JP2678868B2 - Polyester foam film and foam defibrated material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has biodegradability, is molded from an aliphatic polyester having a practically sufficient high molecular weight and specific melting characteristics, and is excellent in thermal stability and mechanical strength. Foamed film and defibration degree of aliphatic polyester,
The present invention relates to an expanded and defibrated aliphatic polyester fiber having an excellent texture.

[0002]

2. Description of the Related Art High-molecular-weight polyesters (hereinafter, referred to as "polyesters") conventionally used for molding films, fibers, and other molded articles.
The term "high molecular weight polyester" as used herein means a number average molecular weight of 20,000 or more. ) Was limited to polyethylene terephthalate, which is a condensate of terephthalic acid (including dimethyl terephthalate) and ethylene glycol, or butylene terephthalate from terephthalic acid and butylene glycol.

However, these films have high rigidity and high strength as ordinary inflation films as a factor of the molecular structure of terephthalic acid, but they are brittle when unstretched. It had no use value as a film and was widely used as a stretched film. Although the stretched polyester film is extremely excellent in transparency, strength, etc., it has a problem in heat sealing properties, so it was bonded to a polyolefin resin or film excellent in heat sealing properties as a heat sealing packaging film. It could only be used as a laminate.

For this improvement, instead of terephthalic acid,
Although there is an example using 2,6-naphthalenedicarboxylic acid,
There is no practical example of forming a polyester, using an aliphatic dicarboxylic acid as a dicarboxylic acid, into a sheet, a film, a fiber or the like and putting it into practical use.

[0005] One of the reasons why it has not been put to practical use is that even if it is crystalline, the melting point of aliphatic polyester is almost 100 ° C. or less, and furthermore, the thermal stability upon melting is poor. More importantly, the properties of the aliphatic polyester, particularly the mechanical properties represented by tensile strength, are extremely low, and even at the same level of the number average molecular weight as polyethylene terephthalate, it shows only a remarkably inferior value. There is no other way than it was.

[0006] In the research for improving the physical properties by further increasing the number average molecular weight of the aliphatic polyester, it seems that the thermal stability has not been sufficiently developed from the place where the thermal stability is poor.

Further, since polyesters such as polyethylene terephthalate have no microbial degradability, they are not decomposed forever by simply discarding them after use, and incineration is required for complete treatment. Was there.

Although there is a demand for a film, a foamed film or the like having heat stability, mechanical strength and biodegradability, there is no plastic that can meet the demand.

[0009] The foamed film is hydrophilic and hydrophilic in a film used for sowing seeds of plants on sloping grounds for preventing landslides, since it is lightweight and requires mechanical strength to some extent. , Materials that are not biodegradable and have no adverse effect on plants have been required, but none of them meet all of these requirements, and even though they have some defects, they are currently used in a compromised manner. is there.

On the other hand, the expanded and defibrated material of plastic utilizes the large surface area to separate oil spilled into the sea,
It is used as an adsorbent for the removal of harmful floating substances in rivers and the removal of nicotine from cigarettes. In addition to this, it is also used for industrial materials such as scabbard by utilizing the soft texture of the expanded and defibrated material.

Also in this case, the high-molecular-weight polyester usually used for molding a foamed defibrated body as a harmful substance removing material is polyethylene terephthalate, which is a condensate of terephthalic acid (including dimethyl terephthalate) and ethylene glycol. It is no exaggeration to say that it is limited.

[0012] Therefore, even in such a field of purpose, the idea of molding a foamed defibrated body using an aliphatic polyester having a biodegradability and using an aliphatic type for a dicarboxylic acid has been considered. I'm glad to say there is none.

One of the reasons for this is that even if the expanded defibrated material is required to have special molding conditions and physical properties of the molded article, the melting point of the aliphatic polyester is 100 ° C. or less even if it is crystalline. Almost all of them have poor thermal stability upon melting, and mechanical properties typified by tensile strength show only a significantly inferior value even at the same level as the number average molecular weight of the polyethylene terephthalate. It has been difficult to obtain a molded product requiring strength and the like.

Nonetheless, it is speculated that one of the reasons is that the research for increasing the number average molecular weight of the aliphatic polyester to improve the physical properties has not progressed sufficiently due to its poor thermal stability. To be done.

[0015]

DISCLOSURE OF THE INVENTION The present invention has a practically sufficient high molecular weight, excellent thermal stability and mechanical properties typified by tensile strength, and generates heat by combustion even if it is discarded after use. It is an object of the present invention to provide a foamed film of an aliphatic polyester which has a small amount, can be decomposed by microorganisms, etc., is easy to dispose, and has heat sealability as it is.

Furthermore, the present invention has a practically sufficient high molecular weight, is excellent in defibration and texture, and is biodegradable as one of the means for disposal, that is, it can be decomposed by microorganisms.
An object is to provide a foamed defibrated material that can be easily disposed of after use.

[0017]

According to the present invention, a melt viscosity at a temperature of 190 ° C. and a shear rate of 100 sec ⁻¹ , which is mainly synthesized from glycol and an aliphatic dibasic acid or its derivative, is 1.0 × 10 ³ to The above object was achieved by developing a polyester foam film which is characterized by extruding an aliphatic polyester having a melting point of 70 to 200 ° C. and a porosity of 1.0 × 10 ⁵ poise.

The present invention further relates to a temperature 19 synthesized mainly from glycol and an aliphatic dibasic acid or its derivative.
The melt viscosity at 0 ° C. and a shear rate of 100 sec ⁻¹ is 1.
0 × 10 ^{3 to} 1.0 × 10 ⁵ poise, melting point 70
The above object was achieved by developing a foamed and defibrated material characterized by extruding an aliphatic polyester having a temperature of up to 200 ° C.

