TW200528505A - Biodegradable aromatic polyester and product thereof - Google Patents

Abstract

A biodegradable aromatic polyester comprising polyoxyalkylenepropane diol residues and alkyl diol residues and terephthalic acid residues and together with additional residues, such as ether diol residues, isophthalic acid residues oraliphatic dicarboxylic acid residues, derived from carbohydrates. This invention also relates to the products, such as film and fiber, by using the composition of biodegradable aromatic polyester along or with cellulose as the material.

Description

200528505 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a biodegradable aromatic polyester and a molded article thereof. More specifically, it relates to a biodegradable aromatic polyester and various molded articles such as a film, fiber, cloth, or nonwoven fabric. [Previous technology] In the past, most of the synthetic polymer compounds were extremely difficult to decompose in nature, and they were often accused of polluting the environment and becoming the culprits of various public hazards. From these viewpoints, it is required that the polymer material can be easily decomposed in the environment, and when decomposed, the polymer material that does not pollute the nature has the ability to decompose a part or all of it into low molecular compounds by microorganisms in nature, Or, finally, biodegradable plastics that can be decomposed into water and carbon dioxide have become the raw materials for which this kind of raw materials have become the most focused concern. Various aliphatic polyesters have been developed as biodegradable plastics in the past. For example, polycaprolactam is relatively easy to obtain its raw materials in industry, has good stability, and has advantages in biodegradability. However, these raw materials are not advantageous in terms of performance compared with plastics that are widely used in general. Compared with polyethylene terephthalate, they also have low melting points and insufficient strength. The price is high. Polybutylene succinate is also a promising raw material as a biodegradable aliphatic polyester. However, this resin has the same problems as the aforementioned polycaprolactam. In order to improve these shortcomings, the previously proposed Japanese Patent No. -5- 200528505 (2) 3 4 1 1 2 8 9 discloses the polybutylene adipate and polybutylene terephthalate. Copolymer 'Although this copolymer is decomposable, its crystallinity is extremely low, so it has the problem of extremely low melting point or mechanical properties. Also, Japanese Patent Application Laid-Open No. 1-2 3 4 4 2 0 discloses that as a diol component, the following formula ch2- (〇r2V〇Ri hochch2oh is used

Here, Ri represents a hydrocarbon group, R2 represents an alkylene group, and η is an integer of 30 to 140. Aromatic polyester copolymer of the compound shown. U.S. Patent No. 6 3 6 8 7 1 B 1 discloses that (a) more than one aromatic dicarboxylic acid or its ester, (b) more than one aliphatic dicarboxylic acid or its ester, (c) More than one sulfonated compound, such as the polymerization product of dimethyl-5 -sulfoisophthalate and (d) isosorbide, namely 1,4: 3,6-dihydro-D-sorbitol Sulfonated copolymer.

Also, International Publication No. 93/719 discloses a polyethylene terephthalate copolymer. However, although the above-mentioned copolymers have a certain degree of crystallinity and melting point, they are expensive and have the problem of extremely slow biodegradation. On the other hand, polylactic acid is biodegradable and has a high glass transition temperature, which is superior in strength to conventional biodegradable plastics. In addition, environmentally friendly raw materials that can be manufactured from biological materials such as corn are also being accepted. However, this type of polylactic acid also does not have a full melting point as an engineering plastic. Although the cost of the biodegradable polymer in the past is still -6-200528505 (3) lower cost, it is still widely used as a resin. High price. Also, Japanese Patent No. 3 4 1 9 1 2 discloses a copolymer of polylactic acid and an aromatic polyester. However, polylactic acid is lactide produced by depolymerization at a temperature above 230 ° C, so aromatic polyester systems that can be copolymerized are limited /

It is a low-crystalline copolymer with a melting point below 200 ° C, or a copolymer containing poly (V-alkyl ether) to make it polymerizable at low temperature is its disadvantage. In addition, polylactic acid has almost no mutual solubility with most aromatic polyesters, so it is difficult to react under ordinary polymerization reactions. In particular, it can be polymerized with aromatic polyesters with high melting points and should be copolymerized. Known. From the above, it is known that no one can provide a biodegradable polyester having a sufficiently high melting point, excellent physical properties, and a method for manufacturing these at low cost with excellent production efficiency.

In addition, from the viewpoint of low environmental burden in recent years, it is highly desirable to develop and utilize raw materials that can be recycled and sustainably supplied biomass resources in the field of widely used plastics or engineering plastics. In order to achieve these technical developments, especially Macromolecules derived from organisms such as starch and cellulose are useful as resources in terms of production cost. However, compared with general plastics, they are often pointed out that they have low heat resistance, processability, and low mechanical strength. For this reason, some people have adopted techniques such as improving the processability of cellulose and chemically modifying it to make it thermoplastic. However, it is still pointed out that the derivative reagent used in the manufacturing step or its waste liquid is harmful or loses its original biodegradability. It is also pointed out that if the raw materials are low-purity materials such as wood 200528505 (4), it will be difficult to produce, etc. 'especially there are problems on the environmental side.

In terms of improving thermal and mechanical properties, some people have proposed a method of blending cellulose with currently widely used plastics. Compositions that have improved physical properties or thermoplasticity to some extent have been known in the past. However, in this method, the 'plastic compound must have affinity for cellulose, so it is often defined as polar resins such as polyvinyl alcohol or polyacrylic resins, and resins with low heat resistance, such as aliphatic polyesters. 1-1 1 7 1 20, JP-A 1 0-3 1 6 76 7 and JP 200 1 -3 3 5 7 1 0), the use of the admixture is limited to fibers for clothing In order to obtain higher heat resistance in a narrow range such as medical films, those who have strength have proposed using chemically modified cellulose such as cellulose acetate in order to blend with aromatic polymers (see Patent No. 2 73 2 5 54), but it can still come from environmental issues as mentioned above.

In addition, as a method that does not require chemical modification of cellulose and does not generate waste to make cellulose into thermoplastic, a method of mixing with thermoplastic polymers and dry mechanical pulverization has been disclosed (see Patent No. 3 099064). . Compared with cellulose monomers, the cellulose composition obtained here is thermoplastic, so it can be formed into a molten compound with various resins in a wide range of temperatures. In order to improve the biodegradability, the problem of lowering the mechanical strength of the molded product sometimes occurs. [Summary of the Invention] The present invention aims to provide a novel biodegradable aromatic polyester. -8-200528505 (5)

Another object of the present invention is to provide various biodegradable aromatic polyesters with excellent physical properties that can be used as engineering plastics. The present invention has the above-mentioned excellent physical properties, and aims to provide a biodegradable aromatic polyester film and fiber having heat resistance and weather resistance equivalent to those of a film and fiber made of a non-decomposable aromatic polyester. The present invention further provides a biodegradable polyester containing the present invention, and

Aromatic polyester compositions, which can be more biodegradable than they are, serve another purpose. Another object of the present invention is to provide a cloth, a non-woven fabric, a net, or the like made of the biodegradable polyester of the present invention. Still other objects of the present invention are advantageous from the following description. According to the present invention, the above-mentioned object and advantages of the present invention are firstly represented by the following formula (1) R3

ΐ—f R2 Here R1, R2 and R3 can be the same or different, showing hydrogen atom or Cl ~ C6 courtyard, R4 is not C] ~ C6 courtyard, C6 ~ Cio aryl or C7 ~ Cl aralkyl , M is 2, 3, or 4, and η is a number from 3 to 250,000, and the polyoxyalkylene propylene glycol residue is shown by the following formula (2) -9- 200528505 (6) —0 ~ (〇12) ^ 〇—… P Here P is 2, 3 or 4, the diol residues and terephthalic acid residues are shown, and contain at least one selected from the following formula (3)

... (3)

The additional residues grouped by the ether diol residue, isophthalic acid residue and aliphatic dicarboxylic acid residue shown, and when the additional residue is (i) only the ether diol residue, Perdicarboxylic acid residues are mainly formed from the terephthalic acid residues mentioned above, and 10 to 30 moles of perdiol residues are present. Is formed from ether glycol residues, such as ether glycol residues derived from sugars,

