JPH10204720A - Biodegradable flat yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a biodegradable flat yarn excellent in strength, elongation, dimensional stability, heat resistance and formability, and biodegraded in the natural world such as in a soil by forming a composition comprising a specific proportion of a homopolymer of ε-caprolactone and an aliphatic polyester. SOLUTION: The objective biodegradable flat yarn is obtained by forming a composition obtained by compounding (A) (i) 20-99wt.% homopolymer of ε-caprolactone or δ-valerolactone, (ii) 20-99wt.% block copolymer composed of 3.5-99.5wt.% ε-caprolactone or δ-valerolactone, and 96.5-0.5wt.% oxetane, (iii) 20-99wt.% block copolymer of 3.5-99.5wt.% ε-caprolactone or δ-valerolactone, and 96.5-0.5wt.% dimethyltrimethylene carbonate, or (iv) 20-99wt.% mixed polymer composition of 72.5-97.5wt.% poly (ε-caprolactone) or poly (δ-valerolactone), with 27.5-2.5wt.% poly(oxetane), with (B) 80-1wt.% aliphatic polyester obtained by performing dehydration and polycondensation of glycols and aliphatic dicarboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aliphatic polyester (E) obtained by a dehydration polycondensation reaction of a homopolymer (A) of ε-caprolactone or δ-valerolactone with a glycol and an aliphatic dicarboxylic acid. And an aliphatic polyester obtained by a dehydration polycondensation reaction between a block copolymer (B) of ε-caprolactone or δ-valerolactone and oxetane, and a glycol and an aliphatic dicarboxylic acid ( E) as an essential component, obtained by a dehydration polycondensation reaction between a block copolymer (C) of ε-caprolactone or δ-valerolactone and dimethyltrimethylene carbonate, and a glycol and an aliphatic dicarboxylic acid. And a poly (ε-caprolactone) or poly (δ) -Valerolactone) and a polymer mixture composition (D) comprising poly (oxetane);
One selected from a composition containing an aliphatic polyester (E) obtained by a dehydration polycondensation reaction of a glycol and an aliphatic dicarboxylic acid as an essential component is molded, for example, woven or braided, and is biodegradable. The present invention relates to providing a biodegradable flat yarn suitable for forming a net.

[0002]

2. Description of the Related Art Conventionally, for example, nets used for stabilizing the ground in revetment works and the like, vegetation nets for vegetation for fixing the ground by entanglement of the roots of vegetation, etc., and lawns, etc. are covered. As a flat yarn for weaving or braiding a lawn breeding net or the like for breeding a lawn or the like, it is common to use a flat yarn made of plastics such as polyethylene or polypropylene, or rayon.

[0003] However, a net made by weaving or braiding such a flat yarn made of plastics such as polyethylene and polypropylene requires a great deal of labor to recover after the purpose of use is completed. It is buried in the soil and difficult to recover, so it is left as it is. Such plastics are hardly decomposable in nature such as soil and water, so they do not disintegrate or decompose. Even if they can be recovered, they burn incineration equipment such as incinerators because of their high calorific value when incinerated. There are problems such as. Rayon, on the other hand, has biodegradability and therefore biodegrades in nature, but has low strength and has practical problems. In addition, since it is a natural material, stable supply tends to be difficult. Further, it has been pointed out that in order to produce rayon, trees are cut down and environmental destruction is caused.

In order to solve the above-mentioned problems, in recent years, biodegradable resins which are biodegraded in nature by microorganisms and the like, for example, poly (ε-caprolactone), 3-hydroxybutyrate and 3-hydroxyvalerate have been developed. It has been proposed to use a biodegradable net that is woven or braided using a flat yarn made of a copolymer, polylactic acid, or the like.
However, since poly (ε-caprolactone) has a low melting point, there is a problem in, for example, processing of a net, the strength is low after heat setting, and the biodegradation rate tends to be high and the biodegradation rate cannot be selected. The copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate is hard and brittle,
In addition, a flat yarn made of the polymer is woven or braided. For example, a net tends to have a high biodegradation rate and cannot select a biodegradation rate. Further, the flat yarn made of polylactic acid is hard, and the net made of the flat yarn tends to have poor biodegradability.

Accordingly, flat yarns made of such a biodegradable resin are woven or braided, for example, to entangle nets, plant roots and the like used for stabilizing the ground or the like in revetment work or the like. There is a tendency that it is not preferable for a vegetation net for fixing the ground and the like, and a lawn breeding net for growing the lawn and the like over the lawn.

[0006]

The present invention differs from the conventional flat yarn as described above in that, for example, the yarn is woven or braided, and after the purpose of use is completed, the soil is used as it is in the soil. Even when left in nature such as underwater, the whole is completely biodegraded by microorganisms and has excellent strength, elongation, dimensional stability (shrinkage), heat resistance, moldability, and biodegradation rate It is an object of the present invention to provide a biodegradable flat yarn that can be suitably used for a net or the like that can be selected within a predetermined time.

