JP2752881B2 - Polyester tape - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tape formed of an aliphatic polyester having biodegradability, a practically sufficient high molecular weight and specific melting properties, and having excellent tensile strength and knot strength. It is about.

[0002]

2. Description of the Related Art In recent years, plasticization of packaging materials and agricultural materials has been progressing with the progress of distribution systems and automation of agricultural work, and the waste of plastics used in large quantities has contaminated rivers, the ocean, and soil. In order to prevent this pollution, the emergence of biodegradable plastics has been anticipated, and for example, poly (3- (3-) produced by a fermentation method using microorganisms has been expected.
A blend of starch (hydroxybutyrate) or a blend-type natural polymer with a general-purpose plastic is known. However, in the former, the thermal decomposition temperature of the polymer is close to the melting point, so the moldability is inferior and microorganisms create it.
The raw material unit has a very bad disadvantage. In the latter, since the natural polymer itself is not thermoplastic, there is a difficulty in moldability, and the use range is greatly restricted. On the other hand, although aliphatic polyesters are known to have biodegradability, they have hardly been used because a high molecular weight product sufficient for obtaining practical molded article properties cannot be obtained. Recently,
It has been found that ε-caprolactone has a high molecular weight by ring-opening polymerization, and it has been proposed as a biodegradable resin. . Glycolic acid and lactic acid can also be used for medical fibers, etc., because of their high molecular weight obtained by ring-opening polymerization of glycolide and lactide. It has not been used in large quantities for materials and agricultural materials.

[0003] As one of the packaging materials and agricultural materials which are required to have corrosion resistance and high strength, for example, binding tapes and tapes with a crease (hereinafter collectively referred to as tapes) are high-density polyolefins. The main material is polyethylene or polypropylene resin. Tapes are often used as packing strings, binder tapes for automatic tying, and packing applications, and tapes with streaks are used as tying strings and ropes for packing, agriculture, construction, and forestry. Polyester-based polyethylene terephthalate, polypropylene terephthalate, and the like are used for high-strength applications for special applications. However, the high-molecular-weight polyester used in the molded article (the high-molecular-weight polyester referred to herein has a number average molecular weight of 10 Is not limited to polyethylene terephthalate, which is a condensate of terephthalic acid (including dimethyl terephthalate) and ethylene glycol. In some cases, 2,6-naphthalenedicarboxylic acid is used in place of terephthalic acid, but no attempt has been made to impart biodegradability at present. Therefore, conventionally,
Using aliphatic type dicarboxylic acid, using an aliphatic polyester having biodegradability, forming a tape,
It can be said that there is no idea of practical use.

[0004] One of the reasons why this idea of practical use has not been born is that even if the tape is required to have special molding conditions and physical properties of the molded product, even if the tape is crystalline,
Most of the aliphatic polyesters have a melting point of 100 ° C. or lower, and furthermore, have poor thermal stability upon melting, and more importantly, the properties of aliphatic polyesters, especially properties represented by tensile strength. However, even at the same level of the number average molecular weight as the above polyethylene terephthalate, the compound showed a remarkably inferior value, and it is considered that it was difficult to make a concept of obtaining a molded product requiring strength or the like. It is presumed that one of the reasons is that the study for increasing the number average molecular weight of the aliphatic polyester to improve the physical properties has not sufficiently progressed due to the poor thermal stability.

[0005]

The present invention uses these aliphatic polyesters as components, has a practically sufficient high molecular weight, has excellent mechanical properties represented by tensile strength, Biodegradability as one of the disposal means,
That is, an object of the present invention is to provide a tape which can be decomposed by microorganisms or the like and which can be easily disposed after use.

[0006]

The present inventors have studied various reaction conditions for obtaining a polyester having a high molecular weight and sufficient practicality and having a tape formability. A specific aliphatic polyester having a practically sufficient high molecular weight was obtained, and a tape molded therefrom was found to have not only the above-mentioned biodegradability but also excellent thermal stability and mechanical strength. It was completed.

That is, the gist of the present invention is obtained by reacting a coupling agent with an aliphatic polyester prepolymer synthesized mainly from glycols and an aliphatic dicarboxylic acid (excluding a hydroxyl group-containing dicarboxylic acid). The melt viscosity at a temperature of 190 ° C. and a shear rate of 100 sec ⁻¹ is 1 × 10 ³ to 4 × 10 ⁴ poise, and after uniaxial stretching after extrusion molding using an aliphatic polyester having a melting point of 70 to 190 ° C. as a main component. It is on the tape.

The aliphatic polyester referred to in the present invention includes glycols and aliphatic dicarboxylic acids (or their anhydrides).
And a polyester prepolymer having a relatively high molecular weight having a hydroxyl group at the terminal of the molecule, which is further increased in molecular weight by a coupling agent.

Conventionally, a low molecular weight polyester prepolymer having a number average molecular weight of 2,000 to 2,500, whose terminal group is a hydroxyl group, is reacted with diisocyanate as a coupling agent to form polyurethane, rubber, Foams, paints and adhesives are widely used.

