JPH09100395A - Oil adsorbing aliphatic polyester composition and oil adsorbing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aliphatic polyester composition having a low wetting index, biodegradability and superior oil absorbency, heat stability, mechanical strengths, etc., by compounding a specified aliphatic polyester and a wax. SOLUTION: A prepolymer of an aliphatic polyester is produced by using mainly an aliphatic glycol (e.g. ethylene glycol) and an aliphatic dicarboxylic acid (e.g. adipic acid). Then, this prepolymer is subjected to deglycolation reaction to produce an aliphatic polyester with a molecular weight of not less than 40,000. Then, 100 pts.wt. this aliphatic polyester is blended with 0.1-5 pts.wt. of a wax selected from a synthetic wax, natural wax with a number average molecular weight of not more than 10,000 and a mixture of them to obtain an aliphatic polyester composition with a wetting index of not more than 38dyne/cm. Then, 100 pts.wt. composition is blended with 0.2-5 pts.wt. blowing agent and the mixture is molded by extrusion foaming and stretching at 150-220 deg.C to prepare an oil adsorbing foamed open fiber article.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a biodegradable composition,
Fatty polyester composition that adsorbs oil, foam opener for adsorbing oil, foam opener mat for adsorbing oil, and foam opener for adsorbing oil useful as a material for oil fences with excellent oil adsorbability and buoyancy Body sheet laminates.

[0002]

2. Description of the Related Art In recent years, such as the spillage of crude oil due to marine accidents such as grounding and sinking of tankers, the recovery of oil spilled into the sea such as spillage from oil tanks, the removal of liquid oily hazardous suspended matter from rivers, etc. Oil-adsorbing polypropylene for processing,
An oil-adsorptive mat using a foam-opening material such as polyethylene is used. These oil adsorbents are post-treated as plastics after use, and because they are contaminated with oil, there is a problem in recycling.For example, incineration is necessary, and if they are discarded as they are, they will contaminate rivers, oceans, and soil. This post-treatment has become an important issue in terms of cost, and development of a biodegradable plastic has been desired to prevent contamination.

As a biodegradable plastic,
For example, poly (3-hydroxybutyrate) produced by a fermentation method, a blend of starch and polyethylene, which are natural polymers, and the like are known. However, the former has a problem that the melting point of the polymer and the thermal decomposition temperature are close to each other, and the processability of a molded article such as a foamed molded article is poor.
In the latter case, since starch itself is not thermoplastic, there is a problem in molding processability, which greatly restricts the range of use. On the other hand, aliphatic polyester has been known to have biodegradability, but it has hardly been used because a polymer having a high molecular weight sufficient to obtain physical properties as a practical molded product cannot be obtained. Recently, ε-caprolactone was found to have a high molecular weight by ring-opening polymerization and has been proposed as a biodegradable resin, but it has a melting point of 6
The temperature is as low as 2 ° C, which increases the cost of raw materials, so it is limited to very special applications. Glycolic acid, lactic acid, etc. are also used in medical fibers, etc., because a high molecular weight polymer is obtained by ring-opening polymerization of glycolide or lactide, and this polymer also has a melting point and a decomposition temperature close to each other. These polymers have not been used in large quantities as plastic materials because of their workability defects.

Recently, a melting point of 70 ° C. has been obtained by a polycondensation reaction using an aliphatic glycol and an aliphatic dicarboxylic acid as main raw materials.
A biodegradable high molecular weight aliphatic polyester having the above melting point and a method for producing the same are disclosed in US Pat. No. 5,306,787.
No. 5 (polymerization), No. 5,310,782 (polycondensation catalyst) and No. 5,436,056 (long-chain branched structure). Further, the invention relating to the foam spreader of these aliphatic polyesters is disclosed in US Pat.
No. 2,765. The aliphatic polyester produced by the polycondensation method is excellent in moldability, has a degree of openness when formed into a foamed open body, has a good texture, and is biodegradable by microorganisms in soil, sandy soil and sea. It was possible to produce a possible foam opening. However, the foam-opened body thus obtained does not always have sufficient adsorbability of oil, and has a drawback that it becomes difficult to adsorb oil particularly when it is brought into contact with water or seawater in advance.

[0005]

DISCLOSURE OF THE INVENTION The present invention uses a biodegradable aliphatic polyester as a raw material, and does not reduce the oil adsorbability even when it is previously contacted with water. Provided are a polyester composition, a foam-opening body for adsorbing oil, a foam-opening mat for adsorbing oil, and a foam-opening sheet laminate for adsorbing oil, which is capable of floating and adsorbing oil on water. The purpose is to do.

[0006]

The present inventors have made it possible to incorporate a small amount of waxes into an aliphatic polyester,
It has been found that the surface of the aliphatic polyester is made lipophilic while maintaining biodegradability, and the oil adsorbability can be kept high even when it is first contacted with water or seawater. Further, in the extrusion molding of the foam-opening body for oil adsorption, an aliphatic polyester obtained by mixing an aliphatic polyester having a linear structure with an aliphatic polyester having a long-chain branched structure is suitable, and is manufactured using these aliphatic polyesters. Further, the present invention has completed the aliphatic polyester composition, the foam-opening body for adsorbing oil, the foam-opening body mat for adsorbing oil, and the foam-opening sheet laminate for adsorbing oil.

That is, the present invention is as follows: An aliphatic polyester prepolymer (A) mainly obtained from an aliphatic glycol and an aliphatic dicarboxylic acid is subjected to a deglycol reaction to give a number average molecular weight of 4
Aliphatic polyester (I) of 10,000 or more ...
100 parts by weight and B.I. A synthetic wax having a number average molecular weight of 10,000 or less,
A natural wax or a wax of any of these mixtures, which is comprised of 0.1 to 5 parts by weight and has a wetting index of 38.
an aliphatic polyester composition having a dyne / cm or less, A. Primarily, an aliphatic polyester polyol (B) having a terminal hydroxyl group, which is obtained by subjecting an aliphatic glycol and an aliphatic dicarboxylic acid to an esterification reaction and then a deglycolization reaction, is reacted with a polyfunctional isocyanate to give a number. Aliphatic polyester polyol (II) having an average molecular weight of 40,000 or more ... 100 parts by weight and B. A synthetic wax having a number average molecular weight of 10,000 or less,
Either natural waxes or mixtures thereof
・ ・ ・ 0.1 to 5 parts by weight, wetting index 38 dy
an aliphatic polyester composition having a ne / cm or less,