[0007]

The feature of the present invention is that a homopolymer of ε-caprolactone or δ-valerolactone (A) is 20 to 99% by weight, ε-caprolactone or δ.
-Block copolymer (B) 2 of valerolactone 3.5 to 99.5% by weight and oxetane 96.5 to 0.5% by weight
0 to 99% by weight, 20 to 99% by weight of a block copolymer (C) of 3.5 to 99.5% by weight of ε-caprolactone or δ-valerolactone and 96.5 to 0.5% by weight of dimethyltrimethylene carbonate. % And poly (ε-caprolactone) or poly (δ-valerolactone) 72.5 to
97.5% by weight and poly (oxetane) 27.5 to 2.5
% Of a polymer mixture composition (D) composed of 20 to 99% by weight, and an aliphatic polyester (E) obtained by a dehydration polycondensation reaction of a glycol and an aliphatic dicarboxylic acid with 80 to 80% by weight. The purpose is to provide a biodegradable flat yarn formed from a composition containing 1% by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the biodegradable polymer constituting the biodegradable flat yarn according to the present invention, ε-
Homopolymer of caprolactone or δ-valerolactone (A), block copolymer of ε-caprolactone or δ-valerolactone and oxetane (B), block of ε-caprolactone or δ-valerolactone and dimethyltrimethylene carbonate Copolymer (C) is preferred. Such a homopolymer (A) of ε-caprolactone or δ-valerolactone is obtained by using ε-caprolactone or δ-valerolactone.
-Valerolactone is preferably obtained by, for example, ring-opening polymerization using an organometallic compound catalyst. The block structure of such a block copolymer is not particularly limited, and may be a random block type, a diblock type, a linear type such as a triblock type, a branched type, or a radial type, but any may be used. In consideration of biodegradability, a random block copolymer is preferred.

The homopolymer (A), block copolymer (B) and block copolymer (C) of ε-caprolactone or δ-valerolactone constituting the biodegradable flat yarn according to the present invention were measured by GPC. The number average molecular weight in terms of standard polystyrene is 1,000 to 1,000,000
0, preferably 10,000 to 500,000, more preferably 30,000 to 300,000. When the number average molecular weight is less than 1,000, the liquid component is large at room temperature, and when it exceeds 1,000,000, the production is substantially difficult, and the biodegradability tends to decrease.

[0010] In the block copolymer according to the present invention,
The content of ε-caprolactone or δ-valerolactone in the entire block copolymer is 3.5 to 99.5% by weight, preferably 43%, based on 100% by weight of the total amount of oxetane or dimethyltrimethylene carbonate.
To 99% by weight, more preferably 64 to 97.4% by weight. If the content of ε-caprolactone or δ-valerolactone is less than 3.5% by weight, the biodegradability tends to be poor, and if it exceeds 99.5% by weight, the biodegradability tends to be fast. The choice of speed becomes difficult. Therefore, for example, nets used for stabilization of the ground in revetment work, etc., vegetation nets for vegetation to entangle the roots of vegetation, etc. to fix the ground, breeding nets for breeding lawns, etc. over grass etc. This tends to be undesirable as a woven or braided flat yarn, but can be used in some applications.

The binding of ε-caprolactone or δ-valerolactone constituting the biodegradable flat yarn according to the present invention is represented by the following chemical formula (1) or (2), and the binding of ε-caprolactone and oxetane is represented by chemical formula (3). The bond is chemical formula 4, the bond between ε-caprolactone and dimethyltrimethylene carbonate is chemical formula 5, and the bond between δ-valerolactone and dimethyltrimethylene carbonate is chemical formula 6.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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Further, the biodegradable polymer mixture composition (C) constituting the biodegradable flat yarn according to the present invention is obtained by polymerizing ε-caprolactone or δ-valerolactone and oxetane monomers. It is a biodegradable polymer mixture composition obtained by blending poly (oxetane) with poly (ε-caprolactone) or poly (δ-valerolactone).

The mixing ratio of such a biodegradable polymer mixture composition is 72.5 to 97.5% by weight of poly (ε-caprolactone) or poly (δ-valerolactone) and 27.5% by weight of poly (oxetane). A biodegradable polymer mixture composition containing 5 to 2.5% by weight is preferred. Poly (oxetane)
If the proportion of the biodegradation is less than 2.5% by weight, the biodegradation rate is high, and if it exceeds 27.5% by weight, the biodegradability tends to be inferior and it is difficult to select the biodegradation rate. Although it is not preferable as a net for stabilizing the ground, a vegetation net for fixing the ground or the like by entanglement of the roots of plants or the like, or a breeding net for lawns, etc., it can be used depending on the application.