However, polyester prepolymers used for these polyurethane foams, paints and adhesives are low-molecular-weight prepolymers having a maximum number average molecular weight of 2,000 to 2,500 which can be synthesized without a catalyst. With respect to 100 parts by weight of the low molecular weight prepolymer,
In order to obtain practical physical properties as a polyurethane, the amount of diisocyanate used must be as large as 10 to 20 parts by weight.
When added to a molten low molecular weight polyester above ℃
It gels and ordinary melt-moldable resins cannot be obtained. Therefore, a polyester obtained by using such a low-molecular-weight polyester prepolymer as a raw material and reacting a large amount of diisocyanate cannot be used as a raw material for a tape of the present invention.

As in the case of polyurethane rubber, a method of converting a hydroxyl group into an isocyanate group by adding a diisocyanate and further increasing the number average molecular weight with a glycol may be considered. As described above, the amount is 10 parts by weight or more based on 100 parts by weight of the prepolymer, so that practical properties are obtained. If a polyester prepolymer having a relatively high molecular weight is to be used, the heavy metal catalyst required for the synthesis of the prepolymer significantly promotes the reactivity of the isocyanate group used in the above amount, resulting in poor storage stability, crosslinking reaction, and branching. Since it is not preferable to use a polyester prepolymer synthesized without a catalyst as a polyester prepolymer, the number average molecular weight is limited to about 2,500 at the highest even if it is high.

The polyester prepolymer for obtaining the aliphatic polyester used in the present invention has a relatively high molecular weight as described above containing a synthesis catalyst,
A saturated aliphatic polyester having a terminal group substantially a hydroxyl group, a relatively high molecular weight having a number average molecular weight of 5,000 or more, preferably 10,000 or more, and a melting point of 60 ° C. or more; And a polybasic acid (or an anhydride thereof) in a catalytic reaction. When the number average molecular weight is less than 5,000, the number average molecular weight of 0.1 to
With a small amount of the coupling agent of 5 parts by weight, a polyester for tape having good physical properties cannot be obtained.
A polyester prepolymer having a number average molecular weight of 5,000 or more has a hydroxyl value of 30 or less, and is not affected by the remaining catalyst even under severe conditions such as a molten state by using a small amount of a coupling agent. A high molecular weight polyester can be synthesized without generating a gel therein.

That is, the polymer constituting the tape of the present invention has a number average molecular weight (Mn) comprising an aliphatic glycol and an aliphatic dicarboxylic acid of 5,000 or more, preferably 1 or more.
The polyester prepolymer having a melting point of 60 ° C. or more and a molecular weight of 000 or more has a structure linked via a urethane bond derived from, for example, a diisocyanate as a coupling agent. Furthermore, the polymer constituting the tape of the present invention is such that the polyester prepolymer has a long-chain branch derived from a polyfunctional component, and this is, for example, via a urethane bond derived from diisocyanate as a coupling agent. It has a chained structure. When an oxazoline, a diepoxy compound, or an acid anhydride is used as a coupling agent, the polyester prepolymer takes a chain structure via an ester bond.

The glycols used include, for example, ethylene glycol, 1,4-butanediol, 1,6
-Hexanediol, decamethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol and the like. Ethylene oxide can also be used. These glycols may be used in combination.

Aliphatic dicarboxylic acids (or acid anhydrides thereof) which react with glycols to form aliphatic polyesters include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanoic acid, succinic anhydride, and succinic anhydride. Adipic acid and the like are generally commercially available and can be used in the present invention. Aliphatic dicarboxylic acids (or their acid anhydrides) may be used in combination.

(Third component) In addition to these glycols and dicarboxylic acids, if necessary, as a third component, a trifunctional or tetrafunctional polyhydric alcohol or oxycarboxylic acid (provided that a hydroxy group is contained) At least one polyfunctional component selected from polycarboxylic acids (excluding dicarboxylic acids) and polycarboxylic acids (or acid anhydrides thereof) may be added and reacted. By adding this third component, long-chain branching occurs in the molecule, so that the molecular weight increases and Mw / Mn increases, that is, the molecular weight distribution increases, and desirable properties are imparted to film forming and the like. be able to. The amount of the polyfunctional component to be added is 0.1% in the case of trifunctionality with respect to 100% by mole of the total components of the aliphatic dicarboxylic acid (or its anhydride) so as not to cause a danger of gelling. ~ 5 mol%, 4
In the case of a functional case, it is 0.1 to 3 mol%.

The trifunctional polyhydric alcohol component is typically trimethylolpropane, glycerin or its anhydride, and the tetrafunctional polyhydric alcohol component is typically pentaerythritol.

The trifunctional oxycarboxylic acid component has one carboxyl group and two hydroxyl groups in the same molecule. There are the following two types of tetrafunctional oxycarboxylic acid components. That is, (i) a type sharing three carboxyl groups and one hydroxyl group in the same molecule, and (ii) a type sharing three hydroxyl groups and one carboxyl group in the same molecule. Yes, any type can be used, but citric acid is practically advantageous from the viewpoint that a commercially available product is easily available at low cost, and is sufficient for the purpose of the present invention.