The aliphatic polyester referred to in the present invention is mainly composed of a polyester synthesized from glycols and an aliphatic dibasic acid or an acid anhydride thereof, and has both ends in order to have a sufficiently high molecular weight. It is a product obtained by synthesizing a relatively high molecular weight polyester prepolymer having a hydroxyl group in and then further coupling these prepolymers with a coupling agent.

Conventionally, a low molecular weight polyester prepolymer having a hydroxyl group as a terminal group and a number average molecular weight of 2,000 to 2,500 is reacted with a diisocyanate to obtain a polyurethane, which is used as a rubber, foam, paint or adhesive. It is widely used as an agent.

However, the polyester prepolymers used in 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 catalyst. is there. In order to obtain practical physical properties as a polyurethane with respect to 100 parts by weight of the low molecular weight prepolymer, it is necessary to use 10 to 20 parts by weight of the diisocyanate. However, when such a large amount of diisocyanate is added to the melted low molecular weight polyester at 150 ° C. or higher, gelation occurs and a melt-moldable resin cannot be obtained.

Therefore, a polyester obtained by reacting such a low molecular weight polyester prepolymer as a raw material with a large amount of diisocyanate cannot be used as the raw material for the foamed film or the foamed defibrated material 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, but the amount of the diisocyanate used may be reduced as described above. 10 parts by weight or more is required per part by weight. At this time, if a heavy metal-based catalyst is used for the synthesis of the polyester, the reactivity of the isocyanate group is remarkably promoted, resulting in poor storage stability, crosslinking reaction, and branch formation, so that the polyester prepolymer is synthesized without a catalyst. As a result, the number average molecular weight is limited to about 2,500 at the highest.

In the polyester prepolymer for obtaining the aliphatic polyester used in the present invention, the terminal group obtained by reacting glycol with an aliphatic polybasic acid or an anhydride thereof is substantially a hydroxyl group, It is a saturated aliphatic polyester having an average molecular weight of 5,000 or more, preferably 10,000 or more, a relatively high molecular weight, and a melting point of 60 ° C. or more.

When the number average molecular weight is less than 5,000,
Even if a small amount of the coupling agent of 0.1 to 5 parts by weight is used, a foamed film or foamed defibrated body of an aliphatic polyester having good physical properties cannot be obtained. Polyester prepolymers having a number average molecular weight of 5,000 or more have a hydroxyl value of 30 or less, and use of a small amount of a coupling agent does not cause gelation during the reaction even under severe conditions such as a molten state. Polyester can be synthesized.

Examples of glycols used include 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 dibasic acids or their derivatives which react with glycols to form aliphatic polyesters include succinic acid, adipic acid, suberic acid, sebacic acid,
There are dodecanoic acid, succinic anhydride, adipic anhydride, and lower alcohol esters such as dimethyl ester thereof, which are commercially available and can be used in the present invention. You may use together a dibasic acid or its acid anhydride. These compounds may be preliminarily converted into low molecular esters to be polymerized by a glycol removal reaction.

As the aliphatic polyester which is the object of the present invention, these glycols and dibasic acids are mainly composed of an aliphatic type, but a small amount of other components, for example, trifunctional or tetrafunctional.
It is preferable to use a functional polyhydric alcohol, an oxycarboxylic acid or a polycarboxylic acid together.

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

Malic acid is practically advantageous as the trifunctional oxycarboxylic acid, and citric acid is practical because the tetrafunctional oxycarboxylic acid component is easily available as a commercial product at low cost.

As the trifunctional polycarboxylic acid (or acid anhydride thereof) component, for example, trimesic acid, propanetricarboxylic acid and the like can be used, but trimellitic anhydride is advantageous in practical use.

Examples of the tetrafunctional polyvalent carboxylic acid (or acid anhydride thereof) include pyromellitic dianhydride, benzophenonetetracarboxylic acid anhydride, cyclopentanetetracarboxylic acid anhydride and the like.

The polyfunctional component is used in such a proportion that the glycol component, the aliphatic component (including cycloaliphatic component), or the dicarboxylic acid (or its acid anhydride) component has a molar ratio of 10 or less.
5 mol% or less in the case of a trifunctional component with respect to 0 mol%,
It is preferably 0.5 mol% or more and 3 mol% or less, and in the case of a tetrafunctional component, 3 mol% or less, preferably 0.2 mol%.
Not less than 2 mol%.

If the proportion of the trifunctional component used exceeds 5 mol%, or if the proportion of the tetrafunctional component exceeds 3 mol%, the risk of gelation during the esterification reaction increases significantly.

The polyester prepolymer for an aliphatic polyester used in the present invention has a terminal group which is substantially a hydroxyl group. For that purpose, glycols and polybasic acids (or their acid anhydrides) used in the synthesis reaction are used. The use ratio of is required to use some excess of glycols.

The synthesis of relatively high molecular weight polyester prepolymers requires the use of a deglycolization catalyst during the deglycolization reaction following esterification.

Examples of the deglycolization catalyst include titanium compounds such as acetoacetoyl type titanium chelate compounds and organic alkoxy titanium compounds.
These titanium compounds can be used in combination. Examples of these include diacetacetoxyoxytitanium (“Nasem Titanium” manufactured by Nippon Chemical Industry Co., Ltd.), tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium and the like. The use ratio of the titanium compound is 0.001 to 100 parts by weight of the polyester prepolymer.
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.

As a result, a polyester prepolymer having an acid average molecular weight of 5,000 or more and a melting point of 60 ° C. or more can be easily obtained, and it is more preferable if it has crystallinity.

To obtain the aliphatic polyester of the present invention, the number average molecular weight is more than 5,000, preferably 1.
Coupling agents are used to further increase the number average molecular weight on polyester prepolymers where the terminal groups at or above 000 are substantially hydroxyl groups.