As the aliphatic polyester (E) obtained by the dehydration polycondensation reaction between the glycols and the aliphatic dicarboxylic acid constituting the biodegradable flat yarn according to the present invention, glycols and aliphatic dicarboxylic acids (or the same) are used. Acid anhydride), or, if necessary, as a third component selected from trifunctional or tetrafunctional polyhydric alcohols, oxycarboxylic acids and polycarboxylic acids (or acid anhydrides thereof). An aliphatic polyester obtained by adding at least one polyfunctional component and esterifying by a dehydration polycondensation reaction as a main component, a relatively high molecular weight polymer or copolymer having a hydroxy group at a terminal of the molecule, Chemical 7
Can be mentioned. At this time, x / y
≧ 1.0, m and n indicate the length of the methylene group.

[0021]

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Specifically, polyethylene succinate (m = 2, n = 2) and polybutylene succinate (m = 2
4, n = 2) and polybutylene succinate adipate (m = 4, n = 2, 4) are preferred, but there is no particular limitation.

The number average molecular weight (Mn) of the aliphatic polyester is 5,000 or more, preferably 10,000.
As described above, a saturated aliphatic polyester having a melting point of 60 ° C. or more can be exemplified, but such a numerical value is not particularly limited.

If the number average molecular weight (Mn) is less than 5,000, the number average molecular weight tends to be small, and it tends to be impossible to obtain a polyester having good physical properties. Since a polyester polymer having a number average molecular weight (Mn) of 5,000 or more does not tend to form a gel during a polycondensation reaction even under severe conditions such as a molten state, an aliphatic polyester having a good high molecular weight can be synthesized.

The glycols constituting the aliphatic polyester obtained by the dehydration polycondensation reaction between the glycols constituting the biodegradable flat yarn and the aliphatic dicarboxylic acid according to the present invention include ethylene glycol and 1,4-butane. Examples thereof include diol, 1,6-hexanediol, decamethylene glycol, neopentyl glycol, and 1,4-cyclohexane dimethanol, and these glycols may be used in combination. Among them, ethylene glycol and 1,4-butanediol are preferred, but are not particularly limited.

The aliphatic dicarboxylic acids (including acid anhydrides) which constitute the aliphatic polyester by the dehydration polycondensation reaction with the above glycols include succinic acid, adipic acid, speric acid, sebacic acid, dodecanoic acid, Examples thereof include succinic anhydride and adipic anhydride, and these dicarboxylic acids may be used in combination. Among them, succinic acid and adipic acid can be mentioned as preferred, but not particularly limited.

Further, in addition to the above-mentioned glycols and aliphatic dicarboxylic acids, if necessary, a trifunctional polyhydric alcohol component (for example, trimethylolpropane, glycerin or an anhydride thereof) as a third component, or a tetrafunctional polyhydric alcohol component may be used. Trihydric alcohol component (for example, pentaerythrite), trifunctional polyhydric oxycarboxylic acid component (for example, malic acid), tetrafunctional polyhydric oxycarboxylic acid component (for example, citric acid, tartaric acid, etc.), and trifunctional Polycarboxylic acids (including their anhydrides)
Components (eg, trimesic acid, propanetricarboxylic acid, etc.) and tetrafunctional polycarboxylic acids (including their acid anhydrides) (eg, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, cyclopentanetetracarboxylic anhydride) And the like, may be added to synthesize an aliphatic polyester. The addition of the third component tends to cause long-chain branching in the molecule, which tends to increase the molecular weight and broaden the molecular weight distribution, and can be expected to impart favorable properties to film molding and the like. At this time, the amount of the third component added is 3 parts per 100% by mole of the total components of the aliphatic dicarboxylic acid (including the acid anhydride) so that gelation does not occur.
0.1 to 5 mol% for the functional component and 0.1 for the 4 functional component
３3 mol% can be exemplified, but there is no particular limitation, and it is not necessary to add.

The biodegradable flat yarn according to the present invention comprises:
20 to 99% by weight of homopolymer (A) of ε-caprolactone or δ-valerolactone, ε-caprolactone or δ
-Biodegradable block copolymer of valerolactone and oxetane (B) (preferably random block copolymer)
20 to 99% by weight, 20 to 99% by weight of a biodegradable block copolymer (C) of ε-caprolactone or δ-valerolactone and dimethyltrimethylene carbonate (preferably a random block copolymer) and poly (ε-caprolactone) ) Or a biodegradable polymer mixture composition of poly (δ-valerolactone) and poly (oxetane) (D) 20 to 9
At least one selected from 9% by weight is formed from a composition containing 80 to 1% by weight of an aliphatic polyester (E) obtained by a dehydration polycondensation reaction between a glycol and an aliphatic dicarboxylic acid as an essential component. Are preferred.