As the trifunctional polycarboxylic acid (or acid anhydride) component, for example, trimesic acid, propanetricarboxylic acid and the like can be used, but trimellitic anhydride is advantageous from a practical viewpoint. Is sufficient for the purpose. Tetrafunctional polycarboxylic acid (or its acid anhydride)
There are various types such as aliphatic, cycloaliphatic, and aromatic in the literature, but from the viewpoint that commercially available products can be easily obtained, for example, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, cyclopentane Tetracarboxylic anhydrides are mentioned and are sufficient for the purposes of the present invention.

These glycols and aliphatic dicarboxylic acids are mainly composed of aliphatic compounds, but may be used in combination with a small amount of other components such as aromatic compounds. However, if other components are introduced, the biodegradability deteriorates, so the content is 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less. The terminal group of the polyester prepolymer for aliphatic polyester used in the present invention is substantially a hydroxyl group. For this purpose, use of glycols and aliphatic dicarboxylic acids (or acid anhydrides thereof) used in the synthesis reaction is required. The proportions require the use of some excess glycols.

In order to synthesize a polyester prepolymer having a relatively high molecular weight, it is necessary to use a deglycol-reaction catalyst during the deglycolization reaction following the esterification.

Examples of the deglycol-reaction catalyst include titanium compounds such as acetoacetoyl-type titanium chelate compounds and organic alkoxytitanium compounds.
These titanium compounds can be used in combination. Examples of these include diacetacetoxyoxytitanium ("Narcem Titanium" manufactured by Nippon Chemical Industry Co., Ltd.), tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium and the like. The use ratio of the titanium compound is 0.00% with respect to 100 parts by weight of the polyester prepolymer.
The amount is 1 to 1 part by weight, preferably 0.01 to 0.1 part by weight. The titanium compound may be added from the beginning of the esterification, or may be added immediately before the deglycolization reaction.

Further, the number average molecular weight is 5,000 or more,
Desirably, a coupling agent is used to further increase the number average molecular weight of the polyester prepolymer in which 10,000 or more terminal groups are substantially hydroxyl groups. Examples of the coupling agent include diisocyanates, oxazolines, diepoxy compounds, acid anhydrides, and the like.
Particularly, diisocyanate is preferable. In the case of an oxazoline or diepoxy compound, it is necessary to react a hydroxyl group with an acid anhydride or the like and convert the terminal to a carboxyl group before using a coupling agent. The type of diisocyanate is not particularly limited.
4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-
Naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, in particular, hexamethylene diisocyanate,
It is preferable from the viewpoint of the hue of the formed resin, the reactivity at the time of adding the polyester and the like.

The amount of the coupling agent to be added is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight based on 100 parts by weight of the polyester prepolymer. If the amount is less than 0.1 part by weight, the coupling reaction is insufficient, and if it exceeds 5 parts by weight, gelation is liable to occur.

The addition is desirably carried out under conditions in which the polyester prepolymer is in a homogeneous molten state and can be easily stirred. It is not impossible to add to the solid polyester prepolymer and melt and mix through an extruder, but it is added to the aliphatic polyester production equipment or to the molten polyester prepolymer (for example, in a kneader). It is practical to do.

The aliphatic polyester used in the present invention requires specific melting properties in order to be extruded into a tape. That is, temperature 190 ° C., shear rate 1
The melt viscosity at 00 sec ^-1 is 1 × 10 ³ to 4 × 10
^{It is 4} poise, preferably 6 × 10 ^{3 to} 3 × 10 ⁴ poise and 1 × 10 ⁴ to 2 × 10 ⁴ poise.
If it is less than 1 × 10 ³ poise, the molding stability becomes poor, and the raw material of the binding tape becomes uneven in thickness, and the stretching becomes uneven and denier becomes uneven. On the other hand, if it exceeds 4 × 10 ⁴ poise, melt fracture occurs, and the tape surface becomes worse, and stretching unevenness occurs due to unstable ejection. The melt viscosity was measured at a shear rate of 100 sec ^-1 from a graph of the relationship between the shear rate measured at a resin temperature of 190 ° C. and the apparent viscosity using a nozzle having a nozzle diameter of 1.0 mm and a nozzle of L / D = 10. The viscosity was determined.

Further, the melting point of the aliphatic polyester used in the present invention needs to be 70 to 190 ° C., more preferably 70 to 150 ° C., and particularly preferably 80 to 135 ° C. If it is lower than 70 ° C., the heat resistance is insufficient, and if it is higher than 190 ° C., it is difficult to manufacture.
In order to obtain a melting point of 70 ° C. or more, the melting point of the polyester prepolymer needs to be 60 ° C. or more.

When the aliphatic polyester used in the present invention contains a urethane bond, the amount of the urethane bond is 0.03 to 3.0% by weight, preferably 0.05 to 2.0% by weight, 0.1 to 1.0% by weight is particularly preferred. The urethane bond amount is measured by C ₁₃ NMR and agrees well with the charged amount. When the amount is less than 0.03% by weight, the effect of increasing the molecular weight by urethane bonds is small, and the moldability is poor. When the amount exceeds 3.0% by weight, a gel is generated.