Examples of the coupling agent include diisocyanate, oxazoline, diepoxy compound, acid anhydride and the like, and diisocyanate is particularly preferable.

In the case of an oxazoline or diepoxy compound, it is necessary to react the hydroxyl group with an acid anhydride or the like to convert the terminal into a carboxyl group before using the coupling agent.

The diisocyanate is not particularly limited,
For example, there are the following types. 2,4-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2,
A mixture with 6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, particularly hexa Methylene diisocyanate is preferred 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 these coupling agents 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 it is less than 0.1 part by weight, the coupling reaction is insufficient, and if it exceeds 5 parts by weight, gelation occurs.

The addition is preferably carried out under the condition that the polyester prepolymer is in a uniform molten state and can be easily stirred. It can be added to a solid polyester prepolymer and melted and mixed through an extruder, but it is added to an aliphatic polyester production apparatus or to a molten polyester prepolymer (for example, in a kneader). It is practical.

The aliphatic polyester resin has a temperature of 190.
° C, the melt viscosity at a shear rate of 100 sec ^-1 is 1.0
× 10 ^{3 to} 1.0 × 10 ⁵ poise, and its melting point is 70
~ 200 ° C. In particular, those used for the foamed film are preferably those of 5,000 to 50,000 poise. On the other hand, the aliphatic polyester used for the foamed defibrated material may be the same as that described above, but is preferably 3.0 × 10 ^{3 to} 3.0 × 10 ⁴ poise. In any case, if the porosity is less than 1.0 × 10 ³ poise, the film becomes extremely unstable in the molding of the foamed film, making the molding difficult, while if the porosity exceeds 1.0 × 10 ⁵ poise, the flow when passing through the die is extremely poor. As a result, heat generation and flow nonuniformity occurred from the die outlet, and a good quality foamed film could not be obtained. MFR (190 ° C) is 20 g /
If it exceeds 10 minutes, the stability of the operation is poor and the workability is deteriorated.

The melt viscosity was measured with a nozzle diameter of 1.0.
mm and using a nozzle of L / D = 10, the resin temperature is 19
The viscosity at a shear rate of 100 sec ^-1 was determined from the graph of the relationship between the shear rate and the apparent viscosity measured at 0 ° C.

The melting point of the aliphatic polyester resin used in the present invention is required to be 70 to 200 ° C., more preferably 70 to 150 ° C., and especially 8
0-135 degreeC is preferable. If it is less than 70 ° C, the heat resistance is insufficient, and if it exceeds 200 ° C, it is difficult to manufacture.

In order to obtain a melting point of 70 ° C. or higher, it is necessary that the polyester prepolymer has a number average molecular weight of 5,000 or higher and a melting point of 60 ° C. or higher.

The aliphatic polyester resin used in the present invention has a number average molecular weight of 10,000 or more, preferably 20,000 or more, and when it contains a urethane bond, the amount of urethane bond is from 0.03 to 0.03. 3.0% by weight
And is preferably 0.05 to 2.0% by weight, and 0.1 to
1.0% by weight is particularly preferred.

The amount of urethane bond is measured by ¹³ C-NMR and agrees well with the charged amount. The amount of this bond is 0.03
When it is less than 3.0% by weight, the effect of increasing the molecular weight by urethane bond is small and the moldability is poor, while when it exceeds 3.0% by weight, gel is generated.

As the foaming agent usable in the present invention, inorganic compounds such as sodium hydrocarbons and azides used in the production of general plastic foams, organic compounds such as azo series, hydrazine series, triazole series and N nitrone series are used. A foaming agent or various foaming aids can be used in combination therewith. Depending on the decomposition temperature of the foaming agent, these may be kneaded into pellets beforehand, or may be dry blended with a mixer or the like. The amount of the foaming agent used varies depending on the type of the foaming agent, the expansion ratio, the molding temperature, etc., but is usually 0.2 to 5 parts by weight based on 100 parts by weight of the polyester resin.

For the molding according to the present invention, in addition to the above-mentioned aliphatic polyester resin, if necessary, in addition to antioxidants, heat stabilizers, UV absorbers, lubricants, waxes, colorants, crystallization accelerators. Of course, etc. can be used together.

That is, as the antioxidant, hindered phenolic antioxidants such as pt-butylhydroxytoluene and ptbutylhydroxyanisole, sulfur such as distearylthiodipropionate and dilaurylthiodipropionate are used. Triphenyl phosphite, trilauryl phosphite, trisnonyl phenyl phosphite, etc. as heat stabilizers such as system antioxidants, and pt-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone as ultraviolet absorbers. 2-hydroxy-4-methoxy-2'-carboxybenzophenone,
Lubricants such as 2,4,5-trihydroxybutyrophenone, calcium stearate, zinc stearate,
Antistatic agents such as barium stearate and sodium palmitate include N, N-bis (hydroxyethyl)
Alkyl amine, alkyl amine, alkyl allyl sulfonate, alkyl sulfonate, etc., flame retardant hexabromocyclododecane, tris- (2,3-dichloropropyl) phosphate, pentabromophenyl allyl ether, etc., inorganic filler calcium carbonate , Silica, titanium oxide, talc, mica, barium sulfate, alumina and the like, and crystallization accelerators such as polyethylene terephthalate and poly-transcyclohexanedimethanol terephthalate.

In the production of a foamed film, a resin containing a foaming agent is sufficiently melted and mixed in an extruder by an extrusion molding method, and then the resin is extruded uniformly from a die in a state where the resin temperature is made uniform. 50 μm thickness
The film can have a thickness of about 300 μm. It is particularly important to set the molding temperature, and the temperature of the extruder cylinder and die is 150 to 240 ° C, preferably 170 to 240 ° C.
The temperature is 200 ° C., and if the temperature is 150 ° C. or less, a good foamed film cannot be formed. On the other hand, when the temperature exceeds 240 ° C., the resin is apt to be deteriorated, a large number of porcelain, which is a problem in forming a foamed film, frequently occurs, and the foamed state is over-foamed, resulting in coarse bubbles, which is not preferable.