At this time, the amount of the aliphatic polyester (E) obtained by the dehydration polycondensation reaction between the glycols and the aliphatic dicarboxylic acid is less than 1.0% by weight [homopolymer (A), block copolymer (B), at least one selected from the block copolymer (C) and the biodegradable polymer mixture composition (D) is more than 99% by weight], the sheet is slit into a narrow width, and the sheet is cut in one direction. When a flat yarn is formed by stretching the sheet, the heat resistance and the adhesion resistance of the sheet tend to decrease, so it is necessary to lower the stretching temperature and the fixing temperature. For this reason, the flat yarn is soft and has a heat shrinkage (80 ° C. × 30 seconds) of, for example, 5.0% or more, and tends to melt at a temperature of about 80 ° C. or less. Properties and strength tend to decrease. Therefore, a net or the like made of such a biodegradable flat yarn easily adheres to a device such as a weaving machine or a knitting machine when weaving or braiding, and tends to have poor strength and dimensional stability.
Furthermore, flat yarns of such compositions tend to biodegrade easily and thus tend to degrade in a relatively short period of time, making it difficult to select a biodegradation rate and adjust it over a period of time. For example, in revetment work, nets that stabilize the ground, nets for vegetation that stabilize the ground, etc. by entangled with the roots of vegetation, and nets for breeding, such as lawns, tend to decompose before completing the purpose. There is a tendency that it cannot be used as a flat yarn for weaving or weaving such a net or the like, which is not preferable.

The content of the aliphatic polyester is 80% by weight.
[Homopolymer (A), block copolymer (B), (C)
And at least one selected from the biodegradable polymer mixture composition (D) is less than 20% by weight], depending on the type of the aliphatic polyester, for example, the flat yarn has a tensile strength of 2.0 g / d or more, tensile elongation is 20
５０50%, heat shrinkage at 80 ° C. for 30 seconds is 0 to 5.0%
In addition, at least one of the characteristics in which the weight loss rate after immersion in returned sludge at 25 ° C. for 9 weeks is 35% by weight or more tends to be out of the above range. For example, polybutylene succinate polymer is biodegradable (for example, net), polybutylene succinate-adipate copolymer has tensile strength and heat shrinkage, and polyethylene succinate polymer has heat shrinkage and biodegradability. (Eg, net) tends to fall outside the above range. Therefore, such a flat yarn or the like is woven or braided, for example, a net used to stabilize the ground in revetment work or the like, a vegetation net that entangles the roots of vegetation and the like to fix the ground, and the like. Although it tends to be unfavorable as a breeding net such as lawn, it can be used depending on the use.

Generally, ε-caprolactone or δ-
Valerolactone homopolymer (A), block copolymer of ε-caprolactone or δ-valerolactone and oxetane (B), block copolymer of ε-caprolactone or δ-valerolactone and dimethyltrimethylene carbonate ( C) and poly (ε-caprolactone) or poly (δ-valerolactone) and poly (oxetane)
The biodegradable polymer mixture composition (D) having the following formula (I) tends to have better biodegradability than the aliphatic polyester (E) obtained by the dehydration polycondensation reaction between glycols and an aliphatic dicarboxylic acid. On the other hand, an aliphatic polyester (E) obtained by a dehydration polycondensation reaction between a glycol and an aliphatic dicarboxylic acid is a homopolymer (A) of ε-caprolactone or δ-valerolactone, ε-caprolactone or δ.
Block copolymer of valerolactone and oxetane (B), block copolymer of ε-caprolactone or δ-valerolactone and dimethyltrimethylene carbonate (C) and poly (ε-caprolactone) or poly (δ-valero) Adhesion resistance, heat resistance and moldability tend to be superior to the biodegradable polymer mixture composition (D) composed of lactone) and poly (oxetane).

Accordingly, for example, a biodegradable net formed by weaving or braiding the biodegradable flat yarn according to the present invention can be obtained by the dehydration polycondensation reaction between glycols and aliphatic dicarlavonic acid. Polyester (E), although not subject to any particular limitation, may be, for example, a polybutylene succinate polymer, a polybutylene succinate-adipate copolymer, or a polyethylene succinate polymer, used alone or in combination of two or more, and An appropriate amount within the range of weight% is determined by adding a homopolymer of ε-caprolactone or δ-valerolactone (A), a block copolymer of ε-caprolactone or δ-valerolactone with oxetane (B), and ε-caprolactone. Or a block copolymer (C) of δ-valerolactone and dimethyltrimethylene carbonate and poly (ε- (Lactone) or poly (δ-valerolactone) and poly (oxetane) in a biodegradable polymer mixture composition (D), and by considering the thickness etc., the biodegradation rate suitable for the application can be improved. You can choose.

Furthermore, the biodegradable net formed by weaving or braiding the biodegradable flat yarn according to the present invention is, for example, a homopolymer (A) of ε-caprolactone or δ-valerolactone (A), ε-caprolactone. Or a block copolymer (B) of δ-valerolactone and oxetane,
Block copolymer (C) of ε-caprolactone or δ-valerolactone and dimethyl trimethylene carbonate and poly (ε-caprolactone) or poly (δ
-Valerolactone) and poly (oxetane) and an aliphatic polyester (E) obtained by a dehydration polycondensation reaction of glycols and an aliphatic dicarboxylic acid with a biodegradable polymer mixture composition (D). Thereby, the homopolymer (A), the block copolymer (B), the block copolymer (C) and the biodegradable polymer mixture composition (D) described above, and the aliphatic polyester described above Due to a synergistic effect with (E), the homopolymer (A), the block copolymer (B), the block copolymer (C) and the biodegradable polymer mixed composition (D) have the above-mentioned drawbacks. Adhesiveness, heat resistance, dimensional stability and the like are improved, and the biodegradability, tensile strength, dimensional stability and the like of the aliphatic polyester (E) tend to be improved.