Or, having a number average molecular weight of 40,
000 or more and a melt flow rate of 10 g / 10
100 parts by weight of an aliphatic polyester composition which is less than or equal to 10 minutes, and a foamed spreader for adsorbing oil, obtained by extrusion foaming and stretching a composition comprising 0.2 to 5.0 parts by weight of a foaming agent at a temperature of 150 to 220 ° C., A foam-opening material for adsorbing oil, which is an aliphatic polyester composition having a number average molecular weight of 60,000 or more, wherein the aliphatic polyester composition has an aliphatic polyester (I) having a linear structure of 95 parts by weight or less, or Polymer selected from aliphatic polyester polyol (II) having a linear structure, and aliphatic polyester (I) having a long-chain branched structure or aliphatic polyester polyol (II) having a long-chain branched structure, 100 to 5 parts by weight A foamed spreader for adsorbing oil, which is an aliphatic polyester composition comprising

When the amount of B heavy oil adsorbed is 20 ° C.,
It is 4 times or more of its own weight. Any one of the following foam-opening bodies for oil-adsorption, or any one of the foam-opening bodies for oil-adsorption is cut into an appropriate size, and a plurality of these are laminated, and at least 2 A foam opening mat for adsorbing oil, in which points are heated and fused,
When laminating the foam spreader for oil adsorption, foaming ratio 2 to
40 times, density 0.6 to 0.03 g / cm ³ , thickness 1 to 5
The above-mentioned problems have been solved by developing a foam open sheet sheet laminate for adsorbing oil, in which a foam sheet of 0 mm or an aliphatic polyester composition is laminated.

The contents of the present invention will be described in detail below. The aliphatic polyester used in the present invention can be manufactured into a linear structure by the method disclosed in US Pat. Nos. 5,306,787 and 5,310,782. Further, by the method disclosed in US Pat. No. 5,436,056, or by reacting a linear structure aliphatic polyester which is an aliphatic polyester polyol having a terminal hydroxyl group with a polyfunctional isocyanate having a functionality of 3 or more. A long chain branched structure can be manufactured.

That is, the aliphatic polyester used in the present invention comprises (1) an aliphatic (including cycloaliphatic) glycol (2) an aliphatic (including cycloaliphatic) dicarboxylic acid (or an acid anhydride thereof). A small amount of (3) trivalent or higher polyhydric alcohol, trivalent or higher polyvalent oxycarboxylic acid (or acid anhydride thereof) or trivalent or higher polyvalent carboxylic acid (or acid anhydride thereof) The number average molecular weight produced is about 5,0
00 polyester (A) in the presence of a catalyst for 180 to 2
The number average molecular weight obtained by a deglycolization reaction at a temperature of 80 ° C. and a high vacuum of 0.05 to 2 mmHg is 40,0.
The aliphatic polyester (I) produced by polycondensation of 00 or more, preferably 45,000 or more, more preferably 60,000 or more. This aliphatic polyester is
The deglycolization reaction may require a long time of 10 to 30 hours in order to obtain a high molecular weight, in which case the polymer tends to become pale yellow and slightly brittle.

Preferably, the aliphatic polyester used in the present invention is a tough polyester polyol (II) obtained by reacting a small amount of a divalent or higher polyvalent isocyanate with the polyester polyol (B) obtained by a polycondensation reaction.
It is. That is, the present aliphatic polyester comprises (1) an aliphatic (including cycloaliphatic) glycol and (2) an aliphatic (including cycloaliphatic) dicarboxylic acid (or an acid anhydride thereof).
In the presence of a small amount of (3) trivalent or higher polyhydric alcohol, polyhydric oxycarboxylic acid (or acid anhydride thereof) or trivalent or higher polyvalent carboxylic acid (or acid anhydride thereof), or After the number average molecular weight is adjusted to about 5,000 by an esterification reaction in the absence, the number average molecular weight having a hydroxyl group at the end obtained by deglycolization is 20,
000-30,000 aliphatic polyester polyol (B) is further reacted with a divalent or higher polyfunctional isocyanate to obtain a number average molecular weight of about 40,000 or more,
Preferably 45,000 or more, more preferably 60,0
This is a polyester polyol (II) containing 00 or more urethane bonds.

The aliphatic glycol used in the present invention is
For example, ethylene glycol, propylene glycol,
1,4-butadiol, 1,6-hexanediol, decamethylene recall, neopentyl glycol, 1,4
-Cyclohexane dimethanol etc. are mentioned. These aliphatic glycols may be used in combination.

Aliphatic dicarboxylic acids (or acid anhydrides) that react with aliphatic glycols to form aliphatic polyesters include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, succinic anhydride, Adipic anhydride,
Alternatively, lower alcohol esters such as dimethyl ester thereof are generally commercially available and can be used in the present invention. You may use together polybasic acid (or acid anhydride).

Examples of the polyfunctional component used as the third component include trifunctional or tetrafunctional polyhydric alcohols, oxycarboxylic acids and polyvalent carboxylic acids. Trifunctional polyhydric alcohol components include trimethylolpropane,
Glycerin or its anhydride is typical. Pentaerythritol is a typical tetrafunctional polyhydric alcohol component. The trifunctional oxycarboxylic acid component is classified into (i) a type having two carboxyl groups and one hydroxyl group in the same molecule, and (ii) a type having one carboxyl group and two hydroxyl groups. I understand. From the standpoint that commercial products are easily available at low cost, (i)
Malic acid, which shares two carboxyl groups and one hydroxyl group in the same molecule, is practically advantageous and sufficient for the purpose of the present invention.

There are the following three types of tetrafunctional oxycarboxylic acid components. That is, (i) 3 carboxyl groups and 1
Type having two hydroxyl groups in the same molecule (eg citric acid), (ii) type having two carboxyl groups and two hydroxyl groups in the same molecule (eg tartaric acid), (iii) There is a type that shares 3 hydroxyl groups and 1 carboxyl group in the same molecule, and any type can be used, but from the viewpoint that commercial products are easily available at low cost, Citric acid and tartaric acid are practically advantageous and sufficient for the purpose of the present invention.

As the trifunctional polycarboxylic acid (or its anhydride) component, for example, trimesic acid, trimellitic acid, propanetricarboxylic acid and the like can be used, but trimellitic anhydride is advantageous in practical use. Yes, it is sufficient for the purposes of the present invention. There are various types of tetrafunctional polycarboxylic acid (or anhydride thereof) components such as aliphatic, cycloaliphatic, and aromatic in the literature, but from the viewpoint of easy availability of commercially available products, for example, Pyromellitic dianhydride, benzophenone tetracarboxylic acid anhydride, cyclopentane tetracarboxylic acid anhydride are mentioned and are sufficient for the purposes of the invention.