In this case, as a method used for forming the film, a general film forming method such as an inflation method or a T-die film forming method can be used, but an inflation method is advantageous because of foaming. For example, a blow ratio of 1.0-3.
By expanding to 0, film thickness 50μm
A tubular foam film with a thickness of about 300 μm can be obtained.

The physical properties of the film thus obtained are usually tensile breaking strength (MD) of 100 kg / cm ² or more, elongation at break of 100% or more, and film Young's modulus of 1,500 kg / cm ^2. That is all. Breaking strength is 1
When it is about 50 kg / cm ² or less, it is weak to be used as a general packaging film as a film, but since it is a foamed film, it has a beautiful pearl-like appearance, and since it is excellent in heat insulation, the strength is increased. Therefore, it can be used as a shopping bag or a packaging container that needs to have impact resistance or heat insulation by increasing its thickness.

Further, the characteristic feature of the present film is that the elongation at break is 100% or more, and at the same time, the foam elongation is 100% or more at the same time with respect to the cushioning effect due to foaming and also against projections and various impacts. It has a great feature as a packaging material that protects the contents without being destroyed. In addition, the Young's modulus is 1,500 kg / cm ² or more, so that the thickness of the film is increased (to 50 μm or more).
By doing so, secondary processing such as automatic packaging and bag making can be performed.

In particular, since the polyester foam film of the present invention has biodegradability by burying it in soil or the like as described later, not only the effect of the conventional cushioning material and appearance (look) but also the new use of the foam film By embedding seeds, fungi, etc. of various plants (for example, turf) in each cell, it can be expected to be widely used for planting plants in rough lands, slopes and the like.

On the other hand, in the foamed defibrated body, the raw material aliphatic polyester resin is usually melt-extruded from the split nozzle, defibrated by cooling with air, and taken into fiber.
Molding temperature is 170-240 ° C, preferably 180-19
0 ° C. If it is less than 170 ° C, the film breaks before defibration, and if it exceeds 240 ° C, the melted film fluctuates greatly and the defibrated product easily breaks. The foaming agent is one that vaporizes or decomposes at a temperature not higher than the molding temperature to generate a gas, and is a solid foaming agent having a decomposition temperature of 165 to 200 ° C, and is preferably used. When the blowing agent is less than 0.2 parts by weight with respect to the aliphatic polyester used in the present invention, the foaming is small and the defibration is low, and when it exceeds 5 parts by weight, the foaming becomes coarse and uneven, and the defibration is rough. Since the homogenization is also caused, a foamed and defibrated material having a low denier cannot be obtained.

The number average molecular weight used in the present invention is 10,0.
An aliphatic polyester having a melting point of 70 to 200 ° C. and a crystallinity of 70 or more, and preferably 20,000 or more, can be made into a tough foam defibrated material, and foreign matter adsorption separation of a cigarette filter, an oil adsorbent, etc. It can be used as a material and widely as an industrial material. Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.

[0062]

【Example】

(Example 1) After replacing a 700 L reactor with nitrogen,
183 kg of 1,4-butanediol, 224 k of succinic acid
g. The temperature was increased in a nitrogen stream, and 192
~ 220 ° C for 3.5 hours, then stop nitrogen and 20 ~
The esterification reaction by dehydration condensation was performed under reduced pressure of 2 mmHg for 3.5 hours. The sample collected had an acid value of 9.2 mg / g, a number average molecular weight (Mn) of 5,160,
The weight average molecular weight (Mw) was 10,670.
Subsequently, 34 g of tetraisopropoxytitanium 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. under 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 prepolymer (A1) is 3 when condensed water is removed.
It was 39 kg.

Polyester Prepolymer (A1) 339
Hexamethylene diisocyanate 5420g was added to the reactor containing kg, and the coupling reaction was performed at 180-200 degreeC for 1 hour. The viscosity increased rapidly but no gelling occurred. Next, 1700 g of Irganox 1010 (manufactured by Ciba Geigy) as an antioxidant and 1700 g of calcium stearate as a lubricant were added, and stirring was further continued for 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 resin (B1) after vacuum drying at 90 ° C. for 6 hours was 300 kg.

The obtained polyester resin (B1) is a slightly ivory white waxy crystal and has a melting point of 1
10 ° C., number average molecular weight (Mn) 35,500, weight average molecular weight (Mw) 170,000, MFR (190
℃) 1.0g / 10 minutes, orthochlorophenol 1
The 0% solution had a viscosity of 230 poise, a temperature of 190 ° C., and a melt viscosity of 1.5 × 10 ⁴ poise at a shear rate of 100 sec ⁻¹ . The average molecular weight is measured by Shodex G
PC System-11 (Showa Denko KK Gel Chromatography), the solvent was CF ₃ COONa hexafluoroisopropyl alcohol 5 mmol solution, concentration 0.
1% by weight, and a calibration curve was performed using Showa Denko KK-made PMMA standard sample Shodex Standard M-75.

Then, this polyester resin (B1) 10
A mixture of 0 parts by weight and 3 parts by weight of azodicarbonamide as a foaming agent was dry blended with a screw diameter of 40 m.
Using an extruder with mφ and L / D = 28, resin temperature 185 ° C.
(Cylinder and die), extruded from a spiral die of 50 mmφ (lip gap 0.5 mm), cooled with air from an air ring by a normal air-cooled inflation method, take-up speed 10 m / min, folding diameter 200
A tubular foamed film having a thickness of 120 mm and a blow ratio of 2.55 was formed. Stable film formation was achieved by adjusting the air volume of the blower and the air ring to control the cooling conditions.