Accordingly, the biodegradable flat yarn according to the present invention can be prepared from a homopolymer (A) of ε-caprolactone or δ-valerolactone, a block copolymer of ε-caprolactone or δ-valerolactone and oxetane ( B), block copolymer (C) of ε-caprolactone or δ-valerolactone and dimethyltrimethylene carbonate and biodegradability of poly (ε-caprolactone) or poly (δ-valerolactone) with poly (oxetane) At least one selected from the polymer mixture composition (D)
The seeds are molded from a composition containing an aliphatic polyester (E), heat resistance, stretchability are improved, heat setting is possible, and nets formed by weaving or braiding such flat yarns include: There is a tendency to be able to select the biodegradation rate.

For example, nets or the like woven or braided using the flat yarn formed with the composition according to the present invention have a tensile strength of 2.0 g / d or more and a tensile elongation of 20%.
As described above, the heat shrinkage (dimensional stability) at 80 ° C. × 30 seconds is 50% or less, and the biodegradation rate can be selected. It can be suitably used for a net for stabilizing the vegetation, a vegetation net for vegetation for fixing the ground and the like by entanglement with the roots of vegetation, and a breeding net for breeding turf and the like over the lawn.

The homopolymer (A), the block copolymer (B), the block copolymer (C) and the biodegradable polymer mixture composition (D) according to the present invention are added with a glycol and an aliphatic dicarboxylic acid. The composition obtained by mixing the aliphatic polyester (E) obtained by the dehydration polycondensation reaction with the above may be copolymerized with other monomers copolymerizable with the above copolymers, if necessary. The above-mentioned polymers may be mixed with each other or other biodegradable polymers or monomers other than the above-mentioned polymers, and there is no particular limitation.

Specifically, other copolymerizable monomers include, for example, cyclic ethers such as ethylene oxide, propylene oxide, oxetane (in the case of dimethyl trimethylene carbonate copolymer), tetrahydrofuran, dioxane and trioxane; β-propyrolactone, methylated caprolactone, ε-caprolactone (δ
Lactones such as valerolactone copolymer), δ-valerolactone (in the case of ε-caprolactone copolymer), lactides or glycolides of lactic acid dimer, and trimethylene carbonate, methyltrimethylene carbonate, dimethyl A cyclic carbonate such as trimethylene carbonate (in the case of an oxetane copolymer) can be exemplified. Examples of other biodegradable polymers include polylactones such as polylactic acid and polyglycolide, starch, cellulose and the like.

The homopolymer (A), the block copolymer (B), the block copolymer (C) and the biodegradable polymer mixture composition (D) constituting the biodegradable flat yarn according to the present invention A composition obtained by mixing at least one member selected from the group consisting of an aliphatic polyester (E) obtained by a dehydration polycondensation reaction between a glycol and an aliphatic dicarboxylic acid,
The method for preparing the biodegradable polymer mixture composition (D) comprising poly (ε-caprolactone) or poly (δ-valerolactone) and poly (oxetane) is not particularly limited, but a conventional polyolefin-based resin is used. Etc., for example, a method of blending with a ribbon blender, a Hensel mixer, a tumbler, etc., a method of using a kneader such as a kneader, a Banbury mixer, a roll, a single screw or twin screw extruder, etc. Can be exemplified.

The biodegradable flat yarn according to the present invention is not particularly limited, and may be formed by an appropriate method. Specifically, one selected from a homopolymer (A), a block copolymer (B), a block copolymer (C) and a biodegradable polymer mixture composition (D), and an aliphatic polyester ( A composition containing E) as an essential component was heated at a cylinder temperature of 1
Melting and kneading with a T-die extruder or an extruder provided with an annular die set at 30 to 230 ° C and a die temperature of 150 to 250 ° C, extruded and cooled to form a flat film (including a sheet) or a tubular film. I do. At this time, the tube-shaped film may be cut open to form a flat film, and there is no particular limitation.

The film obtained above is slit into a predetermined width (for example, 4 to 10 mm) using an appropriate slitter or the like, and is not particularly limited.
Using a roll at 100 ° C., for example, in a uniaxial direction or biaxial direction, preferably in a longitudinal direction (extrusion direction), a stretching ratio of 5
An example is a method of forming a biodegradable flat yarn by uniaxially stretching 10 times and then heat setting using a roll heated to a surface temperature of 20 to 150 ° C. At this time, a flat film (including a sheet) or a tubular film may be stretched, and then, if necessary, further stretched in a uniaxial direction and heat-fixed. The biodegradable flat yarn obtained above may be used, for example, as a yarn for weaving or braiding a net or the like, but may be twisted if necessary, and is not particularly limited.