(Π) When containing an isophthalic acid residue, an aliphatic dicarboxylic acid residue, or a combination thereof, 60 to 85 mol% of the total dicarboxylic acid residue is the above terephthalic acid residue, and 40 to 15 mol% is composed of an isophthalic acid residue, an aliphatic dicarboxylic acid residue, or a combination thereof, and (Hi) contains an isophthalic acid residue, an aliphatic dicarboxylic acid residue, or this In combination with any of the ether glycol residues, 60 to 90 mole% of the total dicarboxylic acid residues are the terephthalic acid residues, and 40 to 10 mole% are the isophthalic acid residues. , Aliphatic dicarboxylic acid residues or combinations thereof, and 0.5 to 25 mol% of the total glycol residues are made of ether glycol residues, which is characterized by a dicarboxylic acid residue and two Aromatic polyesters formed from alcohol residues -10- 200528505 (7) to achieve. According to the present invention, the purpose and advantages of the present invention are secondly, 100 parts by weight of the aromatic polyester of the present invention, and 23 to 39 parts by weight of at least one selected from poly (oxyalkylene) glycols and at least one end thereof. The aromatic polyester composition to be sealed is derived from cellulose and 4.3 to 210 parts by weight of at least one kind of derivatives derived from cellulose and its hydroxyl groups. According to the present invention, the above-mentioned object and advantages of the present invention are thirdly achieved by the film made of the aromatic polyester of the present invention and a laminated paper using the same. According to the present invention, the above-mentioned object and advantages of the present invention are achieved. The fourth is achieved by a fiber made of the aromatic polyester of the present invention, a nonwoven fabric, and a cloth or net made of the fiber. [Embodiment]

The present invention is described in detail below. The aromatic polyester of the present invention contains a polyoxyalkylene propylene glycol residue represented by the above formula (1) and an alkylene glycol residue represented by the above formula (2) as a diol component, and contains terephthalic acid Residues are used as dicarboxylic acid components. The aromatic polyester of the present invention further contains at least one additional residue selected from the group consisting of an ether glycol residue, an isophthalic acid residue, and an aliphatic dicarboxylic acid residue represented by the formula (3). . In addition, the aromatic polyester of the present invention may contain the additional residues in any of the cases (i), (ii), and (iii) described above. -11-200528505 (8) Below, for the aromatic polyester of the present invention containing additional residues in the cases of (i), (ii) and (iii), the first aromatic polyester and the second aromatic Polyester and the third aromatic polyester are called. Polyoxyalkylene propylene glycol residue The polyoxyalkylene propylene glycol residue in the present invention is represented by the above formula (1). This residue is derived from the following formula (Γ)

HO—C—C—OH R CH2 —— (CH2 ^ • · ·

OR 4 (1,) Here, the definitions of R1, R2, R3, R4, m and η are the same as those of the above formula (1), and those shown are polyoxyalkylene propylene glycol. That is, this polyoxyalkylene propanol reacts with a carboxylic acid component to form an ester residue.

In the formulae (1) and (Γ), R1, R2, and R3 may be the same or different, and they represent a hydrogen atom or an alkyl group, R4 represents an alkyl group, a C6 to C10 aryl group, or a C7 to Cu aralkyl group, and m is 2 , 3 or 4, η is a number from 3 to 250. The above (:) ~ (: 6 alkyl group may be linear or branched, and may be methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, n- Amyl, n-hexyl, etc. In addition, aryl groups of C6 to CIG include phenyl, tolyl, naphthyl, etc. In addition, C7 to CM aralkyl groups include benzyl, phenethyl, and naphthylmethyl.- 12- 200528505 〇) R1, R2, and R3 are preferably hydrogen atoms, and R4 is preferably methyl. M is 2, 3, or 4, preferably m is 2. Also, η is 3 ~ 2 50, It is preferably 6 to 1 2 0. The weight average molecular weight (Mw) of the polyoxyalkylene propylene glycol represented by the above formula (Γ) is preferably 3 00 to 2,500, and more preferably 5 00 to 2,000. Shigaichi 3 00 ~ 2,500 00 is 111, Chi 2 and 113 are hydrogen atoms, 114 is methyl, and 111 is 2 when, for example, η is equivalent to about 4 to about 54. Polyoxyalkylene propylene glycol system When m is 2, polyoxyethylene propylene glycol is suitable. Polyoxyalkylene propylene glycol residues are preferably from 0.1 to 6.0 mol% of all glycol residues, especially It is more preferable to account for 0.2 5 to 5.0 mole%. The biodegradable foot, while the aromatic polyester of the present invention than a higher decomposition of the conventional bio-resin with a melting point glass transition temperature.

Alkanediol residue The alkanediol residue in the present invention is represented by the above formula (2). This residue is derived from an alkanediol represented by the following formula (2,). HCMCH2-) p-OH · · · (2,) Here p is 2, 3 or 4. That is, the "alkanediol residue" is a residue when an alkanediol reacts with a carboxylic acid component to form an ester group. In the formulae (2) and (2,), p is 2, 3, or 4, preferably p is 2-13-200528505 (10) The alkanediol-based ethylene glycol, propylene glycol, or Butylene glycol, preferably ethylene glycol. The alkanediol residue is preferably 70 to 99.9 mol%, and more preferably 70 to 99.75 mol%. '' The first aromatic polyester The first aromatic polyester is a terephthalic acid residue based on a dicarboxylic acid component, and the diol component is a polyoxyalkylene propylene glycol residue and an alkane as described above. In addition to the diol residue, an ether diol residue represented by the formula (3) is further added. The ether diol residue in the formula (3) is derived from an ether diol represented by the following formula (3 ').

That is, the "ether-alcohol residue" is a residue when the ether-alcohol reacts with a dicarboxylic acid mainly composed of terephthalic acid to form an ether. The ether glycol may be, for example, 1,4: 3,6-dihydro-D-sorbitol (hereinafter referred to as isosorbide) represented by the following formula (4), and represented by the following formula (5) 1, 4: 3,6 · —water_D -mannitol (hereinafter referred to as isomannitol), which is represented by the following formula (6) 1,4: 3,6-dihydroanhydrol · ^ iditol (hereinafter referred to as Yi Aidu &?). Isosorbide, isomannitol, and isodide are available from -14-200528505 (11) D-glucose, D-mannose, and L-idose, respectively. For example, isosorbide is obtained by hydrogenating D-glucose and dehydrating it with an acid catalyst. These ether glycols are substances that can be obtained from biomass in nature and are called renewable ones. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and dehydrating it. Other ether glycols can be obtained by the same reaction except that the starting materials are different.

Of these, isosorbide is preferred. Isosorbide is an ether diol that can be simply manufactured from starch. It can be obtained in large quantities as a resource, and it is easy to manufacture. -15- 200528505 (12) Properties and wide range of applications Idolol

In the aromatic polyester according to the present invention, when all the diol residues are 100 mol%, the ether diol residues derived from the saccharide are in the range of 10 to 30 mol%, and the range is from 10 to 25 mol. The percentage is appropriate. In this range, the biodegradability can be improved, and the effect of increasing the glass transition temperature can be fully exerted. When it exceeds this range, its crystallinity is extremely easy to decrease, and it is difficult to sufficiently increase the polymerization degree, heat resistance, and mechanical properties. The aromatic polyester-based dicarboxylic acid residues related to the present invention are mainly formed from terephthalic acid residues. More specifically, when the total dicarboxylic acid residue is 100 mole%, the range of 91 to 100 mole% is preferable. If the number of terephthalic acid residues is smaller than this range, the melting point or the glass transition temperature will be easily reduced, and it will be difficult to obtain sufficient heat resistance and mechanical properties. A more preferable range is 95 to 100 mole%.