When the above-mentioned aliphatic polyester is used for forming the tape according to the present invention, a lubricant, an anti-blocking agent, a light stabilizer, etc. may be used, if necessary, in addition to an antioxidant, a heat stabilizer, an ultraviolet absorber and the like. Of course, antibacterial agents, flame retardants, antistatic agents, waxes, coloring agents, fillers and the like can be used in combination. That is, as an antioxidant, pt
-Butylhydroxytoluene, hindered phenolic antioxidants such as pt-butylhydroxyanisole,
Examples of heat stabilizers such as sulfur antioxidants such as distearyl thiodipropionate and dilauryl thiodipropionate, and heat stabilizers such as triphenyl phosphite, trilauryl phosphite, and trisnonyl phenyl phosphite; , Pt-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone, etc., as lubricants, calcium stearate, zinc stearate, barium stearate, sodium palmitate, etc., as antistatic agents, Hexabromocyclododecane, tris (2,3-dichloropropyl) phosphate, pentabromophenyl allyl ether as a flame retardant such as N, N-bis (hydroxyethyl) alkylamine, alkylamine, alkylallyl sulfonate, alkyl sulfonate, etc. Such as inorganic filler,
As a crystallization accelerator, such as calcium carbonate, silica, titanium oxide, talc, mica, barium sulfate, and alumina,
Polyethylene terephthalate, poly-trans-cyclohexane dimethanol terephthalate, and the like.

The raw material mainly composed of the aliphatic polyester used in the present invention can be made into a tape by extruding the raw material. Tapes include binding tapes and creased tapes. They are,
Usually, it can be manufactured as follows.

(1) Manufacture of binding tape In the present invention, the binding tape has a thickness of 3,000 denier or more, and is made of a material mainly composed of an aliphatic polyester using a circular die, a T die, or the like. And then stretching after melt extrusion using a molding machine. The extrusion temperature is generally between 170 ° C. and 230
° C, preferably 180 ° C to 210 ° C. This 230
When the temperature exceeds ℃, gel is generated, which causes unstretched and snake balls. It may be melt-extruded into a film or directly extruded into a tube with a circular die. After cooling and solidifying, the film is slit into a ribbon shape, stretched, and subjected to relaxation heat treatment. In the melt extrusion, for the purpose of satisfying the physical properties of the binding tape and the like, a multilayer binding tape formed by laminating the polyester and another resin in two or three layers and co-extruding is also possible. The stretching method may be a wet stretching, a dry stretching, that is, an ordinary hot stretching in a bath, a steam hot roll, or an oven hot plate, and the stretching can be performed at a high stretching ratio of 3 to 9 times, preferably 4 to 8 times. The stretching method may be one-stage stretching or two-stage stretching.

The stretching temperature is 40 ° C. to 130 ° C., preferably 60 ° C. to 100 ° C., and the two-stage stretching is 30% of the total stretching ratio.
-90%, preferably stretched in the range of 60% -85%,
Second stage: 80 ° C to 120 ° C, preferably 90 ° C to 1 ° C
00 ° C. Stretching is performed in the range of 70% to 10%, preferably 40% to 15% of the total stretching ratio. One stage temperature is 40
Stretching is possible even at a temperature of less than or equal to ° C, but the fiber separation resistance is lowered and it is easily broken. If the temperature exceeds 100 ° C., uneven stretching occurs. Further, the relaxation heat treatment is performed at 90 ° C to 140 ° C, preferably at 110 ° C to 1 ° C.
50 ° C is good. The relaxation rate is preferably 5% to 30%, and more preferably 10% to 20%. Relaxation heat treatment temperature is 90 ° C
If it is less than 5% or the relaxation rate is less than 5%, the binding tape temporal shrinkage rate increases. Conversely, if the former exceeds 140 ° C. or the latter exceeds 30%, the tape shape becomes kelp-like and the winding appearance deteriorates.

The aliphatic polyester having a number average molecular weight of 10,000 or more, desirably 20,000 or more according to the present invention can be formed into a tough binding tape as long as it has a melting point of 70 ° C. to 190 ° C. or more and is crystalline. It can be used as packaging and packing materials such as tied strings and agricultural materials.

(2) Production of Tape with Polyester Crease The tape with polyester crease of the present invention is obtained by molding a raw material containing a high molecular weight crystalline aliphatic polyester as a main component by a molding method such as an inflation method or a T-die method. After being extruded from a creased die to form a film, the film slit to an appropriate width is stretched by a hot plate, an oven, a hot roll, or the like to form a creased tape. Extrusion temperature is 120-260
° C, preferably 130 to 240 ° C. If the temperature is lower than 120 ° C., the surface of the film tends to be rough, and if the temperature exceeds 260 ° C., the shaking of the film becomes large and stable molding cannot be performed.
The stretching temperature is from 30 to 160 ° C, preferably from 40 to 150 ° C.
° C. The stretching ratio is 3 to 7 times. The shape of the streak is U
The height, width, and interval of the streak may be determined as appropriate.

[0035]

The present invention will be described below with reference to examples and comparative examples.