The amount of the polyfunctional component added should be trifunctional with respect to 100 mol% of the total amount of the components of the aliphatic dicarboxylic acid (or its anhydride) in order to prevent gelation risk. 0.1-2 mol%, preferably 0.2-1.
0 mol%, more preferably 0.25 to 0.50 mol%
In the case of tetrafunctionality, it is 0.1 to 1 mol%, preferably 0.1 to 0.5 mol%. When the amount of the trifunctional or tetrafunctional component is less than 0.1 mol%, the effect represented by molding processability is not observed, and the amount of the trifunctional component exceeds 2 mol% or the amount of the tetrafunctional component is If it exceeds 1 mol%, there is a risk that the gel component will increase and the practicality will be greatly reduced.
Further, the added amount varies within this range depending on the intended molding method.

The aliphatic polyester (A) used in the present invention is not limited, but the aliphatic polyester polyol (B) has a terminal group substantially a hydroxyl group,
For that purpose, it is necessary to use the glycols and polybasic acid (or the anhydride thereof) used in the synthetic reaction in an excessive amount, for example, 5 to 10 mol% of the glycols.

In order to synthesize high molecular weight polyester (I) and aliphatic polyester polyol (B), it is necessary to use a deglycolization reaction catalyst in the deglycolization reaction following the esterification. Examples of the deglycolization reaction catalyst include titanium compounds such as acetoacetoyl titanium chelate compounds and organic alkoxy titanium compounds. These titanium compounds can be used in combination. Examples of these include diacetoacetoxyoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetraptoxytitanium and the like. The ratio of titanium compound used is polyester prepolymer 10
It is 0.001 to 1 part by weight, preferably 0.01 to 0.1 part by weight, based on 0 part by weight. The titanium compound may be added from the beginning of the esterification, or may be added immediately before the deglycolization reaction. The deglycolization reaction varies depending on the raw material composition, the number average molecular weight of the desired reaction product, etc., but is generally at a temperature of 180 to 280 ° C. and 0.05 to 2.0.
It can be obtained by carrying out under vacuum such as mmHg.

In the aliphatic polyester polyol (B), a prepolymer having a number average molecular weight of 10,000 or more, preferably 20,000 to 30,000, whose terminal groups are substantially hydroxyl groups, is used. A coupling agent is used to increase the value to 40,000 or more.

To obtain the aliphatic polyester polyol (II) having a linear structure, a divalent diisocyanate is used. The type of diisocyanate is not particularly limited, but examples thereof include the following types. 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate,
Diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. Is preferable from the viewpoint of the hue, the reactivity at the time of adding polyester, and the biodegradability.

The amount of these coupling agents added is 0.1 to 100 parts by weight of the polyester polyol (B).
5 parts by weight, preferably 0.5 to 1.5 parts by weight.
If it is less than 0.1 part by weight, the coupling reaction is insufficient, and if it exceeds 5 parts by weight, gel is likely to occur.

The coupling agent is preferably added under the condition that the polyester polyol (B) is in a uniform molten state and can be easily stirred. It is not impossible to add the coupling agent to the polyester polyol (B) in the kneader and melt, mix, and react through the extruder. Generally, it is practical to add the polyester polyol (B) in a molten state at 180 to 220 ° C. in an aliphatic polyester production apparatus.

To obtain the aliphatic polyester polyol (II) having a long-chain branched structure, a trivalent or higher polyvalent isocyanate is used. 3 for polyvalent isocyanate
Functional isocyanates are preferred. As the trifunctional isocyanate, trimethylolpropane / hexamethylene diisocyanate / adduct, hexamethylene diisocyanate cyclic trimer or hexamethylene diisocyanate / water / adduct is preferably used.

When the polyvalent isocyanate is reacted, the number average molecular weight of the aliphatic polyester polyol (B) is preferably increased in advance to about 40,000 to 45,000. When the amount is less than this value, the polyester polyol (I
It is preferable to avoid I) since it tends to partly gel or the entire plastic becomes rubbery. The amount of polyvalent isocyanate added is usually 0.5 to 2 parts by weight, preferably 0.8 to 1.2 parts by weight.

The aliphatic polyester composition of the present invention includes an aliphatic polyester (I) having a linear structure number average molecular weight of 40,000 or more, or an aliphatic polyester polyol having a linear structure, and a divalent polyfunctional isocyanate. Aliphatic polyester polyol (I having a urethane bond having a number average molecular weight of 40,000 or more, obtained by reacting
I) may be used, but preferably 0 to 95 parts by weight of this linear structure aliphatic polyester, aliphatic glycol, aliphatic dicarboxylic acid and a small amount of trivalent or higher polyhydric alcohol, polyhydric oxycarboxylic acid or polyhydric acid. Aliphatic polyester having a long-chain branched structure obtained by reacting an aliphatic polyester having a long-chain branched structure produced from a carboxylic acid or an aliphatic polyester polyol having a terminal hydroxyl group with a polyfunctional isocyanate having a valence of 3 or more. Is preferable to be blended with 100 to 5 parts by weight of the aliphatic polyester composition. It is preferable to add 60 to 10 parts by weight, more preferably 30 to 50 parts by weight.

The aliphatic polyester composition has a melt flow rate (specified by JIS K7210: measurement temperature 190 ° C., test load 2.16 kgf: hereinafter referred to as MFR) of 10 g / 10 minutes or less, preferably 5%.
˜0.5 g / 10 min, more preferably 2-1 g / 10 min. In this aliphatic polyester composition, the melt tension is related to the physical properties related to the production of the foam spreader, in addition to MFR. Usually, an aliphatic polyester having a linear structure has a low melt tension, and bubbles are likely to burst during foam molding, which makes it difficult to manufacture a foam-opening body. On the other hand, the aliphatic polyester having a long-chain branched structure has a high melt tension, and therefore both of them can be blended to improve this difficulty.

The waxes that can be used in the present invention are synthetic waxes, natural waxes and mixed waxes of them. In particular, synthetic wax synthesized from petroleum is preferable because it has a large effect of imparting lipophilicity to the present fatty acid polyester. The amount of wax added is 0.1 to 5 parts by weight based on 100 parts by weight of the aliphatic polyester (I) or the aliphatic polyester polyol (II). 0.1
If it is less than 5 parts by weight, the effect is small. On the other hand, if it is more than 5 parts by weight, it is difficult to be compatible with the resin and the layers are separated. Natural waxes are generally preferred over synthetic waxes to promote biodegradability.