The dicarboxylic acid residue other than the terephthalic acid residue is preferably 9 mol% or less, and more preferably 5 mol% or less. The other dicarboxylic acid that can give a dicarboxylic acid residue may be, for example, isophthalic acid, dianedioic acid, diphenoxyethanecarboxylic acid, diphenyl ether dicarboxylic acid, diphenylsulfonic acid, and the like. Aromatic dicarboxylic acids, aliphatic cyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroisophthalic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, etc., p-A-hydroxyl Bifunctional carboxylic acids such as hydroxy acids such as ethoxybenzoic acid and ε-hydroxybenzoic acid. These may be used singly or in combination of two or more kinds. The first aromatic polyester-based perdiol group is formed from a polyoxyalkylene propylene glycol residue, an alkanediol residue, and the above-mentioned ether diol residue. Based on the whole diol, the polyoxyalkylene propylene glycol is The residue is 0.2 6 ~ 5.0 mole%, the alkanediol-16-200528505 (13)% the residue is 75 ~ 94.75 mole%, and the ether glycol residue is 10 ~ 24.75 mole%; the above polyoxidation The alkylene propylene glycol residue is derived from polyoxyethylene propylene glycol; the alkanediol residue is derived from ethylene glycol and the ether glycol residue is derived from isosorbide; the dicarboxylic acid residue is mainly composed of terephthalic acid In the case of a formic acid residue and the terephthalic acid residue is 91 to 100 mol% based on the dicarboxylic acid residue, it is more suitable. This more suitable first aromatic polyester can be manufactured at a practical cost, has sufficient mechanical and thermal properties, and has excellent biodegradability. As the first aromatic polyester, a compound corresponding to the above-mentioned diol residue or di-residue acid residue can be used as a monomer or oligomer, and a known method can be used, for example, a titanium catalyst, an antimony catalyst, or a tin catalyst Catalysts, germanium-based catalysts, etc. are polymerized. For the polymerization, a melt polymerization method or a method using a melt polymerization method and a solid phase polymerization method can be used. And there is no problem of mutual solubility when polylactic acid is copolymerized with many aromatic polyesters. Such a compound may be, for example, a diol residue or an ester thereof for a diol residue, or a dicarboxylic acid or an ester thereof for an dicarboxylic acid residue, or an anhydrous substance. In addition, although the content of the diol residue or the dicarboxylic acid residue in the present invention can be obtained by actually analyzing the aromatic polyester related to the present invention, it can also be determined by the amount of the starting material and the polymerization reaction. Obtained before and after the mass balance calculation. For example, if the raw material to be used for an acid residue is usually high in boiling point or boiling, it can be easily obtained from the amount of polymer used. In addition, the raw materials corresponding to the diol residues also have low boiling points, and some of them will come out of the polymer. In the pursuit, the mass balance can be subtracted from the remaining portion to obtain the polymerization. Content in the content. -17- 200528505 (14) The second aromatic polyester The second aromatic polyester is a dicarboxylic acid residue consisting of terephthalic acid residue, isophthalic acid residue, aliphatic diacid residue or These combinations are formed, and the total diol residues are formed from polyoxyalkylene propylene glycol residues and alkanediol residues. Isophthalic acid and aliphatic dicarboxylic acid residues are derived from isophthalic acid and aliphatic dicarboxylic acid, respectively. That is, these residues are isophthalic acid or _ aliphatic dicarboxylic acid which is a residue when reacted with polyoxyalkylene propylene glycol and alkanediol to form an ester. The aliphatic dicarboxylic acid is preferably c2 to c] 0 aliphatic dicarboxylic acid. The aliphatic dicarboxylic acid residue includes a residue of a linear or branched aliphatic dicarboxylic acid from ethylene glycol to sebacic acid. These may be, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like. Of these, succinic acid is preferred.

The ratio of terephthalic acid residues contained in the second aromatic polyester is 65 to 85 mol%, preferably 65 to 80 mol%, based on perdicarboxylic acid residues, 70 to 80. Mole% is best. Further, based on the total residual acid residue, the isophthalic acid residue, the aliphatic dicarboxylic acid residue, or a combination thereof is such that it is in the range of 15 to 40 mole%. When less than this range, the biodegradability is significantly hindered. In addition, when it is out of this range, the characteristics mainly based on the crystallinity of the resin are significantly reduced, which is not practically practical. It is preferably in the range of 20 to 35 mole%, and more preferably in the range of 20 to 30 mole%. The second aromatic polyester-based perdiol residue is made of polyoxyalkylene propylene -18- 200528505 (15)

Alcohol residues and alkanediol residues. Based on the total diol residues, the polyoxyalkylene propylene glycol residues are 0.25 to 5.0 mole%, and the alkanediol residues are 9 5.0 ~ 99.7 5 mol% • The polyoxyalkylene propylene glycol residue is derived from polyoxyethylene propylene glycol, and the alkanediol residue is self-ethylene glycol; the dicarboxylic acid residue is made from p-benzene Dicarboxylic acid residues, isophthalic acid residues, aliphatic dicarboxylic acid residues, or combinations thereof. Based on the total dicarboxylic acid residues, terephthalic acid residues account for 70 to 80 mole%. And the isophthalic acid residue, the aliphatic dicarboxylic acid residue or a combination thereof accounts for 20 to 30 mol%, and the aliphatic dicarboxylic acid residue is a succinic acid residue is more suitable. In addition, if the second aromatic polyester is not described here, it should be understood here that the relevant records of the first aromatic polyester can be directly applied, or it can be changed and applied according to circumstances known by the industry. Tertiary aromatic polyester

The third aromatic polyester-based full diol residue is formed from a polyoxyalkylene propylene glycol residue, an alkane diol residue, and the above-mentioned ether diol residue, and the dicarboxylic acid residue is made from terephthalic acid. A formic acid residue, an isophthalic acid residue, an aliphatic dicarboxylic acid residue, or a combination thereof. The total diol residues of the third aromatic polyester are the same as the total diol residues in the first aromatic polyester, so this is removed from the description of the first aromatic polyester about the total diol residues. Other than the content ratio, it is applicable. In addition, since the dicarboxylic acid residue of the third aromatic polyester is the same as the dicarboxylic acid residue of the second aromatic polyester, the second aromatic polyester has -19- 200528505 (16) The descriptions concerning the residues of all-dicarboxylic acid can be applied including the descriptions of the content ratios.

The ratio of terephthalic acid residues contained in the third aromatic polyester is 60 to 90 mole% of the total dicarboxylic acid residues. 70 to 90 mole% is more preferable, and 75 to 90 is more preferable. Mol%. The isophthalic acid residue, the aliphatic dicarboxylic acid residue, or a combination thereof is set to a range of 10 to 40 mole% in terms of the dicarboxylic acid residue. When it is smaller than this range, it is difficult to have good biodegradability. On the other hand, when it is larger than this range, the crystallinity or glass transition temperature of the aromatic polyester is significantly reduced, so it is not suitable. It is preferably in the range of 10 to 30 mole%, and more preferably 10 to 25 mole%. The ratio of the ether diol residues contained in the third aromatic polyester is 0.5 to 25 mol% for the total glycol residues.

The third aromatic polyester-based perdiol residue is formed from a polyoxyalkylene propylene glycol residue, an alkanediol residue, and the ether glycol residue. The alkyl propylene glycol residue is 0.2 5 to 5.0 Moore. / 〇, the alkanediol residue is 75 to 94.7 5 mol%, and the ether diol residue is 5.0 to 25.0 mol%, and the polyoxyalkylene propylene glycol residue is derived from polyoxyethylene Propylene glycol; the alkanediol residue is derived from ethylene glycol and the ether diol residue is derived from isosorbide; the full diol residue is composed of terephthalic acid residue 'and isophthalic acid residue, aliphatic Dicarboxylic acid residues or combinations of these, based on the total dicarboxylic acid residues, terephthalic acid residues account for 60 to 90 mol%, and isophthalic acid residues, aliphatic two The carboxylic acid residue or a combination thereof is preferably 10 to 40 mol%, and the aliphatic dicarboxylic acid residue is preferably a succinic acid residue. -20- 200528505 (17) In addition, matters not mentioned here regarding the third aromatic polyester may be applied in accordance with the matters described in the first aromatic polyester, or by changes made by the manufacturer.

The reduction viscosity of the aromatic polyester of the present invention (except for special mention, hereinafter refers to the first, second and third aromatic polyesters) is preferably 0.5 to 2 dl / g. The glass transition temperature is preferably 0 to 75 ° C, and more preferably 20 to 75 ° C. The melting point is preferably 150 to 250 ° C, and more preferably 180 to 240 ° C.