Example 1 A 700 L reactor was replaced with nitrogen, and 183 kg of 1,4-butanediol and 224 kg of succinic acid were charged. Raise the temperature under a nitrogen stream and
3.5 hours at 92-220 ° C.
The esterification reaction by dehydration condensation was performed for 3.5 hours under reduced pressure of 0 to 2 mmHg. The collected sample had an acid value of 9.2 mg / g and a number average molecular weight (Mn) of 5,16.
0, and the weight average molecular weight (Mw) was 10,670. Subsequently, 34 g of tetraisopropoxy titanium as a catalyst was added under a nitrogen stream at normal pressure. The temperature was increased, and a deglycol-reaction was performed at a temperature of 215 to 220 ° C. and a reduced pressure of 15 to 0.2 mmHg for 5.5 hours. The collected sample had a number average molecular weight (Mn) of 16,800 and a weight average molecular weight (Mw) of 43,600. The yield of this polyester (A1) was 339 kg excluding condensed water.

To a reactor containing 339 kg of polyester (A1), 5.42 kg of hexamethylene diisocyanate was added, and a coupling reaction was carried out at 180 to 200 ° C. for 1 hour. The viscosity increased rapidly but no gelling occurred. Then, Irganox 1010 was used as an antioxidant.
1.70 kg (manufactured by Ciba Geigy) and 1.70 kg of calcium stearate as a lubricant were added.
Stirring was continued for another 30 minutes. This reaction product was extruded into water with an extruder and cut into a pellet by a cutter. The yield of the polyester (B1) after vacuum drying at 90 ° C. for 6 hours was 300 kg.

The obtained polyester (B1) is a slightly ivory white wax-like crystal having a melting point of 110.
° C, the number average molecular weight (Mn) is 35,500, the weight average molecular weight (Mw) is 170,000, the MFR (190 ° C) is 1.0 g / 10 min, the viscosity of a 10% solution of orthochlorophenol is 230 poise, Temperature 190 ° C, shear rate 10
The melt viscosity at ⁰ sec ^-1 was 1.5 × 10 ⁴ poise. The average molecular weight is measured by Shodex GPC
System-11 (manufactured by Showa Denko KK, gel chromatography), solvent: CF ₃ COONa, HFIPA 5 mm
ol solution, concentration 0.1% by weight, calibration curve is Showa Denko KK
PMMA standard sample Shodex Standard
d Performed on M-75.

The polyester (B1) was dried at 120 ° C. for 3 hours using a hot-air circulating drier having a dew point adjustment type, and then extruded into a 90φ extruder using a T-die having a die width of 1200 m / m and a lip gap of 0.7 m / m. Using an apparatus, the extruded sheet was cooled and solidified by a water-cooled chill roll to form an original sheet. The raw sheet was slit to a width of 20 m / m, stretched by a hot plate, and subjected to relaxation heat treatment. Stretching was performed at a magnification of 4.5 times, at a temperature of 90 ° C., at a relaxation temperature of 120 ° C., at a relaxation rate of 10%, and at a stretching speed of 80 m / min. The physical properties of the obtained binding tape were 4.3 g / d in tensile strength, which was sufficient for practical use. Hereinafter, production conditions of Examples and Comparative Examples, appearance evaluation,
Table 1 summarizes the physical property results of the obtained binding tape.
In addition, the physical properties such as the tensile speed were measured by the measuring method of JIS Z1533. When this binding tape was buried in the soil for 5 months, it was decomposed to a strength unsuitable for practical use.

(Examples 2 to 3) A binding tape was manufactured under the same conditions as in Example 1 except that the yarn width and the denier were changed. Table 1 shows the physical properties of the binding tape. The result of embedding the binding tape in the soil for 5 months was the same as in Example 1.

Example 4 A 700 L reactor was purged with nitrogen and charged with 177 kg of 1,4-butanediol, 198 kg of succinic acid and 25 kg of adipic acid. The temperature was raised under a nitrogen stream, and the temperature was increased to 190 to 210 ° C. for 3.5 hours.
2. Further stop nitrogen, and under a reduced pressure of 20 to 2 mmHg.
The esterification reaction by dehydration condensation was performed for 5 hours. The collected sample had an acid value of 9.6 mg / g, a number average molecular weight (Mn) of 6,100, and a weight average molecular weight (M
w) was 12,200. Subsequently, 20 g of a catalyst, tetraisopropoxytitanium, was added under a nitrogen stream at normal pressure. Raise the temperature, 15 ~
The glycol removal reaction was performed under a reduced pressure of 0.2 mmHg for 6.5 hours. The collected sample is number average molecular weight (Mn)
Is 17,300, and the weight average molecular weight (Mw) is 46,
400. The yield of this polyester (A2) was 337 kg excluding condensed water.

To a reactor containing 333 kg of polyester (A2), 4.66 kg of hexamethylene diisocyanate was added, and a coupling reaction was carried out at 180 to 200 ° C. for 1 hour. The viscosity increased rapidly but no gelling occurred. Then, Irganox 1010 was used as an antioxidant.
1.70 kg (manufactured by Ciba Geigy) and 1.70 kg of calcium stearate as a lubricant were added.
Stirring was continued for another 30 minutes. This reaction product was extruded into water with an extruder and cut into a pellet by a cutter. The yield of the polyester (B2) after vacuum drying at 90 ° C. for 6 hours was 300 kg.