The obtained film had a tensile breaking strength (JIS
Z-1702, same hereafter) is 120 kg / cm ² , tensile elongation (JIS Z-1702, hereafter same) 150%,
Young's modulus (ASTM D-822, same hereafter) is 220
The pearl-like fine cells were formed at 0 kg / cm ² and the expansion ratio was 2.0 times, and the texture was excellent. In addition, heat sealing of the hot plate of this film enables heat fusion, and
1.2kg / at 1 ° C, time 1sec, pressure 1kg / cm ²
A seal strength of 15 mm width was obtained.

When the film was buried in soil for 2 months and the strength was measured, the breaking strength and elongation were significantly reduced to 30 kg / cm ² and 50%, respectively, and decomposition occurred in the soil. It became clear that there is.

(Example 2) 100 parts by weight of the polyester resin (B1) used in Example 1 and 3 parts by weight of azodicarbonamide as a foaming agent were dry-blended, and an extruder having a screw diameter of 40 mmφ and L / D = 28 was used. Use, resin temperature 170 ℃ (cylinder and die), 50mmφ
Extruded from a spiral die (lip gap 0.5 mm), cooled with air from an air ring by a normal air-cooled inflation method, and a take-up speed of 6 m / min,
Folding diameter 200 mm (blow ratio 2.55), thickness 200 μm
The tubular foamed film of was molded. Stable film formation was achieved by adjusting the air volume of the blower and the air ring to control the cooling conditions.

The film obtained has a tensile strength at break of 150.
kg / cm ² , tensile elongation 180%, Young's modulus 20
Fine cells having a pearl-like appearance were formed at 00 kg / cm ² and a foaming ratio of 1.8, and the texture was excellent. This film can be heat-sealed with a heat plate heat sealer, and the temperature is 120 ° C, the time is 1 sec, and the pressure is 1 kg /
A seal strength of 1200 g / 15 mm width in cm ² was obtained.

Example 3 A 700 L reactor was purged with nitrogen, and then 177 kg of 1,4-butanediol, 198 kg of succinic acid and 25 kg of adipic acid were charged. The temperature is increased under a nitrogen stream, and the temperature is 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 tetraisopropoxytitanium as a catalyst was added under a nitrogen stream under normal pressure. Raise the temperature to 15 at a temperature of 210-220 ° C.
The deglycol-reaction was performed under a reduced pressure of 0.2 mmHg for 6.5 hours. The collected sample has a number average molecular weight (M
n) is 17,300 and the weight average molecular weight (Mw) is 4
6,400. The yield of this polyester prepolymer (A2) was 337 kg when condensed water was removed.

Polyester Prepolymer (A2) 333
4.66 kg of hexamethylene diisocyanate was added to the reactor containing kg, and the coupling reaction was performed at 180 to 200 ° C. for 1 hour. The viscosity increased rapidly but no gelling occurred. Then, 1.70 kg of Irganox 1010 (manufactured by Ciba Geigy) as an antioxidant and 1.70 kg of calcium stearate as a lubricant were added, and 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 resin (B2) after vacuum drying at 90 ° C. for 6 hours was 300 kg.

The polyester resin (B2) thus obtained was a slightly ivory white waxy crystal and had a melting point of 1
03 ° C, number average molecular weight (Mn) of 36,000, weight average molecular weight (Mw) of 200,900, MFR (190
° C.) is 0.52 g / 10 min, a viscosity of 680 poises in a 10% orthochlorophenol solution, temperature 190 ° C., was melt viscosity 2.2 × 10 ⁴ poise at a shear rate of 100 sec ^-1.

A mixture of 100 parts by weight of this polyester resin (B2) and 0.7 parts by weight of azodicarbonamide as a foaming agent was dry blended, and the screw diameter was 40 mmφ.
Using an extruder of L / D = 28, at a resin temperature of 180 ° C. (cylinder and die), extruded from a spiral die of 50 mmφ (lip gap 0.5 mm), cooled with air from an air ring by a normal air-cooled inflation method, Take-up speed 10m / min, folding diameter 160mm
(Blow ratio 2.0), a tubular foam film having a thickness of 100 μm was formed. Stable film formation was achieved by adjusting the air volume of the blower and the air ring to control the cooling conditions.

The film obtained has a tensile breaking strength of 160.
kg / cm ² , tensile elongation 180%, Young's modulus 2400k
Sufficient physical properties as a packaging film were obtained at g / cm ² and an expansion ratio of 1.7. This film can be heat-sealed with a heat plate heat sealer at a temperature of 115 ° C for 1 s.
A seal strength of 1100 g / 15 mm width was obtained at ec and a pressure of 1 kg / cm ² .

When the film was buried in soil for 3 months and the strength was measured, the breaking strength and elongation were significantly reduced to 60 kg / cm ² and 50%, respectively, and decomposition occurred in the soil. It became clear.

(Example 4) After replacing a 700 L reactor with nitrogen, 145 kg of ethylene glycol and 2 parts of succinic acid were used.
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 sample collected 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 tetraisopropoxytitanium as a catalyst was added under a nitrogen stream under normal pressure. Raise the temperature, 15 ~
The glycol removal reaction was performed under a reduced pressure of 0.2 mmHg for 4.5 hours. The collected sample is number average molecular weight (Mn)
Is 33,400 and the weight average molecular weight (Mw) is 13
It was 7,000. The yield of this polyester prepolymer (A3) was 323 kg when condensed water was removed.