If the aromatic polyester of the present invention is biodegradable, it can be decomposed by light, especially by sunlight. At this time, the photodecomposition system can reduce the molecular weight of the aromatic polyester and significantly reduce the mechanical properties. The photodecomposition of the aromatic polyester of the present invention is mainly caused by the intensity of photodegradation and subsequent decay. The rate of decay is 2 weeks to 1 year after exposure to sunlight. A film thickness of 20 μm with a thickness of 10 cm x 5 cm can be reduced to a range of less than 2 mm. Therefore, in contact with soil and other microorganisms, it has the effect of accelerating the microorganisms to complete the rate of decomposition and so on. Therefore, it is extremely suitable for applications that are best decomposed as soon as possible. For example, it is suitable for agricultural use to be able to be decomposed into small pieces of less than 2 mm between 2 months and 6 months. Also, when used as a civil material, it may be suitable to change to small pieces in about 2 weeks to 1 month. In addition, the rate of photodecomposition can be adjusted by adding light stabilizers and photooxidation inhibitors that are commonly used to aromatic polyesters. Such light-fastening agents may be, for example, benzotriazole-based, benzophenone-based, cyanoacrylate-based, or salicylate-based compounds. These compounds may be used in combination of two or more kinds. -21-200528505 (18) Specifically, the benzotriazole-based compound may be, for example, 2- (2'-hydroxy-51-

Tolyl) benzotriazole, 2- (2'-hydroxy-5 '· third-butylphenyl) benzotriazole, 2- (2hydroxy-3', 5'-di-tert-butylphenyl) benzene Benzotriazole, 2- (2, -hydroxy-third butyl-5'-tolyl) -5-chlorobenzotriazole, 2- (2f-hydroxy-3f, 5'-di-tert-butylbenzene ) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tertiarypentylphenyl) benzotriazole, 2- {2, -hydroxy-3'-( 3 ”, 4”, 5 ”, 6” -tetrahydrophthalimidemethyl) -5'-tolyl} benzotriazole, and 2,2-methylenebis {4- (1,1, 3,3-tetramethylbutyl) -6- (211-benzotriazol-2-yl) phenol}. In addition, the benzophenone-based compound may be, for example, 2,4-dienylbenzophenone, 2-hydroxy-4-methoxybenzophenone, or 2-hydroxy-4-octyloxybenzophenone. Methanone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4, two Methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, and bis (2-methoxy-4-hydroxy-5-benzylphenyl) methane .

Aromatic polyester composition The aromatic polyester of the present invention has a high affinity between polyoxyalkylene propylene glycol and cellulose, so it can form biodegradability when mixed with cellulose that is originally biodegradable组合 物。 Composition. That is, the aromatic polyester composition of the present invention is composed of 100 parts by weight as described above. The aromatic polyester of the present invention and 23 to 39 parts by weight are at least one selected from poly (oxyalkylene) ethylene glycol and at least A derivative of which one end is closed, and 4.3 to 2 10 parts by weight of at least one kind selected from cellulose and derivatives thereof having a base of -22-200528505 (19). The poly (oxyalkylene) ethylene glycol may be, for example, poly (oxyalkylene) ethylene glycol, poly (oxypropylene) ethylene glycol, poly (oxybutylene) ethylene glycol, or the like. In addition, the derivatives whose one end is blocked are at least one end of which is an alkoxy group such as a methoxy group, an ethoxy group, or an ethoxy group such as an ethoxy group, or a benzyloxy group. Or phenyl, tolyl, octyl phenoxy and the like are blocked as described above poly (oxyalkylene) ethylene glycol.

Examples of the derivatives of the hydroxyl group of cellulose include carboxymethyl cellulose and methyl cellulose. Each of the above components can be combined together, or any two components can be pre-mixed and then another component can be blended. It is more suitable to mix at least one kind of poly (oxyalkylene) ethylene glycol and its derivative with at least one kind of cellulose or its derivative before pulverizing the obtained mixture, and then to blend the aromatic polyester of the present invention. According to this method, the three ingredients can be rapidly mixed under milder conditions to obtain a composition with excellent physical properties.

The cellulose and its derivatives are preferably fine powders. The average particle diameter is preferably 50 μm or less, and more preferably 30 μm or less. Poly (oxyalkylene) ethylene glycol and its derivatives are preferably those having a number average molecular weight in the range of 10,000 to 5 million, and more preferably those in the range of 10,000 to 3 million. The above-mentioned pulverizing treatment is to process the mixture of cellulose and poly (oxyalkylene) ethylene glycol by using a micro-powder generating device, and any type of device can be used, for example, ball milling, planetary ball milling, stirring ball milling, vibration mill, rod Mill and so on. -23- 200528505 (20) In addition, when the composition of the present invention is to be obtained according to the above method, the above three components are melt-kneaded under the condition that the aromatic polyester of the present invention can be melted, and the apparatus used for the melt-kneading may be any device For example, it is preferable to use a polycondensation reaction device or a uniaxial or biaxial melt-kneading extruder.

In addition, the aromatic polyester of the present invention can also be combined with other biodegradable polymers and used as a miscible or non-miscible composition. Biodegradable polymers include polylactic acid resins such as poly-L-lactic acid, poly-D-lactic acid, poly-DL-lactic acid, and stereo-complex polylactic acid, aliphatic polyesters such as polysuccinate, butylene succinate, etc. , Polycaprolactone, Polyglycolide, Polyhydroxybutyrate, Polyhydroxyalkanoate and other polyhydroxy acid-based resins, "Biomax", "ECoFlex" and other similar aromatic biodegradable polyesters and similar polyesters Polyamine copolymer, acetate resin, plasticizable starch, etc. As a result, the aromatic polyester of the present invention or the biodegradable polymer is combined with these polymers to form a composition, so that the aromatic polyester of the present invention can impart mechanical properties such as impact resistance. , Or physical properties such as gas permeability, lamination and other properties, so it is more suitable. The composition of the composition is 1 to 99% by weight of the aromatic polyester of the present invention, 99 to 1% by weight of other biodegradable polymers, preferably 10 to 90% by weight of aromatic polyester, 90 to 10% by weight. Other biodegradable polymers. Uses of the aromatic polyester of the present invention The aromatic polyester of the present invention can be used as various shaped bodies, such as fibers (woven cloth, non-woven cloth, woven cloth, etc.), films, sheets, bags, foams, Forms of bottles, various injection molded products, etc. are used for various applications-24-200528505 (21). These uses can be, for example, nets or ropes for civil materials or plant production, food, clothing, electronic parts, packaging for medical and medical applications, films for civil or agricultural, horticultural, tailoring, sheets or bags, paper, Films and the like are laminated films, containers for foods, water filters, shrinkable films, stationery, and printing inks. It is preferable that the above-mentioned fibers and films use the aromatic polyester of the present invention having a melting point of 180 to 240 ° C or a glass transition temperature of 20 to 75 ° C.

Examples Hereinafter, examples will be described in more detail. The numbers in Examples 1 to 30 are obtained by the following method. (1) Determination of reduction viscosity:

A 120 mg sample was accurately weighed, 10 ml of a mixed solvent of tetrachloroethane / phenol = 50/50 (weight ratio) was added, and it was dissolved in a 140 ° C hot bath. The viscosity of the obtained solution was measured at 35 ° C using an Ubbellohde viscosity tube to obtain the reduced viscosity (7? Sp / c). The unit is dL / g. (2) Measurement of melting point and glass transition temperature: Weigh the sample in an aluminum sample pan, and obtain a chart by using a T e X asinstrume η ta 1 differential scanning calorimeter (TA-2 920) Read the melting point and glass transition temperature. At a heating rate of 2 (TC, measured 0 to 2 80 ° C per minute.) (3) Measurement of biodegradability: -25- 200528505 (22) Biodegradability is measured by the decrease in decay weight in compost. After using the aromatic polyester sample of the present invention or the casting film obtained by casting according to the method described in the examples, it is placed in a polyethylene sieve with a sieve opening of 1 mm and 'buried in a compost kept at 40 to 50 ° C. Medium, sometimes agitated and aerated culture 'to determine the weight loss of the sample remaining in the sieve. Compost is matured in a household biodegradable food waste processor. Use 20% more than 50% weight reduction after 20 days 〇 (Good) rating

(4) Measurement of tensile strength and elongation at break: According to the method of JIS K7127, a tensile tester (RTC- 1250) manufactured by A & D was used to measure the formed piece or film of the sample. (5) Measurement of thermal deformation temperature: The test specimens were measured using Toyo Seiki HDT TESTER in accordance with JIS C224 1 (low load weight 4.6kgf). Φ The polyoxyethylene propylene glycols in Examples 1 to 30 are those having a methoxy group at each terminal. The numbers 各 in Examples 3 1 to 37 were obtained by the following methods. (6) Measurement of melting point (Tm): · The melting point was measured using a differential scanning calorimeter of 9 1 0 manufactured by Du ρ ο n t, and the temperature was increased at a rate of 2 per minute under a nitrogen gas flow to measure. The melting point is 18 (TC or more, more preferably 1 90 ° C or more. The heat resistance is judged to be excellent. -26- 200528505 (23) (7)) Measurement of reduction viscosity: same as (1) above. (8) Biological Degradability test: The biodegradability of the aromatic polyester is evaluated using a laboratory-scale composting device. The decay of the mature compost is visually observed to determine the biodegradability. The specific steps are described below. 5g of each aromatic The polyester was dissolved in 50 ml of phenol: tetrachloroethyl k = 1.1 · (wt / wt), cast with a 100 μm doctor blade, and dried by a hot air dryer to obtain a film thickness of 20 μm. Film samples (Examples 36 and 37) 〇 Put 1.72 kg of porous wood chips (biochips manufactured by Matsushita Electric Works Co., Ltd.) as plant seeds in a compost container (volume 11 liters). 0 · 0 7 5 kg Stomatal cellulose particles (biospheres made by Panasonic Electric Works), replenish about 1 ~ 1.5 kg of vegetable crumbs every day, stir for about 2 minutes every 3 hours, and manually agitate once a week to maintain 50 ~ 60% Moisture, ρΗ7.5 · 5 ~ 8.5, internal temperature 45 ~ 5 5. (: in the state, A sample of 50 mm square slices was placed in the compost, and the sample was sampled after a predetermined period of time. The material attached to the film was washed and removed. After air-drying, the surface appearance of the film was visually observed. 'Weigh the film. After 10 days of compost treatment After that, the film with a weight residual ratio of 10% or less is judged to be highly biodegradable (indicated by ◎ in the table). When the weight residual ratio is 50% or less, it is judged to be biodegradable (0 in the table), When it is less than 95%, it is judged to be low in biodegradability (X in the table). -27- 200528505 (24) (9) Mechanical strength of the film: The mechanical properties of the film are based on the RTC-1210A tensile tester manufactured by ORIENTEC, according to JIS K7 Obtained by the method described in 127. The breaking point stress was 10 MPa or more, the elongation was 500% or more, and the elastic modulus was 400 MPa or more.