The tensile strength, tensile elongation, and shrinkage of the biodegradable flat yarn according to the present invention may be appropriately set according to the application. For example, in the case of a net used for ground stabilization in revetment work, Tensile strength is 2.0 g / d or more, tensile elongation is 20 to 50%, and shrinkage is 0 to 5 at 80 ° C. × 30 seconds.
It is preferably 0%. Further, when used for vegetation nets of vegetation, the tensile strength is 2.0 g / d or more, the tensile elongation is 20 to 50%, and the shrinkage is 80 to 30 seconds at 0 to 5.
It is preferably 0%. Further, when used for breeding nets for lawns, the tensile strength is 2.0 g / d or more, the tensile elongation is 20 to 50%, and the shrinkage is 80 to 30 seconds at 0 to 5.
It is preferably 0%.

When a net or the like is formed by using the biodegradable flat yarn according to the present invention, it is necessary to form a net or the like after forming into a woven or knitted fabric by, for example, plain weaving or Russell knitting by an appropriate method. For example, the present invention is not limited to this, and a net or the like may be formed by other methods.

For example, a net formed by using the biodegradable flat yarn according to the present invention has excellent strength, dimensional stability and biodegradability, and the biodegradation rate can be selected. It can be suitably used for stabilizing the ground in revetment work, for fixing the ground and the like by entanglement with the roots of plants and the like, and for spreading lawns on the lawns. Needless to say, even if the purpose of use is completed, it does not need to be collected, and if left as it is, it is decomposed into harmless water and carbon dioxide by microorganisms in the natural world. Therefore, nets formed from the biodegradable flat yarn according to the present invention may reduce the problem of environmental pollution.

[0044]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. However, the present invention is not limited only to the following examples.

Each test item in the following examples of the present invention was performed by the following method.

[Tensile strength]: Measured and evaluated according to JIS K-6782.

[Tensile elongation]: Measured and evaluated according to JIS K-6782.

[Shrinkage ratio]: To evaluate dimensional stability, circulating hot air in an oven set at 80 ° C.
The shrinkage upon heating for 0 seconds was measured.

[Biodegradability]: A biodegradable net having a predetermined weight was immersed in returned sludge collected and treated at a purification center (Konan Chubu Works, Shiga Sewerage Public Corporation), and after 9 weeks at 25 ° C. The remaining net was taken out, and the weight loss after washing with water and drying was measured.

Example 1 As a resin constituting the biodegradable flat yarn, ε-caprolactone homopolymer (number average molecular weight: 145,00
0) A composition comprising 50% by weight of (A) and 50% by weight of polybutylene succinate (number average molecular weight 16,000) was used. The above composition was heated at a cylinder temperature of 150.
-160 ° C., supplied to a T-die extruder set at a die temperature of 160 ° C., melt-kneaded, extruded, cooled and solidified to a thickness of 6
A 0 μm flat film was obtained. Next, after slitting the film to a width of 8 mm, the film was monoaxially stretched 7.0 times in a longitudinal direction using a heating roll having a surface temperature of 70 ° C.
A biodegradable flat yarn is formed by heat setting with a hot roll at 00 ° C, and the tensile strength, tensile elongation and heat shrinkage (80 ° C x
30 seconds) and the results are shown in Table 1. A net was formed by weaving using the biodegradable flat yarn, and the biodegradability was measured. The results are shown in Table 1.

[0051]

[Table 1]

Example 2 As a resin constituting the biodegradable flat yarn, a block copolymer comprising 60% by weight of ε-caprolactone and 40% by weight of oxetane (number-average molecular weight: 145,00
0) A biodegradable flat yarn was prepared in the same manner as in Example 1 except that 50% by weight of (B) and 50% by weight of polybutylene succinate (number average molecular weight 16,000) were blended. After molding, the tensile strength, tensile elongation and heat shrinkage (80 ° C. × 30 seconds) were measured and are shown in Table 1. A net was formed by weaving using the biodegradable flat yarn, and the biodegradability was measured. The results are shown in Table 1.

Example 3 As a resin constituting a biodegradable flat yarn, 60% by weight of ε-caprolactone and dimethyl tricarbonate 4 were used.
0% by weight (a number average molecular weight of 1).
45,000) (C) 50% by weight of polybutylene succinate (number average molecular weight 16,000) except that a composition obtained by blending 50% by weight was used in the same manner as in Example 1 except that a biodegradable flat was used. The yarn was formed, and the tensile strength, tensile elongation and heat shrinkage (80 ° C. × 30 seconds) were measured and the results are shown in Table 1. A net was formed by weaving using the biodegradable flat yarn, and the biodegradability was measured. The results are shown in Table 1.

Example 4 As a resin constituting the biodegradable flat yarn, ε-caprolactone homopolymer (number average molecular weight: 145,00
0) Biodegradable flat yarn in the same manner as in Example 1 except that a composition obtained by blending 70% by weight of polybutylene succinate (number average molecular weight 16,000) with 30% by weight of (A) is used. Was molded, and the tensile strength, tensile elongation and heat shrinkage (80 ° C. × 30 seconds) were measured.
A net was formed by weaving using the biodegradable flat yarn, and the biodegradability was measured. The results are shown in Table 1.