Polyester Prepolymer (A3) 323
Hexamethylene diisocyanate 3.23kg was added to the reactor containing kg, and the coupling reaction was performed at 180-200 degreeC for 1 hour. The viscosity increased rapidly but no gelling occurred. Next, 1.62 kg of Irganox 1010 (manufactured by Ciba Geigy) as an antioxidant and 1.62 kg of calcium stearate as a lubricant were added, and 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. After vacuum drying at 90 ° C. for 6 hours, the yield of the polyester resin (B3) was 300 kg.

The obtained polyester resin (B3) was slightly ivory white waxy crystals and had a melting point of 9
6 ° C, number average molecular weight (Mn) of 54,000, weight average molecular weight (Mw) of 324,000, MFR (190 ° C)
Is 1.1 g / 10 minutes, 10% of orthochlorophenol
The viscosity of the solution is 96 poise, temperature 190 ° C, shear rate 10
The melt viscosity at ⁰ sec ⁻¹ was 1.6 × 10 ⁴ poise.

100 parts by weight of polyester resin (B3),
A mixture obtained by dry blending 1 part by weight of azodicarbonamide as a foaming agent has a screw diameter of 55 mmφ and L / D =
Using an extruder of No. 28, extruded from a spiral die (lip gap 0.5 mm) of 100 mmφ at a resin temperature of 190 ° C. (cylinder and die), cooled with air from an air ring by a normal air cooling inflation method, and a take-up speed of 10 m / min. A tubular foam film having a folding diameter of 314 mm (blow ratio of 2.0) and a thickness of 200 μm was molded. Stable film formation was achieved by adjusting the air volume of the blower and the air ring to control the cooling conditions.

The film obtained has a tensile strength at break of 150.
kg / cm ² , tensile elongation 180%, Young's modulus 2300k
Sufficient physical properties as a packaging film were obtained at g / cm ² and an expansion ratio of 1.8. In addition, the heat sealing strength is such that the sealing condition temperature is 115 ° C., time is 1 sec, and pressure is 1 kg / cm.
² , the width was as large as 2300 g / 15 mm, and good sealing was possible.

Example 5 A 700 L reactor was purged with nitrogen, and 200.2 kg of 1,4-butanediol, 249.8 kg of succinic acid and 2.8 kg of trimethylolpropane were charged. The temperature was increased under a nitrogen stream, and 19
4.5 hours at 0-220 ℃, stop nitrogen further 20
The esterification reaction by dehydration condensation was performed for 5.5 hours under a reduced pressure of -4 mmHg. The sample collected had an acid value of 10.4 mg / g and a number average molecular weight (Mn) of 4,90.
0, and the weight average molecular weight (Mw) was 10,000. Subsequently, 45 g of tetraisopropoxy titanium as a catalyst (0.01 part with respect to 100 parts of the polymer) was added under a nitrogen stream at atmospheric pressure. Raise the temperature to 210
8.0 at 220 ° C. under a reduced pressure of 15 to 1.3 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. The theoretical yield of this polyester prepolymer (A4) was 367 kg, excluding the theoretical amount of condensed water of 76.1 kg.

Polyester Prepolymer (A4) 367
Irganox 1 as an antioxidant in a reactor containing kg
367 g of 010 (manufactured by Ciba Geigy) and 367 g of calcium stearate as a lubricant, and 3.67 kg of hexamethylene diisocyanate were added to obtain 16
The coupling reaction was carried out at 0 to 200 ° C. for 2 hours. Then stirring was continued for a further 30 minutes. The reaction mixture was extruded into water by an extruder and cut into pellets with a cutter. The yield of this polyester resin (B4) was about 350 kg.

The polyester resin (B4) obtained was a slightly ivory white waxy crystal and had a melting point of 1
04 ° C., number average molecular weight (Mn) is 17,900, weight average molecular weight (Mw) is 161,500, MFR (190
℃) 0.2g / 10 minutes, temperature 190 ℃, shear rate 10
The melt viscosity at ⁰ sec ⁻¹ was 2.0 × 10 ⁴ poise.

The polyester resin (B4) was heated at a resin temperature of 1 using an extruder having a screw diameter of 55 mmφ and L / D = 28.
Extruded from a spiral die (lip gap 0.8 mm) of 100 mmφ at 90 ° C. (cylinder and die), cooled with air from an air ring by a normal air-cooled inflation method, take-up speed 10 m / min, folding diameter 314 mm (blow ratio 2. 0), a tubular foam film having a thickness of 250 μm was formed. By controlling the air conditioner and air ring of the blower to control the cooling conditions, the bubbles were very stable and a good quality film could be formed.

The film obtained has a tensile strength at break of 180.
strongly kg / cm ^2, tensile elongation Yes 200%, Young's modulus 2500 kg / cm ^2, sufficient physical properties was obtained as a packaging film with an expansion ratio 1.9 times. Further, the heat sealing strength was as large as 2.0 kg / 15 mm width at a sealing condition temperature of 115 ° C., a time of 1 sec, and a pressure of 1 kg / cm ² , and a good seal was obtained.

When this film was buried in soil for 2 months and the strength was measured, the breaking strength and elongation were significantly reduced to 20 kg / cm ² and 40%, respectively, and decomposition occurred in the soil. It became clear that there is.

(Example 6) A composition obtained by blending the polyester resin (B1) produced in Example 1 with the polyester resin (B4) used in Example 5 in an amount of 50% was used.
Using an extruder with 0 mmφ and L / D = 28, resin temperature 20
It is extruded from a spiral die (lip gap 0.8 mm) of 50 mmφ at 0 ° C (cylinder and die), cooled with air from an air ring by a normal air-cooled inflation method, take-up speed 5 m / min, folding diameter 200.
A tubular film having a thickness of 180 mm and a blown ratio of 2.55 was formed. Stable film formation was achieved by adjusting the air volume of the blower and the air ring to control the cooling conditions.