(10) Mechanical strength of the molded product The mechanical strength of the molded product was evaluated using a cantilever impact tester (with a notch) in accordance with JIS K691 1. (1 1) Blow-molding film formability: Film formability is evaluated by transfer point and melt viscosity. Melt viscosity is using KOKA-FLOW TESTER (nozzle size: L / D = 2.5 / 0.5 (mm / mm)) from Shimadzu Corporation, the tree under load of 50kg / cm2

The fat drop speed was calculated as the number at a shear rate of 100 seconds. The glass transition point is 20T or more, and the moldability is judged to be good if the melt viscosity is 6000 POISE or more at a shear rate. Example 1 194.2 parts by weight of dimethyl terephthalate, 40.0 parts by weight of a polyoxyalkylene propylene glycol having an average molecular weight of 2000, 33.6 parts by weight of isosorbide, and 108.7 parts by weight of ethylene glycol were placed in a stirring blade and In a three-necked flask of JS Vigoureux tube, 22 X 1 (Γ3 weight -28- 200528505 (25) parts of manganese acetate were added, and transesterification was performed at 180-20 (TC. 2 6 X 1 (Γ3 Part by weight of antimony oxide begins to polymerize. The temperature and pressure are reduced for 2 hours from 220 ° C 4 MPa to 240 ° C, 5 Pa, and the reaction is performed in this state for 2 hours. The excess ethylene glycol is distilled off under reduced pressure. polymerization

The obtained lg polymer was dissolved in 10 ml of a solution of tetrachloroethane / phenol = 50/50 (parts by weight), cast with a doctor blade with a gap of 200 μm, and dried at 95 t to obtain a cast film. The polymer composition (calculated 値), reduction viscosity, melting point, and glass transition temperature biodegradability results are shown in Tables 1 and 2 together with the results of Examples 2 to 6 below. Example 2

Except for using 194.2 parts by weight of dimethyl terephthalate, 33.0 parts by weight of polyoxyethylene propylene glycol with an average molecular weight of 2,000, 3 4.1 parts by weight of isosorbide, and 108 · 7 parts by weight of ethylene glycol, All other operations were performed in the same manner as in Example 1. Example 3 Except that 194.2 parts by weight of dimethyl terephthalate, 40 parts by weight of polyoxyethylene propylene glycol having an average molecular weight of 2,000, 2 4.8 parts by weight of isosorbide, and 108.7 parts by weight of ethylene glycol were used. All were carried out in the same manner as in Example 1. -29- 200528505 (26) Example 4 In addition to the raw material composition, 194.2 parts by weight of dimethyl terephthalate, 20 parts by weight of polyoxyethylene propylene glycol with an average molecular weight of 2,000, 33.6 parts by weight of isosorbide, and 108.7 parts by weight Except for ethylene glycol, 6.0 parts by weight of polyethylene glycol with a weight-average molecular weight of 600, everything was performed in the same manner as in Example 1.

Example 5 Except that the raw material composition was 1 94.2 parts by weight of dimethyl terephthalate, 15.0 parts by weight of polyoxyethylene propylene glycol having an average molecular weight of 2,000, 2 4.8 parts by weight of isosorbide, and 108.7 parts by weight of ethylene glycol. All other operations were performed in the same manner as in Example 1. Example 6

Except for using 194.2 parts by weight of dimethyl terephthalate, 5.0 parts by weight of polyoxyethylene propylene glycol with an average molecular weight of 2,000, 3 6.2 parts by weight of isosorbide, and 10 8.7 parts by weight of ethylene glycol. This was carried out in the same manner as in Example 1. Table 1 Example Mole% acid component Mole% diol component dimethyl terephthalate ethylene glycol polyoxyethylene ethyl propylene glycol isosorbide polyethylene glycol 1 10 0 7 5 1.2 5 2 3.75 0 2 10 0 7 5 2 2 3 0 3 10 0 7 5 8 17 0 4 10 0 7 5 1 2 3 1 5 10 0 7 5 0.7 5 2 4.25 0 6 10 0 7 5 0.2 5 24. 7 5 0 -30- 200528505 (27) Table 2 Example 7? S p / c Melting point (° C) Glass transition point (° C) Biodegradability 1 0.927 2 0 8. 9 5 3 8.65 〇2 0.898-4 0.23 〇3 0.749-4 0.81 〇4 1. 0 6 3 2 0 7. 6 6 6 0.72 〇5 0.766 2 2 5 7 3.5 〇6 0.593 2 2 0 8 6.7 〇Example 7

Put 4 6.83 parts by weight of dimethyl terephthalate, 10.33 parts by weight of dimethyl succinate, 4.68 parts by weight of polyoxyalkylene propylene glycol with an average molecular weight of 5 00, and 3 8 .16 parts by weight of ethylene glycol. Into a three-necked flask equipped with a stirring blade and a Vigro tube, add 22 X 1 (Γ3 parts by weight of manganese acetate, and perform transesterification at 1 80 ~ 2 00 ° C. Then add 2 6 X 1 parts by weight of antimony oxide. Polymerization, temperature and decompression for 2 hours from 220 ℃ 4MPa to 240 ℃, 5 Pa, 5 hours reaction in this state, excess ethylene glycol was distilled off under reduced pressure to polymerize

〇The obtained lg polymer was dissolved in 10 ml of tetrachloroethane / phenol = 50/50 (parts by weight) solution, cast with a doctor blade with a gap of 200 μm, and dried at 95 ° C to obtain a cast film. . The polymer composition (calculated 値), reduction viscosity, 瑢 point, glass transition temperature, and biodegradability are shown in Tables 3 and 4 together with the results of Examples 8 to 13 below. Example 8 -31-200528505 (28) Except as raw material composition 4 7.29 parts by weight of dimethyl terephthalate: I 1.3. 8 parts by weight of dimethyl succinate, 1.6 1 parts by weight Except for polyoxyethylene propylene glycol having an average molecular weight of 500, except for 9.72 parts by weight of ethylene glycol, the rest were performed in the same manner as in Example 7. Example 9

Except for using 47.03 parts by weight of dimethyl terephthalate, 11.56 parts by weight of dimethyl succinate, 1.61 parts by weight of polyoxyethylene propylene glycol with an average molecular weight of 1,000, and 39.8 parts by weight of ethylene glycol The rest are performed in the same manner as in Example 7. Example 1

Except for using 45.69 parts by weight of dimethyl terephthalate, 11.11 parts by weight of dimethyl succinate, 4.67 parts by weight of polyoxyethylene propylene glycol with an average molecular weight of 2000, and 38.52 parts by weight of ethylene glycol, Everything else was performed in the same manner as in Example 7. Example 11 1 Except for the raw material composition, 46.2 9 parts by weight of dimethyl terephthalate, 1 1.8 parts by weight of dimethyl succinate, 3. 16 parts by weight of an average molecular weight of 20000 Except for polyoxyethylene propylene glycol, 39.18 parts by weight of ethylene glycol, the rest were performed in the same manner as in Example 7. Example 1 2 -32- 200528505 (29) Except as a raw material composition, 4 6.9 parts by weight of dimethyl terephthalate 11.64 parts by weight of dimethyl succinate, 161 parts by weight of a polyoxymethylene with an average molecular weight of 2000 Ethylene propylene glycol, 3 ^ J 9 · 8 5 parts by weight of ethylene glycol, and the obtained polymer was discharged into a water bath to obtain a strand. # ^ ^ M shake 'to make it into chips, the rest are the same as in Example 7- Conduct Example 1 3

In addition to using 46.9 parts by weight of 64 parts by weight of dimethyl terephthalate, 64 parts by weight of dimethyl succinate, 0.85 parts by weight of polyoxyethylene propylene glycol having an average molecular weight of 2000, 3 9.95 parts by weight of ethylene glycol, and the obtained polymer was discharged into a water bath to obtain strands' to make it into chips, and the rest were performed in the same manner as in Example 7.