In the present invention, as a synthetic wax, a synthetic hydrocarbon type Fischer-Tropsch wax such as Sazole wax (molecular weight 460 to 2,000, freezing point 8) is used.
Petroleum-based synthetic waxes such as polyethylene wax (molecular weight 500 to 10,000, melting point 90 to 130 ° C), polypropylene wax (molecular weight 500 to 10,000, melting point 150 to 170 ° C); fluorine Resin-based waxes, silicone resin-based waxes, natural product-modified waxes such as montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives, and amide-modified waxes can be used.

In the present invention, as natural wax, for example, plant wax, candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil and the like;
Animal waxes such as beeswax, lanolin, and whale wax; mineral waxes such as montan wax,
Ozokerite and ceresin, etc .; petroleum waxes include, for example, paraffin wax, microcrystalline wax, petrolactam, and these can be used.

The foaming agent which can be used in the present invention is an inorganic compound foaming agent such as sodium hydrocarbon and azides used in the production of general plastic foams, azo type, hydrazine type, triazole type, N-nitrone type. And an organic compound foaming agent such as citric acid. It is also a preferred embodiment to use various foaming aids such as calcium carbonate and talc together with these foaming agents. Depending on the decomposition temperature of the foaming agent, these may be pelletized by previously kneading into the same resin, kneading into polycaprolactone of low melting point polyester, or may be directly dry blended with a mixer or the like for use. The blending amount of the foaming agent varies depending on the type of the foaming agent, the expansion ratio of the product, the molding temperature, etc., but the aliphatic polyester composition 100 is usually used.
It is 0.2 to 5.0 parts by weight with respect to parts by weight.

The method for producing the foam-opened product of the present invention can be carried out at an extrusion temperature of 150 to 220 ° C. using an extruder and a manufacturing method used for the foam-opened product such as polypropylene. .

The expanded spreader used in the present invention needs to have an adsorbed amount of B heavy oil at 4 times or more of its own weight at 20 ° C. Therefore, the expansion ratio and other manufacturing conditions are devised to open it. It is necessary to make fine fibers as thin as possible. The amount of adsorption is preferably 10 times or more.

The foam spread mat for oil adsorption of the present invention is
The conventional foamed open fiber mat for absorbing oil can be manufactured by reference. That is, the foam spreader for adsorbing oil is cut into a length of about 45 cm in the TD direction (direction perpendicular to the fiber take-up direction), and a plurality of sheets (5 to 100 sheets, and preferably about 100 sheets, preferably about 5 to 100) are cut to a thickness that is easy to handle. 40
(About 60 sheets) are laminated, and the laminated body is heat-welded at a plurality of places, for example, at intervals of about 5 mm to be used as a mat.

The foam-opening mat for adsorbing oil produced in this manner has a resin density of 1,23 to 1.26 g / cm ^{3 of} the aliphatic polyester composition used, so that the foam-opening mat alone is water-soluble. Alternatively, it is not suitable for collecting and removing the oil film spreading on the water surface because it sinks in seawater. Therefore, as a foam open sheet body laminate for oil adsorption used in rivers, seas, etc., a foam sheet having the same composition as the foam open sheet for oil adsorption is laminated, and the overall density of the foam opened sheet laminate is 1 g. It is necessary to obtain a foamed sheet laminate having a density of / cm ³ or less.

The foamed sheet of aliphatic polyester can be manufactured based on the disclosure of US Pat. No. 5,362,765. That is, by extrusion foam molding, the expansion ratio is about 2 to 40 times, and the sheet density is about 0.6 to
0.03 g / cm ³ , thickness 1 to 50 mm, preferably 1
It is preferable to use it as a foamed sheet having a thickness of 10 to 10 mm, more preferably 2 to 5 mm. When the expansion ratio is low, the density cannot be lowered, so the amount of the sheet must be increased. On the other hand, if the foaming ratio is too high, the rigidity of the sheet is lost and the strength of the laminate is lost. Also, when the thickness of the sheet is thin, the work is troublesome in manufacturing,
There is no problem because it is sufficient to increase the number of layers to be laminated, but when the thickness is made too thick, the proportion of the foam-opening body for oil adsorption in the laminated body becomes small, and the oil adsorption is impaired. In the case of a foam spread sheet laminate for adsorbing oil, a sheet having a diameter of 1 to 10 mm may be formed in the sheet so that water or oil can flow vertically to promote adsorption of oil. preferable.

A normal aliphatic polyester composition has a wetting index (also called critical surface tension) of 39 to 40 dyne /
cm, 30-32 dyne / c of polyethylene
m, which is closer to about 70 dyne / cm of water as compared with 27 to 31 dyne / cm of polypropylene. Therefore, when water and oil coexist, the polypropylene foam spreader absorbs oil more easily than water, but the aliphatic polyester foam spreader absorbs water first and then oil Becomes difficult to adsorb. In the present invention, it is considered that a wax is kneaded into such an aliphatic polyester, which improves the wettability of the surface of the foam-opened body and also serves as a guide for the oil adsorption inside.

[0039]

The present invention will be described below with reference to examples and comparative examples. The analytical equipment and measurement conditions used for physical property measurement are as follows. (A) Measurement of molecular weight The measurement was performed by the GPC method. a. System: Showa Denko KK, SYSTEM-11 b. Column: Sample, Sh (with reference side)
odex GPC K-801 (1 piece) + K-80M (2 pieces) + K800P
(1) c. Solvent: chloroform d. Column temperature: 40 ° C e. Flow rate: 1.0 ml / min f. Polymer concentration: 0.1% by weight g. Detector: Shodex R1 h. Molecular weight conversion standard: PMMA (Shodex
M-75) i. Injection volume: 0.8 ml / min

J. Method for evaluating the wettability of the surface of the aliphatic polyester composition: JIS K-6768-1977 polyethylene and polypropylene film wetting test method (3
0-56 dyne / cm). The aliphatic polyester composition of the present invention is about 0.3 mm at 180 ° C. for about 1 minute.
It was pressed into a thick film. After standing in a constant temperature and constant humidity room for 1 day, a wetness index reagent of Wako Pure Chemical Industries, Ltd. was applied and evaluated. k. Aliphatic polyester composition (aliphatic polyester +
Adsorption test of salt water / oil content of wax): A 0.3 mm thick film press-molded was cut into 50 mm square. It was immersed in kerosene at room temperature for 5 minutes, and the surface was wiped with a tissue paper to measure the weight increase rate (Wa%). Then 3%
The weight increase rate (Wb%) was measured by immersing in saline in advance, and then the increase rate when immersing in kerosene was measured.