The obtained polyester (B2) is a slightly ivory white wax-like crystal having a melting point of 103.
° C, number average molecular weight (Mn) is 36,000, weight average molecular weight (Mw) is 200,900, MFR (190 ° C) is 0.52 g / 10 min, and 10% of orthochlorophenol.
The solution has a viscosity of 680 poise, a temperature of 190 ° C. and a shear rate of 1.
The melt viscosity at 00 sec ^-1 was 2.2 × 10 ⁴ poise.

The polyester (B2) was formed into an extruded fabric in the same manner as in Example 1 and stretched and relaxed in the same manner as in Example 1 to obtain a polyester (B2).
A binding tape with a width of 0 m / m and 12000 denier was manufactured. The tensile strength was 4.5 g / d, which was very tough. Table 1 shows the physical properties of the binding tape. When this binding tape was buried in the soil for 5 months, it was decomposed to a strength that would not withstand practical use.

(Examples 5 to 6) A binding tape was manufactured under the same conditions as in Example 1 except that the denier was changed. When the binding tape obtained here was buried in the soil for 5 months, it was disassembled into a binding band having no practical use.

Example 7 A 700 L reactor was purged with nitrogen, and then 145 kg of ethylene glycol and succinic acid 2 were added.
51 kg and 4.1 kg of citric 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 had an acid value of 8.8 mg / g, a number average molecular weight (Mn) of 6,800, and a weight average molecular weight (Mw) of 13,500. Subsequently, 20 g of a catalyst, tetraisopropoxytitanium, was added under a nitrogen stream at normal pressure.
Raise the temperature to 15-0.2 at a temperature of 210-220 ° C.
The glycol removal reaction was performed under reduced pressure of mmHg for 4.5 hours. The sample collected had a number average molecular weight (Mn) of 3
3,400, and a weight average molecular weight (Mw) of 137,0
00. The yield of this polyester (A3) was 323 kg excluding condensed water.

3.23 kg of hexamethylene diisocyanate was added to a reactor containing 323 kg of polyester (A3), and a coupling reaction was carried out at 180 to 200 ° C. for 1 hour. The viscosity increased rapidly but no gelling occurred. Then, Irganox 1010 was used as an antioxidant.
1.62 kg (manufactured by Ciba-Geigy) and 1.62 kg of calcium stearate as a lubricant were added.
Stirring was continued for another 30 minutes. This reaction product was extruded into water with an extruder and cut into a pellet by a cutter. The yield of the polyester (B3) after vacuum drying at 90 ° C. for 6 hours was 300 kg.

The obtained polyester (B3) is a slightly ivory-like white wax-like crystal having a melting point of 96 ° C.
The number average molecular weight (Mn) is 54,000, the weight average molecular weight (Mw) is 324,000, and the MFR (190 ° C.) is 1.
1 g / 10 min, viscosity of a 10% solution of orthochlorophenol is 96 poise, temperature 190 ° C., shear rate 100 sec.
The melt viscosity at c ^-1 was 1.6 × 10 ⁴ poise.

A binding tape was produced from the polyester (B3) under the same conditions as in Example 1. The tensile strength of the obtained binding tape was 4.8 g / d, which was a very strong binding tape. When this binding tape was buried in the soil for 5 months, it was decomposed to a strength unusable for use.

Example 8 A 700 L reactor was purged with nitrogen, and then 200 kg of 1,4-butanediol, 250 kg of succinic acid and 2.8 kg of trimethylolpropane were used.
Was charged. The temperature was raised under a nitrogen stream,
At 4.5 ° C. for 4.5 hours, and further stop nitrogen for 20 to 2 mmH.
The esterification reaction by dehydration condensation was performed under reduced pressure of 5.5 g for 5.5 hours. The collected sample has an acid value of 10.
The number average molecular weight (Mn) was 4,900, and the weight average molecular weight (Mw) was 10,000. Subsequently, 37 g of tetraisopropoxytitanium as a catalyst was added under a nitrogen stream at normal pressure. Raise the temperature to 210
8.0 to 220 ° C. under reduced pressure of 15 to 1.0 mmHg.
The deglycol reaction was performed for a time. The collected sample had a number average molecular weight (Mn) of 16,900 and a weight average molecular weight (Mw) of 90,300. (Mw / Mn =
5.4). The yield of this polyester (A4) was 367 kg theoretically excluding 76 kg of condensed water.

To a reactor containing 367 kg of polyester (A4), 3.67 kg of hexamethylene diisocyanate was added, and a coupling reaction was carried out at 160 to 200 ° C. for 1 hour. The viscosity increased rapidly but no gelling occurred. Then, Irganox 1010 was used as an antioxidant.
367 g (manufactured by Ciba-Geigy) and 367 g of calcium stearate as a lubricant were added, and the mixture was further added with 30 g.
Stirring was continued for minutes. This reaction product was extruded into water with an extruder and cut into a pellet by a cutter. The yield of the polyester (B4) after vacuum drying at 90 ° C. for 6 hours was 350 kg.