Table 3 Example Mole% of the acid component '-15% & Moore% dimethyl terephthalate succinic acid polyoxyethylene propylene glycol ethylene glycol 7 8 0 20 ^^ 3 9 7 8 8 0 ^ 0 ^ 1-9 9 9 8 0 2 O '0 5 9 9.5 10 8 0 2 0 ^^ 1. 2 5 9 8. 75 11 8 0 2 0 〇 7 5 9 9. 2 ~ δ 12 8 0 2 0 ^^ 0 S 9 9.5 13 8 0 2 0 ^ 0.2 5 9 9.75 -33-200528505 (30) Table 4 Example 7) S p / c Melting point (° C) Glass transition point (° C) Biodegradability 7 1.256 19 6.8 3 6. 1 〇8 1. 2 3 4 19 4.5 4 0.7 〇9 0.861 19 6.8 4 1.7 〇10 0.577 19 7.7 1 6. 9 〇11 1. 0 2 6 19 3.9 3 0.3 〇12 0.9 7 19 3.7 3 4.7 〇13 0.907 2 0 1.4 4 0.6 〇 Example 1 4 Using a biaxial extruder equipped with a T die, the polymer obtained in Example 12 was extruded onto a casting drum at 26 ° C. to obtain The physical properties of the obtained film are shown in Table 5. Example 1 5 The polymer obtained in Example 12 was melted at 24 ° C using an injection molding machine (PS 20 manufactured by Nissei Resin Industry Co., Ltd.) and formed at a mold temperature of 80 ° C. The physical properties of the obtained molded products are shown in Table 5. Table 5 Examples Tensile strength (MPa) Elongation at break Degree (%) Heat Deformation Temperature (0014 (film) 3 5 7 — 15 (molded article) 4 2 8 19 6 3.4 Example 1 6 194.2 parts by weight of dimethyl terephthalate and 15 parts by weight of succinic acid Dimethyl acid, 33 parts by weight of polyoxyethylene propylene glycol with an average molecular weight of 2,000, 2 1.9 parts by weight of isosorbide, 1 1 3.9 parts by weight of ethylene glycol, -34-200528505 (31) In a three-necked flask with a mixing blade and a Vigro tube, 22 x 1 (Γ3 parts by weight of manganese acetate was added, and transesterification was performed at 1 80 to 200 ° C. Thereafter, 26 X 1 (Γ 3 parts by weight of antimony oxide was polymerized. The temperature and pressure were reduced from 220 ° C 4 MPa to 240 ° C, 5 Pa for 2 hours, and the reaction was performed in this state for 2 hours. The excess ethylene glycol was distilled off under reduced pressure to polymerize. The obtained lg polymer was dissolved in 10 ml of tetrachloroethane / phenol = 50/50 (parts by weight) solution, cast with a spatula with a gap of 20 μη1, and dried at 95 ° C to obtain a cast film. . The polymer composition (calculated 値), reduction viscosity, melting point, and glass transition temperature biodegradability results are shown in Tables 6 and 7 together with the results of Examples 17 to 28 below. Example 1 7

Except for the raw material composition, 194.2 parts by weight of dimethyl terephthalate, 29 parts by weight of dimethyl succinate, 40 parts by weight of polyoxyethylene propylene glycol having an average molecular weight of 2000, 6.2 parts by weight of isosorbide, 120.3 Except for parts by weight of ethylene glycol, everything was performed in the same manner as in Example 16. Example 18 Except for the raw material composition, 194.2 parts by weight of dimethyl terephthalate, 29 parts by weight of dimethyl succinate, 33 parts by weight of polyoxyethylene propylene glycol having an average molecular weight of 2000, and 6.7 parts by weight of isopropyl alcohol Except for sorbitol, which was 120.3 parts by weight of ethylene glycol, everything was performed in the same manner as in Example 16. -35- 200528505 (32) Example 1 9 Except for the raw material composition, 46.8 3 parts by weight of dimethyl terephthalate, 8.81 parts by weight of dimethyl succinate, and 7.54 parts by weight of a weight average molecular weight of 500 were used for polyoxidation. Except for ethylene propylene glycol, 0.55 parts by weight of isosorbide, and 36.2 parts by weight of ethylene glycol, the rest were performed in the same manner as in Example 16.

Example 20 Except for the raw material composition, 4.92 parts by weight of dimethyl terephthalate, 9.2 parts by weight of dimethyl succinate, 1.57 parts by weight of polyoxyethylene propylene glycol with an average molecular weight of 500, and 2.42 parts by weight of isopropyl Except for sorbitol, 37.89 parts by weight of ethylene glycol, the rest of the procedure was carried out in the same manner as in Example 16. Example 2 1

Except for the raw material composition, 48.8% by weight of dimethyl terephthalate, 9.18% by weight of dimethyl succinate, 1.57% by weight of polyoxyethylene propylene glycol with an average molecular weight of 1,000, and 2.64% by weight of Except for sorbitol, 37.8 parts by weight of ethylene glycol, the procedure was carried out in the same manner as in Example 16. Example 22 Except as a raw material composition, 4 9.8 3 parts by weight of dimethyl terephthalate, 4. 17 parts by weight of dimethyl succinate, and 7. 3 parts by weight of a polyoxyethylene with an average molecular weight of 20 00 were used. Except for ethyl propylene glycol, 6.42 parts by weight of isosorbide, and 3.46 parts by weight of ethylene glycol, everything was performed in the same manner as in Example 16. -36- 200528505 (33) Example 2 3 In addition to the raw material composition, 46.0 7 parts by weight of dimethyl terephthalate, 8.67 parts by weight of dimethyl succinate, and 7.41 parts by weight of a polyoxyethylene with an average molecular weight of 2000 were used. Except for ethyl propylene glycol, 2.17 parts by weight of isosorbide, and 3 5.8 parts by weight of ethylene glycol, everything was performed in the same manner as in Example 16.

Example 24 Except for use as a raw material composition, 5 1. 18 parts by weight of dimethyl terephthalate, 4.28 parts by weight of dimethyl succinate, 4.39 parts by weight of polyoxyethylene propylene glycol having an average molecular weight of 2000, 7.01 Except for parts by weight of isosorbide and 3.3.4 parts by weight of ethylene glycol, everything was performed in the same manner as in Example 16. Example 2 5

Except for the raw material composition, 47.39 parts by weight of dimethyl terephthalate, 8.91 parts by weight of dimethyl succinate, 4.57 parts by weight of polyoxyethylene propylene glycol with an average molecular weight of 2000, and 2.45 parts by weight of isosorbide Except for 6.69 parts by weight of ethylene glycol, the rest were performed in the same manner as in Example 16. Example 2 6 Except as a raw material composition, 4 8.0 5 parts by weight of dimethyl terephthalate, 9.04 parts by weight of dimethyl succinate, 3.09 parts by weight of polyoxyethylene propylene glycol having an average molecular weight of 2000, and 2.6 weight are used. Except for parts of isosorbide and 37.22 parts by weight of ethylene glycol, the rest were performed in the same manner as in Example 16. The physical properties of this thin -37- 200528505 (34) film are those where the tensile strength is 21.9 MPa ', the elastic modulus is 3 7 3 MPa, and the elongation at break is 749%. Example 2 7 Except as raw material composition, 52.61 parts by weight of dimethyl terephthalate, 4.4 parts by weight of dimethyl succinate, 1.51 parts by weight of polyoxyethylene propylene glycol with an average molecular weight of 2000, and 7.22 weight Except for parts of isosorbide and 3 4.2 7 parts by weight of ethylene glycol, the procedure was performed in the same manner as in Example 16. Example 2 8 Except for use as a raw material composition, 4 8 · 7 5 parts by weight of dimethyl terephthalate, 9.17 parts by weight of dimethyl succinate, 1.57 parts by weight of polyoxyethylene propylene glycol having an average molecular weight of 2000, Except for 2.75 parts by weight of isosorbide and 37.76 parts by weight of ethylene glycol, the rest of the procedure was performed in the same manner as in Example 16. Comparative Example 1 Using a biaxial extruder equipped with a T die, p E T polymer (Teijin P-OM) was extruded on a casting drum, and the obtained film was put into compost to evaluate its biodegradability. 200528505 (35) Table 6 Example Mole% acid component Mole% diol component dimethyl terephthalate dimethyl succinate ethylene glycol polyoxyethylene propylene glycol isosorbide 16 9 0 10 8 3.35 1.6 5 15 17 8 0 2 0 9 3.7 2 4. 3 18 8 0 2 0 9 3.75 1.6 5 4. 6 19 8 0 2 0 9 3.7 5 1. 3 2 0 8 0 2 0 9 3.7 1 5. 3 2 1 8 0 2 0 9 3.7 0. 5 5. 8 2 2 9 0 10 8 3.35 1.2 5 15.4 2 3 8 0 2 0 9 3.75 1.2 5 5 2 4 9 0 10 8 3.35 0.7 5 15.9 2 5 8 0 2 0 9 3.75 0.7 5 5. 5 2 6 8 0 2 0 9 3.7 0. 5 5. 8 2 7 9 0 10 8 3.35 0.2 5 1 6. 4 2 8 8 0 2 0 9 3.75 0.2 5 6 Table 7