L. Measurement of oil absorption of the foam spreader: 20 pieces of foam spreaders for adsorbing oil (10 because of inflation film) were laminated and heat-sealed in the TD direction.
A cm open square foamed open body for oil adsorption was produced. 20 ° C B
Float on the oil surface of heavy oil and leave for 5 minutes, then
After the wire is left for 5 minutes on a wire mesh (hereinafter referred to simply as a wire mesh) in which a 17 mm mesh has a mesh of 17 mm, the weight is measured. The value obtained by converting the result per 1 g was taken as the oil absorption amount of the expanded foam.

M. Measurement of the fineness of the filaments of the foam-opened body: 100 yarns having a length of 2 cm were collected, the weight was determined as n = 3, and the denier number was determined. n. Formability: Screw diameter 55 mmφ, L / D = 30
200mm with slit spacing of 0.5mm
1 according to resin MFR from φ annular slit nozzle
Obtaining an optimum temperature between 30 and 240 ° C, melt-extruding at that temperature, blowing air at room temperature from the air ring,
Opening start point immediately after melt extrusion (about 2 from slit nozzle)
cm position) and take-off speed 3
It was taken out at 0, 60, 100, 150 and m / min to form a foamed open body. The denier of the whole spread film and the denier number of the single fibers shown in Table 1 are as follows.
It is the data of the foam spreader at m / min. o. Soil biodegradation test: 90 parts by weight of river sand, 5 parts by weight of compost for commercial horticulture and 5 parts by weight of oil dregs are mixed, put into a planter with a width of about 40 cm, a length of about 80 cm, and a depth of about 40 cm, and water is thoroughly applied. The upper part is covered with a polyethylene sheet and is about 1
Aged for months. The test piece was embedded in the soil about 10 cm below the surface and kept at room temperature for a predetermined time. Then, the test piece was dug out, washed with water and dried, and then the weight loss rate was measured.

Example 1 Butylene succinate adipate copolymer IIB1 (Showa High Polymer Co., Ltd., trade name: Bionole # 3003, which has a good biodegradability as a base polymer, but has a linear structure with a slow molding speed. Melting point 96
° C, MFR 5.0 g / 10 minutes, number average molecular weight 67,000
0, weight average molecular weight 168,000), a film having a thickness of about 30 μm was formed by an air cooling insulation method, and biodegradability in soil was tested. After 20 days at room temperature, the weight loss rate was good at about 46%.

2.5 parts by weight of wax or 5 parts by weight of wax was added to 100 parts by weight of the base polymer, and a kneader ruder with a diameter of 36 mm manufactured by Kasamatsu Kako Laboratories was used. After mixing for about 40 minutes, the mixture was extruded into a strand at 150 to 180 ° C. into water and pelletized. After vacuum drying overnight at 70 to 90 ° C., a 0.3 mm film was formed by press molding. Table 1 shows the results of an adsorption test of kerosene (representing petroleum) in a 3% saline solution simulating seawater for the aliphatic polyester composition with addition of various waxes.

The waxes used are polyethylene wax PE190 (dripping point 135 ° C.), polypropylene wax PP230 (dripping point 158 ° C.), fluororesin wax (seridust 3910), montan wax (Hoechst wax S), Shin-Etsu manufactured by Hoechst. Silicone oil KF96-L manufactured by Kagaku Kogyo KK, deodorized refined beeswax high acid manufactured by Noda Wax Co., Ltd., and carnauba wax manufactured by Kato Yoko. The base polymer alone did not adsorb oil at all, but by using the wax together, the wetting index of the resin surface was improved from 39 dyne / cm to 37 dyne / cm, and it became possible to adsorb kerosene.

[0046]

[Table 1]

Comparative Example 1 Polypropylene (Show Allomer AF) which has been conventionally used as an oil-adsorptive material.
Regarding 2), the same test as in Example 1 was performed. Polypropylene is superior to the present aliphatic polyester in oil adsorption, but it is not suitable for the purpose of the present invention because it has no biodegradability in soil.

(Example 2) Polybutylene succinate IIB2 having a long-chain branched structure with good moldability as a base polymer but slow biodegradability (Showa High Polymer Co., Ltd .: trade name Bionole # 1903, melting point 114 ° C., MFR 8.2g / 10
Min, number average molecular weight 58,000, weight average molecular weight 33
4,000, the weight loss of soil biodegradation was about 22% after 20 days). The same test as in Example 1 was performed. Table 2 shows the results. This aliphatic polyester has a surface wetting index of 38 dyne / cm when used in combination with wax.
To 36 to 37 dyne / cm and the oil adsorbability was improved.

Example 3 105 mol of ethylene glycol, 80 mol of succinic acid, and 2 adipic acid were added to the base polymer.
An aliphatic polyester polyol b3 was synthesized from 0 mol and 0.5 mol of trimethylolpropane by a polycondensation method,
Next, a high-molecular-weight polymer was added with 0.82 mol of hexamethylene diisocyanate. The polyethylene succinate adipate IIB3 having a long-chain branched structure with good moldability and fast biodegradability (melting point 91 ° C, number average molecular weight 45,70).
0, weight average molecular weight 236,000, 40 μm thick blown film has a weight loss due to biodegradation in soil of 2
About 75% after 0 days) was used. Polyethylene wax PE19 is added to 100 parts by weight of this aliphatic polyester.
The composition obtained by kneading 5 parts by weight of 0 had a wetting index of 35 dyn.
It was improved to e / cm and was excellent in both oil adsorption and biodegradability. Table 2 shows the results.

[0050]

[Table 2]

Examples 4 to 10 Synthetic Examples of Aliphatic Polyester and Production of Expanded Fiber: 1) Synthetic Example of Aliphatic Polyester Resin IA1 of the Present Invention Having a Long Chain Branch Structure: 80 L Reactor Was replaced with nitrogen, and then 25.2 kg of succinic acid, 17.7 kg of 1,4-butanediol and 1.62 k of propylene glycol.
g, and 98 g of glycerin (95 mol%, 10 mol% and 0.5 mol% with respect to 100 mol% of succinic acid) were charged. The temperature was raised under a nitrogen stream, the reaction was conducted at 190 to 220 ° C. for 3.5 hours, and then the nitrogen was stopped to conduct the esterification reaction by dehydration condensation for 5.5 hours under a reduced pressure of 20 to 2 mmHg for 5.5 hours. The collected material has an acid value of 16 mg / g,
Number average molecular weight is 6,400 and weight average molecular weight is 1
It was 0,600. Subsequently, 2.0 g of tetraisopropoxy titanium as a catalyst was added under a nitrogen stream under normal pressure,
Raise the temperature to 1.8-0.5m at 210-220 ℃
The deglycol reaction was performed for 15 hours under reduced pressure of mHg. The theoretical yield of this prepolymer (a1) was 35.2 kg when condensed water was removed.