The obtained polyester (B4) is a slightly ivory white wax-like crystal having a melting point of 110.
° C, the number average molecular weight (Mn) is 17,900, and the weight average molecular weight (Mw) is 161,500 (Mw / Mn = 9.
0), the MFR (190 ° C.) was 0.21 g / 10 min, the temperature was 180 ° C., and the melt viscosity at a shear rate of 1000 sec ⁻¹ was 2.0 × 10 ⁴ poise. The average molecular weight was measured by Shodex GPC System-11 (gel chromatography manufactured by Showa Denko KK), and the solvent was CF _3.
A 2 mmol solution of COONa in HIPPA, a concentration of 0.1% by weight, and a calibration curve were performed with a PMMA standard sample Shodex Standard M-75 manufactured by Showa Denko KK.

The polyester (B4) was dried at 120 ° C. for 3 hours using a hot air circulating drier of dew point control type, and then extruded into a 90φ extruder with a die width of 1200 m / m and a lip gap of 0.7 m / m. Using an apparatus, the extruded sheet was cooled and solidified by a water-cooled chill roll to form an original sheet. This material was slit to a width of 20 m / m, stretched by a hot plate, and subjected to a relaxation heat treatment. Stretching was performed at a magnification of 4.5 times, at a temperature of 90 ° C., at a relaxation temperature of 120 ° C., at a relaxation rate of 10%, at a stretching speed of 80 m / m minutes, at a width of 10 m / m, and with a denier of 10,000 denier. The physical properties of the obtained binding tape were 4.0 g / d in tensile strength, which was sufficient for practical use.

(Comparative Example 1) The extrusion temperature condition in Example 1 was set to 1
The temperature was changed to 80 ° C. The motor amp soared, and after a while, the raw fabric became rough and surging occurred. The film was stretched by slitting, but the breaking was stopped.

(Comparative Example 2) Example 1 The total magnification of stretching was set to 3 times. Unstretching occurred, but stretching was possible. However, there were many ayaku in the roll.

(Comparative Example 3) The polyester (A1) was molded under the same production conditions as in Example 1, but was cut in the middle of stretching, and the desired binding tape could not be obtained.

(Comparative Example 4) The polyester (A2) synthesized in Example 4 was used. Polyester (A2) was molded under the same conditions as in Example 1, but was cut by a factor of 4 during stretching.
The desired binding tape could not be obtained.

Comparative Example 5 The polyester (A3) synthesized in Example 7 was used. Polyester (A3) was molded under the same conditions as in Example 1, but was cut by a factor of 4 during stretching.
The desired binding tape could not be obtained.

(Comparative Example 6) The film was stretched only in the bath under the conditions of Example 1, and the total magnification was 4.5 times, and the temperature was lowered by 20 ° C to 70 ° C. The neck point was shifted from the bathtub to the rear, causing uneven yarn stretching. The tensile strength was 2.8 g / d.

Example 9 The polyester (B1) obtained in Example 1 was molded at a molding temperature of 190.degree.
After extruding from a die to form a film, slit it to a width of 200 mm and stretch 5 times with a hot plate stretching machine at 70 ° C.
A 00 denier tape was produced. The shape of the streak is U
A mold having a depth of 0.8 mm, a lip gap of 0.8 mm, and a streak spacing of 2.5 mm was used. The obtained tape with a crease had a tensile strength of 4.6 g / d, had a volume, and was excellent in a soft feeling. When the striped tape was buried in the soil for 5 months, the tape was decomposed and changed to an impractical strength.

Example 10 A striped tape was produced under the same conditions as in Example 9 except that the polyester (B1) obtained in Example 1 was stretched at 80 ° C. The obtained tape with a crease had a tensile strength of 4.2 g / d, had a volume, and was excellent in a soft feeling. When the striped tape was buried in soil for 5 months, the tensile strength was decomposed and changed to a state where it was not practical.

Example 11 A striped tape was produced under the same conditions as in Example 9 except that the polyester (B1) obtained in Example 1 was formed into a film at 220 ° C. The obtained tape with a crease had a tensile strength of 4.4 g / d, had a volume feeling, and was excellent in a soft feeling. When the striped tape was buried in the soil for 5 months, almost the same results as in Example 1 were obtained.

Example 12 The polyester (B2) obtained in Example 4 was formed into a film at a molding temperature of 190 ° C.
A striped tape was manufactured under the same conditions as in Example 9 except that the tape was stretched. The obtained tape with a crease had a tensile strength of 5.0 g / d, had a volume feeling, and was excellent in a soft feeling. When the striped tape was buried in the soil for 5 months, it was decomposed and changed to a state where it had no practical strength.

(Example 13) A striped tape was produced from the polyester (B3) obtained in Example 7 under the same conditions as in Example 12. The resulting striped tape has a tensile strength of 5.
At 4 g / d, there was a volume and the soft feeling was excellent. Although this striped tape was buried in the soil for 5 months, almost the same results as in Example 10 were obtained.