The film obtained has a tensile strength at break of 200.
The strength was as strong as kg / cm ² , the tensile elongation was 230%, and the Young's modulus was 2800 kg / cm ^2, which was sufficient physical properties as a packaging film. In addition, this film can be heat-sealed with a heat sealer of a hot plate, the temperature is 120 ° C, the time is 1 sec.
c, a seal strength of 1300 g / 15 mm width was obtained at a pressure of 1 kg / cm ² .

When the film was buried in soil for 2 months and the strength was measured, the breaking strength and elongation were significantly reduced to 50 kg / cm ² and 60%, respectively, and decomposition occurred in the soil. It became clear that there is.

(Example 7) 100 parts by weight of the polyester resin (B1) produced in Example 1 was dry blended with 0.8 part by weight of azodicarbonamide as a foaming agent, and 55
mmφ extruder, slit spacing 0.5mm, 200m
While melt-extruding from the mφ annular slit nozzle at a molding temperature of 230 ° C., air at room temperature is blown from the air ring to cool the fiber immediately after melt-extrusion to the defibration start point (position 2 cm from the slit nozzle) and thereafter, Collection speed 150m
/ Min, and a foamed defibrated body was formed.

The foamed defibrated material obtained was a reticulated body with almost no yarn breakage, and as a whole, 36,000 denier and 5-20 denier reticulated fibers showed a uniform and fine defibration degree and an excellent texture.

When it was buried in soil for 5 months, it was decomposed and changed to a state in which it had no practical tensile strength.

(Example 8) 100 parts by weight of the polyester resin (B1) produced in Example 1 was dry blended with 0.8 part by weight of azodicarbonamide as a foaming agent, and 55
200m with slit interval 0.5mm by mmφ extruder
While melt-extruding from a mφ annular slit nozzle at a molding temperature of 170 ° C., air at room temperature is blown from an air ring to cool the fiber immediately after melt-extrusion to a portion after the defibration start point (position 2 cm from the slit nozzle). Collection speed 150m
/ Min, and a foamed defibrated body was formed.

The foamed defibrated material obtained was a reticulated body with almost no yarn breakage. The overall denier was 36,000 denier, and the reticulated yarn was 5 to 20 denier, showing a uniform fine defibration degree and an excellent texture.

When this defibrated material was buried in soil for 5 months, it was decomposed and changed to have a very low tensile strength.

(Example 9) 100 parts by weight of the polyester resin (B1) produced in Example 1 was dry blended with 3.0 parts by weight of azodicarbonamide as a foaming agent, and 55
200m with slit interval 0.5mm by mmφ extruder
While melt-extruding from a mφ annular slit nozzle at a molding temperature of 170 ° C., air at room temperature is blown from an air ring to cool the fiber immediately after melt-extrusion to a portion after the defibration start point (position 2 cm from the slit nozzle). Collection speed 150m
/ Min, and a foamed defibrated body was formed.

The foamed defibrated material obtained was a reticulated body with almost no yarn breakage. As a whole, the woven denier was 36000 denier, and the reticulated fiber was 5 to 20 denier, showing a uniform fine defibration degree and an excellent texture.

When this defibrated material was buried in soil for 5 months, it was decomposed and changed into a foamed defibrated material having no practical tensile strength.

(Example 10) 100 parts by weight of the polyester resin (B2) produced in Example 3 was dry blended with 0.8 part by weight of azodicarbonamide as a foaming agent to give 5 parts.
200 with a slit interval of 0.5 mm using a 5 mmφ extruder
Melt extrusion at a molding temperature of 230 ° C. from an annular slit nozzle of mmφ, and air at room temperature is blown from the air ring to start defibration immediately after the melt extrusion (2 cm from the slit nozzle.
Position) and the take-up speed is 150 m
/ Min, and a foamed defibrated body was formed.

The foamed defibrated material obtained was a reticulated body with almost no yarn breakage. The overall denier was 36,000 denier and the reticulated yarn was 5 to 20 denier, showing a uniform fine defibration degree and an excellent texture.

When the expanded and defibrated material was buried in soil for 5 months, it was decomposed and changed to a state having almost no practical tensile strength.

(Example 11) 100 parts by weight of the polyester resin (B2) produced in Example 3 was dry-blended with 0.8 part by weight of azodicarbonamide as a foaming agent, and 5
200 with a slit interval of 0.5 mm using a 5 mmφ extruder
Melt extrusion at a molding temperature of 170 ° C. from an annular slit nozzle of mmφ, and air blowing at room temperature from an air ring to start defibration immediately after the melt extrusion (2 cm from the slit nozzle.
Position), and take over speed 150 while air-cooling to the subsequent parts.
It was taken up at m / min to form a foamed defibrated body.

The foamed defibrated material obtained was a reticulated body with almost no yarn breakage, and as a whole, 36,000 denier and 5-20 denier of the reticulated fiber showed a uniform and fine defibration degree and an excellent texture.

When the expanded and defibrated material was buried in soil for 5 months, the same results as in Example 10 were obtained.

(Example 12) 100 parts by weight of the polyester resin (B2) produced in Example 3 was dry blended with 0.8 part by weight of azodicarbonamide as a foaming agent to give 5 parts.
200 with a slit interval of 0.5 mm using a 5 mmφ extruder
Melt extrusion at a molding temperature of 230 ° C. from an annular slit nozzle of mmφ, and air at room temperature is blown from the air ring to start defibration immediately after the melt extrusion (2 cm from the slit nozzle.
Position) and the take-up speed is 150 m
/ Min, and a foamed defibrated body was formed.

The foamed defibrated material obtained was a reticulated body with almost no yarn breakage, and the net defibration was 36,000 denier as a whole and the woven fiber was 5 to 20 denier, showing a uniform fine defibration degree and an excellent texture.

