as follows. (1) GPC measurement The GPC apparatus was 150C manufactured by Waters, the elution temperature was 140 ° C, and the column used was Shodex manufactured by Showa Denko KK
Packed Column A-80M, molecular weight standard substance is polystyrene (for example, Tosoh Corporation, molecular weight 68
-8,400,000). The obtained polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (M
n), and this ratio (Q value = Mw / Mn) was taken as the molecular weight distribution. The measurement sample was prepared by adding about 5 mg of polymer to 5 ml of o-
Dissolve in dichlorobenzene to a concentration of about 1 mg / ml. 400 μl of the obtained sample solution was injected, and the elution solvent flow rate was set to 1.0 ml / min, and detected by a refractive index detector. (2) Tensile stress samples were press-molded at 0.99 ° C., after obtaining a 2mm thick sheet, conforming to JIS-K-6251, were measured tensile stress M ₁₀₀ of the copolymer. A dumbbell-shaped No. 3 test piece was used. (3) Mooney viscosity The Mooney viscosity of the copolymer: ML1 + 4100 ° C. was measured in accordance with JIS-K-6300.

Example 1 (Synthesis of Component (A)) Hexane was used as a polymerization solvent from a lower part of a 100-L stainless steel polymerization tank equipped with a stirrer at 62.8 K / h.
g, ethylene and propylene each at 5.90 kg / h, 2
Feed continuously at a rate of 2.44 Kg. V as catalyst
O (Oiso-C ₃ H ₇ ) ₃ , ethyl aluminum sesquichloride (EASC) 2.22 g / hr, 7.7
The mixture was continuously supplied at a rate of 9 g, and the temperature of the polymerization tank was maintained at 50 ° C. A part of the polymerization solution in the first tank was withdrawn, and the polymer was precipitated by steam stripping. After drying, 600 ppm of Irganox 1076 (an antioxidant manufactured by Ciba Specialty Chemicals) was added, and the mixture was granulated by an underwater cut method. By doing so, an ethylene-propylene copolymer pellet was obtained. In this way, 4.6 kg of an hourly copolymer was obtained. The molecular weight was adjusted with hydrogen. as a result,
Propylene content 27.6% by weight, Mooney viscosity: ML1 +
4100 ° C. = 40.9, Q value in GPC measurement = 6.
6. Ethylene-propylene copolymer pellets for modifying biodegradable resin were obtained, which had a tensile stress M ₁₀₀ = 1.1 MPa and showed a bimodal molecular weight distribution curve.

[0059]

As described above, by blending with the biodegradable resin according to the present invention, the incinerator has excellent flexibility, extrudability and calender moldability, and generates little heat when the final product is incinerated. A biodegradable resin-modifying ethylene-α-olefin copolymer, which can reduce damage to a biodegradable resin, a biodegradable resin composition thereof, and an extruded product obtained by extruding the biodegradable resin composition or A calender molded article obtained by calender molding can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 101/16 C08L 101/16 // B29K 23:00 B29K 23:00 B29L 7:00 B29L 7: 00F term (reference) 4F071 AA09 AA15X AA20X AA44 AA76 AA80 AA88 AH05 AH12 AH19 BA01 BC01 BC04 BC05 4F204 AA03E AA04E AA08K AA11E AA24K AA49K AG01 FA06 FB02 FF01 FF21 4F207 AA03A AA03C AA03E AA11E AA24K AG01 AG08 KA01 KA11 KA17 4J002 AB02X AB04X BB05W CF03X CF18X CF19X CL08X FD010 FD170 GC00 GG01 GG02 GQ00 4J100 AA02P AA03Q AA04Q AA09Q AA15Q AA16Q AA17Q AA19Q AA21Q CA04 DA01 DA09 DA51 JA43 JA57 JA58

Claims (8)

[Claims] 1. An ethylene-α-olefin copolymer for modifying a biodegradable resin, comprising ethylene and an α-olefin having 3 to 12 carbon atoms and satisfying the following conditions (a) to (d). (A) α-olefin content is 5 to 95% by weight (b) Mooney viscosity: ML _{1 + 4} 100 ° C. is 5 to 150 (c) Tensile measured according to JIS-K-6251 it can stress M ₁₀₀ is equal to or less than 8 MPa (d) Q value in the GPC measurement (weight average molecular chain length / number average molecular chain length) is 4 or more 2. The ethylene-α-olefin copolymer for modifying a biodegradable resin according to claim 1, which satisfies the conditions (a) to (d) according to claim 1 and the following condition (e). (E) The molecular weight distribution curve shows two or more peaks 3. It contains the following (a) to (b), the content of (a) is 5 to 95 parts by weight, and the content of (b) is 5 to
A biodegradable resin composition which is 95 parts by weight. (A): ethylene for modifying the biodegradable resin according to claim 1;
α-olefin copolymer (b): biodegradable resin 4. The method according to claim 3, wherein (b) is a starch biodegradable resin, a corn starch biodegradable resin, a microbial biodegradable resin, a succinic polyester biodegradable resin,
A biodegradable resin composition containing at least one component selected from a polyesteramide-based biodegradable resin, a polycaprolactone-based biodegradable resin, a cellulose acetate-based biodegradable resin, and a polylactic acid-based biodegradable resin. 5. An extruded product obtained by extruding the biodegradable resin composition according to claim 3. 6. A hose, tube, gasket, packing, sheet or film obtained from the molded product according to claim 5. 7. A calender molded article obtained by subjecting the biodegradable resin composition according to claim 3 to calender molding. 8. A sheet or film obtained from the molded article according to claim 7.