The reaction product was operated by operating a gear pump under a kettle to extrude four strands into water from a die at 190 to 200 ° C. and cut with a cutter to form pale yellow pellets. The yield of the aliphatic polyester (IA1) after vacuum drying at 90 ° C. for 3 hours was about 29 kg. Not containing the urethane bond thus obtained,
The aliphatic polyester (IA1) (polybutylene / propylene succinate copolymer) of the present invention having a long-chain branched structure has a melting point of 110 ° C. and a number average molecular weight of 48,40.
0, weight average molecular weight 277,300, MFR 1.7g
/ 10 minutes.

2) Linear aliphatic polyester copolymer (I
Synthesis example of IB1): 1,4-butanediol 17.4 kg, succinic acid 17.3 kg, adipic acid 5.4 kg (molar ratio of succinic acid to adipic acid = 80: 20) was prepared. The temperature is raised under a nitrogen stream, and the temperature is raised at 190 to 210 ° C. for 3.5 hours. Further, nitrogen is stopped and the pressure is reduced to 3.5 at 20 to 2 mmHg.
The esterification reaction by dehydration condensation was performed over time.
The collected sample had an acid value of 9.6 mg / g, a number average molecular weight of 6,100, and a weight average molecular weight of 12,200. Subsequently, 2.0 g of tetraisopropoxy titanium as a catalyst was added under a nitrogen stream under normal pressure. The deglycolization reaction was carried out at a temperature of 210 to 220 ° C. under a reduced pressure of 15 to 0.2 mmHg for 6.5 hours. The collected sample had a number average molecular weight of 26,000 and a weight average molecular weight of 69,600. Met. This prepolymer (b1)
When the condensed water was removed, the theoretical yield was 32.6 kg.
Next, 34 g of Irganox 1010 (Ciba Geigy) as an antioxidant and 34 g of calcium stearate as a lubricant were added, and stirring was continued for another 30 minutes.

To a reactor containing 32.6 kg of this prepolymer (b1), 310 g of hexamethylene diisocyanate (0.975 parts by weight relative to 100 parts by weight of prepolymer (b1)) was added with stirring to give a mixture of 160- The binding reaction was performed at 190 ° C. for 1 hour. The viscosity increased rapidly but no gel formed. The reaction product was extruded into water with a kneader ruder and cut into pellets with a cutter. Aliphatic polyester (IIB after vacuum drying at 70 ° C. for 6 hours
The yield of 1) was 30.0 kg. This polybutylene succinate adipate copolymer (IIB1) is
Slightly ivory-like white color, melting point 95.8 ° C, heat of dissolution (△ H) 45.3 Joules / g, number average molecular weight 7
5,000, weight average molecular weight 18,8,000, MFR
(190 ° C.) 1.8 g / 10 minutes.

3) Synthesis example of aliphatic polyester resin (IIb2) having a long-chain branched structure: 1,4-butanediol 17.7 after replacing 80 L reactor with nitrogen
kg, succinic acid 22.1 kg, and trimethylolpropane 126 g (0.5 mol% based on succinic acid) were charged. The temperature was raised under a nitrogen stream, and the esterification reaction by dehydration condensation was performed at 190 to 210 ° C. for 3.5 hours, and further with the nitrogen stopped, under a reduced pressure of 20 to 2 mmHg for 5.5 hours. The collected sample has an acid value of 12 mg /
g, number average molecular weight 6,800, and weight average molecular weight 1
3,500. Subsequently, 2.0 g of tetraisopropoxy titanium as a catalyst was added under a nitrogen stream under normal pressure.
15-0.7m at a temperature of 210-220 ℃
The deglycolization reaction was performed for 4.5 hours under a reduced pressure of mHg. The collected samples had a number average molecular weight of 36,450 and a weight average molecular weight of 83,400. This prepolymer (b2) has a theoretical yield of 35.4 when condensed water is removed.
kg.

To a reactor containing 35.4 kg of this prepolymer (b2), 3.5 g of phosphorous acid as a coloring inhibitor was added at 160 ° C., and then Irganox B225 (Ciba Geigy) as an antioxidant was added at 35. 4 g and 35.4 g of calcium stearate as a lubricant were added and stirring was continued for another 30 minutes. Then, with stirring, 319 g of hexamethylene diisocyanate (prepolymer (b2) 10
180 to 2 by adding 0.9 part by weight to 0 part by weight)
Coupling reaction was performed at 00 ° C. for 1.5 hours, then under reduced pressure of 200 to 400 mmHg for 30 minutes under reduced pressure, further stopped for 1.5 hours with stirring, and left standing (total 3.5 hours). The viscosity increased rapidly but no gel formed. This reaction product is operated by a gear pump under the kettle to generate 190 to 2
Four strands were extruded into water from a die at 00 ° C. and cut with a cutter into white pellets. 90 ° C
Aliphatic polyester (II
The yield of B2) was about 29 kg. The aliphatic polyester (IIB2) (polybutylene succinate polymer) of the present invention having a long-chain branched structure thus obtained
Had a melting point of 114 ° C., a number average molecular weight of 55,100, a weight average molecular weight of 221,100, and an MFR of 5.4 g / 10 minutes.

4) Synthesis of aliphatic polyester resin (IIB3) having long long-chain branched structure: 1,4-butanediol 20.
0 kg and 25.0 kg of succinic acid were charged. The temperature was raised under a nitrogen stream, the esterification reaction was carried out by dehydration condensation at 190 to 220 ° C. for 3.5 hours, and further, nitrogen was stopped and the pressure was reduced at 20 to 1.2 mmHg for 2.5 hours. . The acid value of the collected sample was 23.1 mg / g. Subsequently, 2.0 g of tetraisopropoxy titanium as a catalyst was added under a nitrogen stream under normal pressure. The temperature was raised and the deglycolization reaction was carried out at a temperature of 210 to 220 ° C. under a reduced pressure of 1.5 to 0.7 mmHg for 4.5 hours. The collected sample had a number average molecular weight of 24,000 and a weight average molecular weight of 477. , 40. This prepolymer (b
For 3), the theoretical yield was 36.4 kg when condensed water was removed. In a reactor containing 36.4 kg of this prepolymer (b3), 9 g of phosphorous acid as a coloring inhibitor and Irganox B225 (Ciba Geigy) as an antioxidant were added at 160 ° C.
36 g and 36 g of calcium stearate as a lubricant
Was added and stirring was continued for another 30 minutes.