Example η S p / c Melting point OC) Glass transition point biodegradability CC) 1 6 0 · 8 5 2 0 1. 2 9 3 5. 8 1 〇1 7 1. 0 7 5 19 3. 4 6 1 2. 9 8 〇1 8 1. 0 7 9 1 9 1. 1 18 · 4 5 〇 1 9 0. 9 7 1 2 0 0 · 3 2 8 • 6 〇 2 0 0.6 6 5 1 2 0 7. 6 5 4 • 9 〇 2 1 0. 6 9 9 2 0 3. 7 5 2 • 3 〇 2 2 0. 6 2 7 2 0 9. 7 4 6 〇 2 3 0. 9 1 8 2 0 2. 4 2 8 .4 〇2 4 0. 6 7 7 2 0 5. 9 5 6 • 3 〇2 5 0. 9 1 2 1 9 4. 8 3 2 • 8 〇 2 6 0. 9 2 3 1 9 7. 5 4 3 • 2 〇 2 7 0. 5 8 8 2 0 9. 3 6 8.2 〇 2 8 0. 6 7 8 2 0 2. 3 5 2 _ 9 〇 Comparative Example 1 0.9 9 6 2 5 6. 0 7 8 • 0 X Examples 29 and 30 The polymers obtained in Examples 22 and 26 were melted in an injection molding machine at 230 ° C and formed at a mold temperature of 130 ° C. The properties of the obtained molded products are shown in Table 8 -39- 200528505 (36) Table 8 Tensile strength (MPa) of the polymer used in the examples Elasticity (MPa) Elongation at break (%) HDT (° 〇2 9 Example 2 2 3 3 · 4 ττττ ^ 4 0 5 5 1. 3 3 0 Example 2 6 4 7. 1 29 8 9 6.7 Example 3 1 498.3 parts by weight of dimethyl terephthalate and 41.7 parts by weight of butyl terephthalate Dimethyl diacid, 324.6 parts by weight of ethylene glycol, 71.3 parts by weight of the diol compound '6 shown in the following formula (c), 4.2 parts by weight of isosorbide were placed in a three-necked flask equipped with a stirring blade and a Vigro tube, As a transesterification catalyst, 2 2 χ] [〇-2 parts by weight of manganese acetate was added, and transesterification was performed at 180 ° C to 200 ° C. Diol compound (C): ho-ch2-ch-oh (〇- CH 『CH 七 〇—CH3 (C) (where η is an average of 値 as 30), and then as a polycondensation catalyst, 26 χ 1 0_2 parts by weight of antimony oxide was added, and polymerization was started in 220 hours in 2 hours. The temperature was raised at 4 MPa, the pressure was reduced to 240 ° C, and the pressure was reduced to 5 Pa. The reaction was performed for 2 hours in this state. The excess ethylene glycol was distilled off under reduced pressure, and the aromatic polyester (A) was polymerized. A) The result, in The following Table 9 is shown as Reference Example 1. Next, 90 parts by weight of cellulose and 10 parts by weight of polyethylene glycol (Mw = 200,000) were dried at 0.5 Tori ·, 105 ° C for 3 hours. Rotary ball mill, pulverized at room temperature and 1000 rpm for 5 hours to obtain a thermoplastic cellulose composition (tempered composition (B)) ° -40- 200528505 (37) under reduced pressure 1 3 3.3 P a, 2 30 ° C melted 70 parts by weight of the aromatic polyester, then added 30 parts by weight of the mixed composition (B), and stirred for 15 minutes to obtain a square aromatic polyester composition. The results are shown in Table 9. _ Example 3 2 In Example 31, except that 50 parts by weight of the aromatic polyester (A) and 50 parts by weight of the mixed composition (B) were used to obtain the aromatic polyester composition, everything else was the same. The results are shown in Table 9.% Example 3 3 In Example 31, the aromatic polyester (A) and the mixed composition (B) were dried and put into a hopper, and the mixture was extruded by biaxial melting and kneading. The machine melts and kneads with the barrel temperature of 23 0 t and the number of screw rotations of 100 rpm. After the air-cooled extruded strand is pelletized by a chipper, the pellets of the polyester composition are obtained. Different than the 'other operations are the same. The results are shown in Table 9.

Example 3 4 In Example 31, except for using 445.5 parts by weight of dimethyl terephthalate '106.1 parts by weight of dimethyl succinate, 372.8 parts by weight of ethylene glycol, 75.5 parts by weight of a diol compound, but The results are shown in Table 9 except that isosorbide was not used. Example 3 5 In Example 31, 5 3 3.5 parts by weight of dimethyl-41-2005-28505 (38) ester, 44.6 parts by weight of dimethyl succinate, and 3 4 7.5 parts by weight of ethylene were used. Glycol, 7 4.3 parts by weight of isosorbide, except that no diol was used, the rest were operated in the same manner. The results are shown in Table 9. Comparative Example 2

In a nitrogen atmosphere, 100 parts by weight of polydimethyl terephthalate (sp / c = 0.84) was melted at 280 ° C, and then 11 parts by weight of the above diol compound (C) was added. Mix at 28 ° C for 30 minutes. Then, the inside of the system was gradually decompressed, and the mixture was stirred at an internal pressure of 66.7 Pa for 1 hour to obtain a resin. The results are shown in Table 9. Comparative Example 3 In Comparative Example 2, the same operation was performed except that the diol compound (C) was not added. The results are shown in Table 9.

-42- 200528505 (39) s polyester copolymer Tm CC) 00 〇CM 00 ⑦ τ—1 Not obsd. 00 LO (Μ LO ① CO ί6 00 卜 rH ο CD 05 inch 00 溶液 solution viscosity 7? S p / c 00 00 〇00 〇〇 00 ο 〇) ζ £) 〇 Inch 00 〇 Mole% Moore% Isosorbide Inch 1Ω rH 〇〇tr ee 1-Η 〇 〇 〇〇〇 Polyoxyethylene propylene glycol C0 τ-Η CO τ-Η Ο ο 〇 〇〇 鮏 11 N3 inch CO CD 00 00 σ > 00 CO 00 〇 ① α > 〇〇〇rH Mole% of dicarboxylic acid Succinic acid 〇 〇 rH rH One (N1 ο ο τ-Η; ο ο ο ο terephthalic acid ο ο σ > ⑦ LO ο ο 05 ο ο ο 1-Η ο ο ο τ-Η Example 3 1 Example 3 2 Example 3 3 Reference Example 1 Example 3 4 Example 3 5 1 Comparative Example 2 Comparative Example 3

-43- 200528505 (40) § 6 «Mechanical strength Izod impact resistance (kg · cm) LO rH CO LO 〇 Not tested Not tested 1 1 Biodegradability ◎ < 1% ◎ < 1% ◎ < 1% 〇3 5% 〇LO TH 〇3 0% 1 1 Tm (° C) 00 (Nl rH rH 组成 CO without cellulose composition) Compound 00 inch Τ-Η CD 〇0 rH 1 1 NO NO t A <? ^ ss ^ 5¾ ^ w mm 3 0% 5 0% 3 0% (extrusion molding) 3 0% 3 0 % 3 0% 3 0% Carrying result is good Good Good Good Good Cannot be combined Cannot be combined Example 3 1 Example 3 2 Example 3 3 Reference Example 1 Example 3 4 Example 3 5 Comparative Example 2 Comparative Example 3