When the expanded and defibrated material was buried in soil for 5 months, the same results as in Example 10 were obtained.

(Example 13) 100 parts by weight of the polyester resin (B3) produced in Example 4 was dry blended with 0.8 part by weight of azodicarbonamide as a foaming agent to give 5 parts.
200 with a slit interval of 0.5 mm using a 5 mmφ extruder
Melt extrusion at a molding temperature of 230 ° C. from an annular slit nozzle of mmφ, and air at room temperature is blown from the air ring to start defibration immediately after the melt extrusion (2 cm from the slit nozzle.
Position), and take over speed 150 while air-cooling to the subsequent parts.
It was taken up at m / min to form a foamed defibrated body.

The foamed defibrated material obtained was a reticulated body with almost no yarn breakage. The overall denier was 36,000 denier, and the reticulated yarn was 5 to 20 denier, showing a uniform fine defibration degree and an excellent texture.

When this defibrated material was buried in soil for 5 months, it was decomposed and changed to have a very low tensile strength.

(Example 14) 100 parts by weight of the polyester resin (B4) produced in Example 5 was dry blended with 0.8 part by weight of azodicarbonamide as a foaming agent to give 5 parts.
200 with a slit interval of 0.5 mm using a 5 mmφ extruder
Melt extrusion at a molding temperature of 230 ° C. from an annular slit nozzle of mmφ, and air at room temperature is blown from the air ring to start defibration immediately after the melt extrusion (2 cm from the slit nozzle.
1) Picking up speed 1 while air-cooling to the part after
It was taken off at 50 m / min to form a foamed defibrated body.

The foamed defibrated material obtained was a reticulated body with almost no yarn breakage, and as a whole, 36,000 denier and 5-20 denier reticulated fibers showed a uniform and fine defibration degree, and the texture was excellent.

When I buried it in the soil for 5 months,
It decomposed and changed to a state where it had no practical tensile strength.

[0114]

INDUSTRIAL APPLICABILITY According to the present invention, an aliphatic prepolymer having a terminal hydroxy group having a relatively high molecular weight is prepared, which is made into a polymerized aliphatic polyester resin without gelation with a small amount of a coupling agent and foamed therein. A foamed film or a foamed defibrated material is obtained by adding an agent and molding.

The foamed film of the present invention is a polyester film, which is biodegradable and heat-sealable, and has a lower combustion calorific value than that of polyethylene or polypropylene even when incinerated. ,
It is a film with few disposal problems.

Further, since the foamed film is excellent in thermal stability and mechanical strength, it can be used as it is as a heat-sealing packaging material because it is subjected to a coupling treatment even though it is an aliphatic polyester resin.

In particular, since foaming can be carried out uniformly and it is not only a cushioning material or a heat insulating material but also has an excellent texture, it can be used as a film for various packaging, cosmetic packaging, industrial and agricultural films.

Further, even when it is made into a foamed defibrated body, it has excellent defibration degree, texture, thermal stability and mechanical strength, and is widely used as a foreign matter adsorption / separation material for cigarette filters, oil adsorbents, etc. It is useful as a material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location // C08L 67:02 (72) Inventor Tetsuya Takahashi 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Electric Works Co., Ltd. Kawasaki Plastics Research Institute (72) Inventor Ryosuke Kamei 3-2 Chidori-cho, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Showa Electric Works Co., Ltd. Kawasaki Plastics Research Lab. 2 Kawasaki Plastics Research Laboratory, Showa Denko Co., Ltd. (72) Inventor Eiichiro Takiyama 4-12-4 Nishi-Kamakura, Kamakura City, Kanagawa Prefecture

Claims (9)

(57) [Claims] ^1. A melt viscosity of 1.0 × 10 ³ at a temperature of 190 ° C. and a shear rate of 100 sec ^{−1, which} is mainly synthesized from glycol and an aliphatic dibasic acid or its derivative.
~ 1.0 × 10 ⁵ poise, melting point 70 ~ 200 ° C
A polyester foam film, which is obtained by extruding the above aliphatic polyester. 2. A foaming ratio of 1.1 to 2.2 times, a tensile breaking strength (MD) of 100 kg / cm ² or more, and a breaking elongation of 100%.
The polyester foam film according to claim 1, which has a film Young's modulus of 1500 kg / cm ² or more. 3. The aliphatic polyester has a number average molecular weight of 1.
An aliphatic polyester having a content of 50,000 or more and containing 0.03 to 3.0% by weight of a urethane bond.
The polyester foam film according to any one of 1. 4. An aliphatic compound obtained by reacting 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 with 0.1 to 5 parts by weight of diisocyanate. It is polyester, The polyester foam film in any one of Claims 1-3. 5. The polyester foam film according to claim 1, wherein a composition comprising 100 parts by weight of an aliphatic polyester and 0.2 to 5.0 parts by weight of a foaming agent is used. 6. A melt viscosity at a temperature of 190 ° C. and a shear rate of 100 sec ^{−1, which} is mainly synthesized from glycol and an aliphatic dibasic acid or its derivative, is 1.0 × 10 ³ to.
A foamed defibrated body, which is obtained by extruding an aliphatic polyester having a melting point of 70 to 200 ° C. and having a porosity of 1.0 × 10 ⁵ poise. 7. The aliphatic polyester has a number average molecular weight of 1.
The expanded and defibrated material according to claim 6, which is an aliphatic polyester having a urethane bond content of 30,000 or more and 0.03 to 3.0% by weight. 8. An aliphatic compound obtained by reacting 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 with 0.1 to 5 parts by weight of diisocyanate. The expanded and defibrated material according to claim 6, which is a polyester. 9. The expanded and defibrated body according to claim 6, wherein a composition comprising 100 parts by weight of an aliphatic polyester and 0.2 to 5.0 parts by weight of a foaming agent is used.