Then, 291 g of hexamethylene diisocyanate (0.8 parts by weight with respect to 100 parts by weight of prepolymer (b3)) was added with stirring, the mixture was stirred at 160 ° C. for 20 minutes, and then trimethylolpropane hexamethylene diamine was added. 291 g of isocinanate adduct (75 active ingredients)
% Ethyl acetate solution, 0.8 part by weight to 100 parts by weight of prepolymer, Nippon Polyurethane Industry Co., Ltd .: trade name Coronate HL) was further added, and the mixture was reacted at 180 to 200 ° C. for 2 hours. The viscosity increased rapidly but no gel formed. The reaction product was extruded into water via a kneader ruder and cut into white pellets with a cutter.
The yield of the aliphatic polyester (IIB2) after vacuum drying at 90 ° C. for 6 hours was about 32 kg. The thus obtained aliphatic polyester (IIB3) (polybutylene succinate polymer) having a long chain branched structure has a melting point of 116.1 ° C. and a number average molecular weight of 65,13.
0, weight average molecular weight 186, 440, MFR (190
C.) 3.5 g / 10 minutes.

5) Production of foam-opening body: 100 parts by weight of the aliphatic polyester produced alone or a mixture thereof, 2 parts by weight of polyethylene wax PE190, and a mixture of citric acid / sodium bicarbonate as a foaming agent (by weight ratio) 2/5 parts by weight of a mixture of 10/90), and if necessary, 1-5 parts by weight of calcium carbonate are dry blended to obtain 5
Screw temperature 150 ~ 200 ℃ by 5mmφ extruder
With a slit interval of 0.5 mm and a die diameter of 200 mmφ, an annular slit nozzle is melt-extruded at a molding temperature of 150 to 200 ° C., and air at room temperature is blown from the air ring to start the fiber opening immediately after the melt extrusion (about 2 cm from the slit nozzle). (Position) and take-off speed 10m /
It was taken out in minutes to form a foam-opened body.

The foamed open body thus obtained is a net-like body with less yarn breakage due to the combination of the resin structure and the composition, and is 36,000 denier as a whole and 5 to 20 denier as a single yarn. The texture was excellent.

When about 5 g of these foam-opened materials were buried in the soil for 5 months, they were decomposed and changed to a state having almost no practical tensile strength. Further, the amount of the foam-opened body of the composition type having a quick biodegradability was significantly reduced.

(Example 4) 100 parts by weight of polybutylene propylene succinate (IA1) having a long-chain branched structure and 2 parts by weight of a foaming agent were set at a screw temperature of 160 to 200 ° C, a die temperature of 200 ° C, and a nozzle temperature of 190 ° C. The production of the foam-opened body was started at and the take-up speed was 10 m / min. The moldability was good. The foamed open body produced is flexible and strong.
The oil absorption amount of the B-heavy oil was 6 times as large as its own weight.
Further, when about 5 g of the spread fiber was buried under 10 cm in the soil and the biodegradability after 5 months was examined, it was found that the progress was considerably advanced, and the expanded fiber had almost no yarn strength.

(Example 5) The polybutylene-succinate-adipate copolymer (IIB1) having a linear structure has a slow crystallization rate due to the copolymer and is inferior in moldability. The effect of adding ~ 4 parts by weight was also small. In the obtained foam-opened product, the amount of B heavy oil adsorbed was 8 times its own weight, which was relatively good, and the biodegradability in soil after 5 months was extremely excellent with a weight reduction rate of about 80%.

(Example 6) 100 parts by weight of a polybutylene succinate (IIB2) having a long-chain branched structure and a blowing agent (citric acid / sodium bicarbonate = 40/60 weight ratio) 2
~ 4 parts by weight of the mixed composition, screw temperature 155-1
90 ° C, die temperature 185 to 200 ° C, nozzle temperature 18
A foam spreader was produced at 5 to 200 ° C. The take-up speed was 10 to 20 m / min, and the moldability was good. This foam-opened body had an adsorbed amount of B heavy oil that was 5 times its own weight, and the soil-degradability was slow even after 5 months.

Example 7 A foamed spreader of polybutyl succinate (IIB3) having a long long-chain branched structure was produced in substantially the same manner as in Example 6. Moldability was relatively good. The foamed spreader had a B heavy oil oil adsorption amount as low as 4 times its own weight, and its soil degradability was also slow.

(Examples 8 to 10) Pellets 80 using a polybutylene succinate adipate copolymer (IIB1) having a long-chain branched structure with fast biodegradability as a base polymer.
20 parts by weight of long-chain branched polybutyl succinate (IIB2) having excellent moldability was mixed with 20 parts by weight of pellets. Further, polyethylene wax PE190 manufactured by Hoechst Co., Ltd. was not added, and 2 parts by weight and 4 parts by weight were dry blended, and screw temperature was 160 to 200 ° C., die temperature was 180 to 200 ° C., and nozzle temperature was 175 to 190.
A foam spreader was produced at a temperature of 10 ° C. and a take-up speed of 10 to 20 m / min. The moldability was extremely good.

The expanded spreader of the present invention has an excellent effect that the amount of B heavy oil adsorbed increases to 6 times, 12 times and 15 times its own weight as the amount of polyethylene wax added becomes 2 parts by weight and 4 parts by weight. The biodegradability after 5 months in soil was excellent and the weight reduction rate was 70 to 90%. The heat of combustion of the foamed open body is as low as 5,800 to 6,000 kcal / kg, which is about half that of polyolefins, and can be easily incinerated. The results of Examples 4 to 10 are summarized in Table 3.

[0068]

[Table 3]

(Comparative Example 2) A similar test was performed on a polypropylene foam spreader. Although it has a large oil adsorption amount, it has no biodegradability in soil and is not suitable for the purpose of the present invention.

(Example 11) The cylindrical foam spreader of the present invention obtained in Examples 8 to 10 was cut into a length of 45 cm in the direction perpendicular to the molding direction (MD) (TD), and 45 sheets ( 90
Layer), heat-seal the cut portion to a width of 5 mm,
A foam open mat for adsorbing oil having a width of 50 cm was prepared.
Water was poured into the rectangular container, a small amount of B heavy oil was floated on the water surface, and then the B heavy oil was adsorbed on the oil-adsorbing expanded fiber mat. The oil adsorption rate was also improved as the amount of polyethylene wax added increased.