Example 5 As a resin constituting the biodegradable flat yarn, ε-caprolactone homopolymer (number average molecular weight: 145,00
0) 30% by weight of (A), 30% by weight of polybutylene succinate (number average molecular weight 16,000) and 40% by weight of polybutylene succinate / adipate copolymer (number average molecular weight 16,000) A biodegradable flat yarn was formed in the same manner as in Example 1 except that the composition was used, and the tensile strength, tensile elongation and heat shrinkage (8
(0 ° C. × 30 seconds) and the results are shown in Table 1. A net was formed by weaving using the biodegradable flat yarn, and the biodegradability was measured. The results are shown in Table 1.

Example 6 As a resin constituting the biodegradable flat yarn, ε-caprolactone homopolymer (number average molecular weight 145,00
0) A composition comprising 30% by weight of (A), 30% by weight of polybutylene succinate (number average molecular weight 16,000) and 40% by weight of polyethylene succinate (number average molecular weight 16,000). Except for the above, a biodegradable flat yarn was formed and the tensile strength, tensile elongation and heat shrinkage (80 ° C. × 30 seconds) were measured in the same manner as in Example 1 and the results are shown in Table 1. A net was formed by weaving using the biodegradable flat yarn, and the biodegradability was measured.
It was shown to.

Example 7 As a resin constituting the biodegradable flat yarn, ε-caprolactone homopolymer (number average molecular weight: 145,00
0) 45% by weight of (A), 45% by weight of polybutylene succinate (number average molecular weight 16,000) and 10% by weight of polybutylene succinate / adipate copolymer (number average molecular weight 16,000) A biodegradable flat yarn was formed in the same manner as in Example 1 except that the composition was used, and the tensile strength, tensile elongation and heat shrinkage (8
(0 ° C. × 30 seconds) and the results are shown in Table 2. A net was formed by weaving using the biodegradable flat yarn, and the biodegradability was measured and the results are shown in Table 2.

Example 8 As a resin constituting the biodegradable flat yarn, ε-caprolactone homopolymer (number average molecular weight: 145,00
0) 45% by weight of (A), 45% by weight of polybutylene succinate (number average molecular weight 145,000) and 1% of polyethylene succinate (number average molecular weight 145,000)
A biodegradable flat yarn is formed in the same manner as in Example 1 except that a composition containing 0% by weight is blended, and the tensile strength, tensile elongation and heat shrinkage (80 ° C. × 30 seconds) are measured. The results are shown in Table 2. A net was formed by weaving using the biodegradable flat yarn, and the biodegradability was measured. The results are shown in Table 2.

Example 9 As a resin constituting the biodegradable flat yarn, a biodegradable polymer mixed composition (D) composed of poly (ε-caprolactone) or poly (δ-valerolactone) and poly (oxetane) A biodegradable flat yarn was formed in the same manner as in Example 1 except that a composition obtained by mixing 50% by weight of polybutylene succinate (number average molecular weight 16,000) with 50% by weight was used. Table 2 shows the tensile strength, tensile elongation and heat shrinkage (80 ° C. × 30 seconds).
A net was formed by weaving using the biodegradable flat yarn, and the biodegradability is shown in Table 2.

Comparative Example 1 100% by weight of ε-caprolactone homopolymer was used as a resin constituting a biodegradable flat yarn;
A biodegradable flat yarn was formed in the same manner as in Example 1 except that the stretching roll temperature and the heat setting roll temperature were set to 30 ° C., and its tensile strength, tensile elongation and heat shrinkage (80%) were obtained.
C. × 30 seconds) are shown in Table 3. Further, a net was formed by weaving using the biodegradable flat yarn, and the biodegradability is shown in Table 3.

Comparative Example 2 A biodegradable flat yarn was produced in the same manner as in Example 1 except that 100% by weight of polybutylene succinate (number average molecular weight: 16,000) alone was used as a resin constituting the biodegradable flat yarn. The yarn was formed, and its tensile strength, tensile elongation and heat shrinkage (80 ° C. × 30 seconds) are shown in Table 3. Further, a net was formed by weaving using the biodegradable flat yarn, and the biodegradability is shown in Table 3.

Comparative Example 3 As the resin constituting the biodegradable flat yarn, 100 wt% of polybutylene succinate / adipate copolymer (number average molecular weight 16,000) alone was used;
A biodegradable flat yarn was formed in the same manner as in Example 1 except that the heat setting temperature was 90 ° C.
Table 3 shows the tensile elongation and the heat shrinkage (80 ° C. × 30 seconds). Further, a net was formed by weaving using the biodegradable flat yarn, and the biodegradability is shown in Table 3.