(Example 14) The polyester (B4) obtained in Example 8 was extruded at a molding temperature of 190 ° C from a circular die with streaks to form a film. Stretched 5 times with a hot plate stretching machine,
A 2,000 denier striped tape was produced. The shape of the streak is U-shaped, depth 0.8 mm, lip gap 0.8 mm,
Those with a muscle spacing of 2.5 mm were used. The obtained tape with a crease had a tensile strength of 3.2 g / d, had a volume, and was excellent in a soft feeling. When the striped tape was buried in the soil for 5 months, the tape was decomposed and changed to an impractical strength.

Comparative Example 7 The polyester (A1) obtained in Example 1 was molded at a molding temperature of 200.degree.
An attempt was made to extrude the film from the die, but it could not be produced stably.

[0067]

[Table 1]

[0068]

According to the present invention, a temperature of 190 ° C. and a shear rate of 10 are used.
The melt viscosity at ⁰ sec ^-1 is 1 × 10 ³ to 4 × 10 ⁴
A tape made of an aliphatic polyester which is poise and has a melting point of 70 to 190 ° C., in particular, a number average molecular weight of 5,0
A tape made of an aliphatic polyester obtained by reacting 0.1 to 5 parts by weight of diisocyanate with 100 parts by weight of an aliphatic polyester prepolymer having a melting point of 60 ° C. or more, When embedded in, it has biodegradability, and even when incinerated, the calorific value of combustion is lower than polyethylene and polypropylene, and as a binding tape, it has excellent tensile strength and flexibility, Useful for binding tapes for automatic binding, useful for packing heavy objects, and has excellent mechanical strength and a sense of volume as tapes with streaks, cords and ropes for binding, packing, agriculture, fishing, forestry, etc. Useful as

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI // B29K 67:00 B29L 7:00 C08L 67:00 (72) Inventor Ryosuke Kamei 3-2 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kawasaki, Showa Denko Inside Kawasaki Resin Research Institute Co., Ltd. No. 2 In Showa Denko KK Kawasaki Resin Laboratory (72) Inventor Eiichiro Takiyama 4-12-4 Nishi-Kamakura, Kamakura-shi, Kanagawa (56) References JP-A-5-271377 (JP, A) JP-A-3-111418 (JP, A) JP-A-3-115418 (JP, A) JP-A-55-145734 (JP, A) JP-A-54-21496 (JP, A) JP-A-51-49591 (JP, A) United States Patent 3850862 (US, A) US Patent 2999851 (US, A) UK Patent 627270 (GB, A)

Claims (11)

(57) [Claims] A temperature of 190 obtained by reacting a coupling agent with an aliphatic polyester prepolymer synthesized mainly from glycols and aliphatic dicarboxylic acids (excluding hydroxyl group-containing dicarboxylic acids).
° C, the melt viscosity at a shear rate of 100 sec ^-1 is 1 ×
10 ³ to 4 × 10 ⁴ poises and a melting point of 70 to 190
A tape formed by extrusion molding of an aliphatic polyester having a main temperature of 100 ° C. and then uniaxially stretching. 2. An aliphatic polyester having a number average molecular weight of 1
2. The tape according to claim 1, which has a urethane bond of not less than 000 and 0.03 to 3.0% by weight. 3. A fat obtained by reacting 0.1 to 5 parts by weight of a diisocyanate with 100 parts by weight of an aliphatic polyester prepolymer having a number average molecular weight of 5,000 or more and a melting point of 60 ° C. or more. 3. The tape according to claim 1, wherein the tape is made of an aromatic polyester. 4. The tape according to claim 1, wherein the tape has a tensile strength of 2 g / d or more. 5. The tape according to claim 1, wherein the tape is a binding tape. 6. The tape according to claim 1, wherein the tape is a tape with a crease.
The tape according to claim 4. 7. The glycols are ethylene glycol,
1,4-butanediol, 1,6-hexanediol,
Decamethylene glycol, neopentyl glycol,
At least one selected from the group consisting of 1,4-cyclohexanedimethanol, wherein the aliphatic dicarboxylic acid is
The tape according to claim 1, wherein the tape is at least one selected from the group consisting of succinic acid, adipic acid, speric acid, sebacic acid, dodecanoic acid, succinic anhydride, and adipic anhydride. 8. When synthesizing the aliphatic polyester prepolymer, a trifunctional or tetrafunctional polyhydric alcohol, oxycarboxylic acid (however, excluding a hydroxyl group-containing dicarboxylic acid) and a polyhydric carboxylic acid or a trihydric carboxylic acid as a third component. The tape according to claim 7, further comprising at least one polyfunctional component selected from the group consisting of anhydrides. 9. The tape according to claim 8, wherein the polyhydric alcohol is at least one selected from the group consisting of trimethylolpropane, glycerin, and pentaerythritol. 10. The tape according to claim 8, wherein the oxycarboxylic acid is citric acid. 11. A polycarboxylic acid comprising trimesic acid, propanetricarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride,
The tape according to claim 8, wherein the tape is at least one member selected from the group consisting of cyclopentanetetracarboxylic acid.