(Example 12) Although the foam spread mats for adsorbing oil components of Examples 8 to 12 have almost sufficient oil adsorption performance, they have a specific gravity larger than water and sink into water. Therefore, it became clear that there are problems when used as an oil mat or oil fence on the sea. As a countermeasure against this, I tried to give buoyancy by laminating a foam sheet on a foam open mat for oil adsorption.

[Example of Production of Foamed Sheet] 100 parts by weight of polybutylene succinate (IIB2) having a long-chain branched structure, 2 parts by weight of polyethylene wax, and 2 parts by weight of talc having an average particle diameter of 2 μm as a foam nucleating agent were added. A foamed sheet having a thickness of about 3 mm was prepared by the gas foaming method. The first extruder of tandem type gas foam molding machine (diameter 61m
m: 170 ° C), 2nd extruder (caliber 90m)
m: 140 ° C to 114 ° C), circular die (1
10 ° C.) and used as a foaming gas for HCFC142b /
Using a mixed gas of HCFC22 (60/40), a mandrel outer peripheral diameter of 640 mm was produced. The obtained foamed sheet had a thickness of 3.0 mm, a width of 1000 mm, a foaming ratio of about 20 times, and a density of 0.032 g / cm ³ .

(Production Method of Foam Opening Sheet Laminate for Oil Adsorption) The above foam sheet was cut into a length of 45 cm and a width of 48 cm, and was inserted into the oil adsorption foam opening mat of Example 11 and heat-sealed. A foam spread sheet sheet laminate for adsorbing oil was produced by fixing in part. A hole having a diameter of 10 mm was opened to facilitate the circulation of seawater and oil. The foam-opened sheet laminate for adsorbing oil easily floated on fresh water and salt water having a concentration of 3% and adsorbed oil well.
Further, the biodegradability of the foam part in soil was considerably eroded by microorganisms after 5 months.

[0074]

The aliphatic polyester composition containing the aliphatic polyester of the present invention as a main component and having improved wettability with a synthetic wax and a natural wax, an expanded foam for adsorbing oil,
The foam-opening mat for oil adsorption and the foam-opening sheet laminate for oil adsorption have biodegradability when embedded in soil, etc., and their calorific value is higher than that of polyethylene or polypropylene even when incinerated. Even so, it is as low as about half that and has excellent thermal stability and mechanical strength. Moreover, since it has sufficient performance as an oil adsorption material, it is widely useful as an industrial material for social and environmental protection.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C08G 63/02 C08G 63/02 63/88 63/88 (72) Inventor Hiroki Iida Tokyo 3-20 Kandanishikicho, Chiyoda-ku, Showa High Polymer Co., Ltd. (72) Inventor Hideo Okura 3-20, Kandanishikicho, Chiyoda-ku, Tokyo Showa Highpolymer Co., Ltd. (72) Inventor Nobuhiro Watanabe Kandanishiki-cho, Chiyoda-ku, Tokyo 3 chome 20 Showa High Polymer Co., Ltd. (72) Inventor Ken Miyadera 238 Dun Isoshima, Mishimacho, Sanmon-gun, Fukuoka Prefecture Dan Sangyo Co., Ltd. (72) Yasutaka Ide 238 Dunn Isojima, Sanbashi, Sanmon-gun, Fukuoka Stock In-house (72) Inventor Mitsuhiro Imaizumi 3-2 Chidori-cho, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Kawasaki Plastics Research Laboratory, Showa Denko KK (72) Inventor Hideharu Kimura, Kan 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kawasaki

Claims (8)

[Claims] 1. A. First Embodiment Aliphatic polyester prepolymer (A) mainly obtained from aliphatic glycol and aliphatic dicarboxylic acid is subjected to a deglycol reaction to have a number average molecular weight of 40,000 or more. 100 parts by weight and B.I. A synthetic wax having a number average molecular weight of 10,000 or less,
A natural wax or a wax of any of these mixtures, which is comprised of 0.1 to 5 parts by weight and has a wetting index of 38.
An aliphatic polyester composition having a dyne / cm or less. 2. A. Primarily, an aliphatic polyester polyol (B) having a terminal hydroxyl group, which is obtained by subjecting an aliphatic glycol and an aliphatic dicarboxylic acid to an esterification reaction and then a deglycolization reaction, is reacted with a polyfunctional isocyanate to give a number. Aliphatic polyester polyol (II) having an average molecular weight of 40,000 or more ...
100 parts by weight and B.I. A synthetic wax having a number average molecular weight of 10,000 or less,
Either natural waxes or mixtures thereof
・ ・ ・ 0.1 to 5 parts by weight, wetting index 38 dy
An aliphatic polyester composition having a ne / cm or less. 3. The number average molecular weight according to claim 1 or 2 is 40,000 or more, and the melt flow rate is 1.
Aliphatic polyester composition 10 of 0 g / 10 minutes or less
A foam spreader for adsorbing oil, which is obtained by extrusion foaming stretch molding a composition comprising 0 parts by weight and 0.2 to 5.0 parts by weight of a foaming agent at a temperature of 150 to 220 ° C. 4. The foam spreader for oil adsorption according to claim 3, which is an aliphatic polyester composition having a number average molecular weight of 60,000 or more. 5. The aliphatic polyester composition comprises 95 parts by weight or less of an aliphatic polyester (I) having a linear structure or an aliphatic polyester polyol (I having a linear structure.
An aliphatic polyester composition comprising a polymer selected from I) and 100 to 5 parts by weight of an aliphatic polyester (I) having a long chain branched structure or an aliphatic polyester polyol (II) having a long chain branched structure oil. The foamed spreader for adsorbing oil according to claim 3 or 4. 6. The foam spreader for adsorbing oil according to claim 3, wherein the amount of B heavy oil adsorbed at 20 ° C. is 4 times or more of its own weight. 7. A foam opening for adsorbing oil, which is obtained by cutting the foam opening body for adsorbing oil according to any one of claims 3 to 5 into a suitable size, laminating a plurality of sheets, and heat-sealing at least two places. Fiber mat. 8. When laminating a foam spreader for adsorbing oil, a foaming ratio is 2 to 40 times and a density is 0.6 to 0.03 g / c.
A foam open sheet sheet laminate for adsorbing oil, comprising a laminated foam sheet made of the aliphatic polyester composition according to claim 1 having a thickness of m ³ and a thickness of 1 to 50 mm.