Comparative Example 4 A biodegradable flat yarn was prepared in the same manner as in Example 1 except that 100% by weight of polyethylene succinate (number average molecular weight: 16,000) alone was used as a resin constituting the biodegradable flat yarn. Was molded, and its tensile strength, tensile elongation and heat shrinkage (80 ° C. × 30 seconds) are shown in Table 3. Further, a net was formed by weaving using the biodegradable flat yarn, and the biodegradability is shown in Table 3.

As is clear from Tables 1 to 3, Examples 1 to
The flat yarn obtained from Comparative Example 9 did not melt at a low temperature (80 ° C.) as in Comparative Example 1, and did not dissolve in Comparative Examples 3 and 4.
Since the tensile strength is higher and the tensile elongation and the heat shrinkage (80 ° C. × 30 seconds) are smaller than those of Comparative Examples 1 to 4, the strength and dimensional stability are extremely excellent. Further woven (or braided) using the flat yarn obtained from Examples 1 to 9
The resulting biodegradable net is obtained by blending poly (ε-caprolactone) with one or a combination of polybutylene succinate, polybutylene succinate adipate and polyethylene succinate to form poly (ε
-Caprolactone) and polybutylene succinate adipate alone can be appropriately selected to have too high a rate of biodegradability.

[0065]

The biodegradable flat yarn according to the present invention has excellent strength, elongation, dimensional stability, heat resistance and moldability. Furthermore, nets formed by weaving or braiding using the biodegradable flat yarn, for example,
After completing its intended use, even if it is left in the natural environment, such as in soil or underwater, the whole is completely biodegraded by microorganisms in the natural world, and the biodegradation rate can be selected within a predetermined period. For example, it can be suitably used for a net for stabilizing the ground in revetment works, a vegetation vegetation net for stabilizing the ground by entanglement of the roots of vegetation, a net for covering lawns, etc., and breeding lawns.

[Table 2]

[Table 3]

Claims (10)

[Claims] 1. An aliphatic polyester (E) 80 obtained by a dehydration polycondensation reaction of 20 to 99% by weight of a homopolymer (A) of ε-caprolactone or δ-valerolactone with a glycol and an aliphatic dicarboxylic acid. A biodegradable flat yarn formed from a composition containing 1% by weight as an essential component. 2. An amount of 3.5 to 99.5% by weight of ε-caprolactone or δ-valerolactone and 96.5 to 5% of oxetane.
Aliphatic polyester (E) 80 obtained by a dehydration polycondensation reaction between a block copolymer (B) of 20 to 99% by weight of 0.5% by weight and a glycol and an aliphatic dicarboxylic acid.
A biodegradable flat yarn formed from a composition containing 1% by weight as an essential component. 3. A block copolymer (C) of 3.5 to 99.5% by weight of ε-caprolactone or δ-valerolactone and 96.5 to 0.5% by weight of dimethyltrimethylene carbonate in an amount of 20 to 99% by weight. And a aliphatic polyester (E) obtained by a dehydration polycondensation reaction between a glycol and an aliphatic dicarboxylic acid, and 80 to 1% by weight of the composition. 4. Poly (ε-caprolactone) or 72.5 to 97.5% by weight of poly (δ-valerolactone);
20-99% by weight of a biodegradable polymer mixture composition (D) comprising 27.5-2.5% by weight of poly (oxetane);
A biodegradable flat yarn formed from a composition containing, as an essential component, 80 to 1% by weight of an aliphatic polyester (E) obtained by a dehydration polycondensation reaction between a glycol and an aliphatic dicarboxylic acid. 5. A homopolymer of ε-caprolactone or δ-valerolactone (A), a block copolymer of ε-caprolactone or δ-valerolactone and oxetane (B), ε-caprolactone or δ-valerolactone. The number average molecular weight of the block copolymer (C) with dimethyltrimethylene carbonate is 1,000 to 1,000,
The biodegradable flat yarn according to any one of claims 1 to 4, which has a range of 000. 6. The glycols constituting the aliphatic polyester (E) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, decamethylene glycol, neopentyl glycol and 1,4-cyclohexane. The biodegradable flat yarn according to any one of claims 1 to 4, which is at least one member selected from the group consisting of dimethanol. 7. The aliphatic dicarboxylic acid constituting the aliphatic polyester (E) is one selected from the group consisting of succinic acid, adipic acid, suberic acid, sebacic acid, dodecanoic acid, succinic anhydride and adipic anhydride. The biodegradable flat yarn according to any one of claims 1 to 4, which is of two or more types. 8. The biodegradable flat yarn according to claim 1, wherein the aliphatic polyester (E) has a number average molecular weight of 5,000 or more. 9. Tensile strength of 2.0 g / d or more, tensile elongation of 20% or more and 50% or less, shrinkage rate (80 ° C. × 30 seconds)
The biodegradable flat yarn according to any one of claims 1 to 4, wherein the ratio is 5.0% or less and a biodegradation rate is selectable. 10. The biodegradable flat yarn according to claim 1, which is woven or braided in a biodegradable net.