-44-200528505 (41) Example 3 6

174.8 parts by weight of dimethyl terephthalate, 14.6 parts by weight of dimethyl succinate, 1 1 3.9 parts by weight of ethylene glycol, 2 5 parts by weight of a diol compound represented by the following formula (C), and 22.5 parts by weight of isocyanate Sorbitol was placed in a three-necked flask with stirring blades and a Vigro tube. Titanium oxide with 0.003 chemical equivalent to the dicarboxylic acid raw material was added, and transesterification was performed at 180 ° C to 200 ° C. Thereafter, the polymerization was started, and the temperature was raised from 22 ° C, 4 MPa in 2 hours, and the pressure was reduced to 240 ° C, 5 Pa. In this state, the reaction was performed for 2 hours. The excess ethylene glycol was distilled off under reduced pressure, and the polymer polyester was copolymerized. Diol compound (C):

HO-CH.-CH-OH (C) (where η is an average 値 is 3 0)

The temperature of the obtained polyester copolymer is from the cylinder: "It's ^" Laboplastmill 'manufactured by Toyo Seiki Seisakusho Co., Ltd. was extruded at a temperature of 21 ° to 225 ° Ci. The film was formed by a blow molding method. The results are shown in Table i. . Example 3 7 155.4 parts by weight of dimethyl terephthalate, 29.2 parts by weight of dimethyl succinate, 12 0.3 parts by weight of ethylene glycol, and 10 parts by weight of the above formula (C) were used. A diol compound, 8.4 parts by weight of isosorbide, was obtained in the same manner as in Example 3 6-to obtain a film. The results are shown in Table 10. -45-200528505 (42) Table 1 0 Determination of heat resistance and moldability Tm Tg Mv Blow ratio (° C) (° C) (Poise) (measurement temperature) Example 3 6 2 0 5 3 7 7 10 0 (2 2 5 ° C) 4. 0 Good Example 3 7 2 0 0 4 1 9 0 0 (2 2 0 ° 4.0. 0 Good Table 1 0 (continued) Mechanical Strength Solution Viscosity Thickness Breaking Point Stress Breaking Point Extension Biodegradability 7] S p / c from m MPa% Example 3 6 0.8 8 2 0 2 7 7 7 0 ◎ Example 3 7 0.8 9 2 0 2 4 7 0 0 ◎ Example 3 8

1 5 5.2 parts by weight of dimethyl terephthalate, 2 5 parts by weight of polyoxyethylene propylene glycol, 19.4 parts by weight of dimethyl isophthalate, 1 1.2 parts by weight of butyl Diacid, 1 2 4 parts by weight of ethylene glycol was placed in a three-necked flask equipped with a stirring blade and a Vigro tube, 0.1 2 parts by weight of titanium tetrabutoxide was added, and transesterification was performed at 180 to 20 ° C. Add 0.5 parts by weight of Irganox, start polymerization, raise the temperature from 220 ° C, 4MPa in 2 hours, and decompress to 24 ° C, 5 Pa, and react in this state for 4 hours. Remove excess ethylene glycol and add 0.07 parts by weight of trimethyl phosphoric acid when polymerization is complete to obtain a polymer. The polymer obtained in ig is dissolved in 10 ml of tetrachloroethane / phenol = 50/50 (by weight) ) Bath, cast with a spatula with a gap of 200μη, and dried at 95 ° C to obtain a film. -46- 200528505 (43) Composition of polymer (calculated 値), reduction viscosity, melting point, glass transition temperature The results of biodegradability are shown in Tables n and 12. Table 1 1 Composition (mole%) (in dicarboxylic acid component) Terephthalic acid Parts 8 0 Isophthalic acid component 10 Succinic acid component 10 (in diol component) Ethylene glycol component 9 9. 8 7 5 Polyoxyethylene propylene glycol component 0.125 Table 1 2 7} SP / C 1.8 Tm 2 0 6. 8 ° C Tg 3 2 ° C Biodegradability 〇 Example 3 9

The polymer obtained in Example 2 3 was dried with a hot air dryer at 120 ° C, and then rolled in a drum-type single-hole spinning machine equipped with a spinning cap with a hole diameter of 0.8 mm and L / D = 5. The spinning speed is 30 m per minute. The spinning situation was very good. The obtained unstretched filamentous fiber was further stretched at an elongation temperature of 50 ° C and a stretching ratio of 6 times to obtain a stretched filamentous fiber having a fineness of 8 dt ex. The physical properties of the obtained extended filamentary fiber were a tensile strength of 3.2 c N / d te x and an elongation of 15% (based on S L 1 0 1 3). Example 4 〇 100 parts by weight of the polymer produced in Example 23 was dissolved in 900 -47- 200528505 (44) parts by weight of tetrachloroethane / phenol (60/40: weight ratio) pre-casting, and a hot air dryer was used. Dry cast film. The thickness of the obtained film was 20 μm. Example 4 1 99.5 parts by weight of the polymer produced in Example 23 and 0.5 parts by weight of stomach TINUVIN-234 (manufactured by Chiba Specialty Chemicals) were dissolved in 900 parts by weight of tetrachloroethane / phenol (60/40). : Weight ratio) for casting and drying with a hot air dryer to obtain a casting film. The thickness of the obtained film was 20 μηι. Example 42 9.9 parts by weight of the polymer produced in Example 23 and 0.5 parts by weight of TINUVIN-23, 0.5 parts by weight of TINUVIN 144 (made by Chiba Specialty • Chemicals) were dissolved in 900 parts by weight. Parts of tetrachloroethane / benzene (60/40: weight ratio) were cast and dried with a hot-air dryer to obtain a cast film. The thickness of the obtained film was 20 μm. φ Example 4 3 The films obtained in the above Examples 40, 41, and 42 and the film of Example 36 were used for evaluation of photodegradability. There are two methods for evaluation: 〇 · Evaluation of photodegradability = Evaluation 1 Fix the film to a 15 cm X 5 cm metal frame, and place it on a 1 cm shelf where it can be placed in a place where it can be exposed to sunlight. Shang 'Guan Ji-48- 200528505 (45) Permanent change, observe the change in its form. Evaluation 2 Hold the film with a net, place it on the soil that can be exposed to the sun, and observe its change over time. The weight reduction was also measured at this time. The results are shown in Tables 13 and 14 below. β Example 44 30 parts by weight of the j polymer of Reference Example 1 in Example 31 and 70 parts by weight of poly L lactic acid (Shimadzu Corporation "Lacty" # 9 03 1: molecular weight 200,000), A biaxial kneading extruder (L ab ο p 1 astmi 11: Toyo Seiki) at 25 0 ° C was used for mixing to obtain a mixture. A small injection molding machine (Nissei Resin PS 30) was used to form the resulting mixture at a barrel temperature of 250 ° C and a mold temperature of 30 ° C. As a result, a good molded product was obtained. This mixture is one with good biodegradability (0).

-49- 200528505 (46) Residual rate (wt%) after 7 weeks of LO morphological breakage Residual rate violation after 5 weeks (%) LO LO Residual rate (wt%) of 4 weeks after morphological break 〇〇rH 〇 No change in form and no residual Residual rate after 3 weeks (% by weight) 〇〇τ-Η 〇 (M morphological change without breakage Residual rate after 1 week (% by weight) 〇〇τ-Η 〇LO morphological change without fracture Example 2 3 Evaluation method 1 Evaluation method 2

-50- 200528505 (47) m VO Ml mn 〇inch 〇τ-Η 〇rH 〇LO 〇 TO TO morphological fracture 1 Fracture fracture fracture 5 month residual rate (wt%) 〇〇LO 〇C0 〇CO 〇〇 rH 〇00 Morphology without residual fracture Fracture Residual rate at the beginning of the fracture 4 months of initial fracture (mm%) 〇〇〇〇τ-Η 〇〇1 ~ 1 〇inch 〇〇τΉ 〇〇r-1 morphological maintenance morphological maintenance No change in fracture Initial stage of fracture / Example 0 inch τ-Η inch CM inch 0 inch r—) inch (N1 inch evaluation method 1 evaluation method 2 -51-200528505 (48) According to the above results, it can be seen that the aromatic polyester of the present invention It is decomposable when exposed to sunlight. In addition, by including a light-resistant agent in the polyester, the rate of photodecomposition can be controlled.

-52-

Claims (1)

200528505 (1) 10. Scope of patent application1. An aromatic polyester formed by forming an ester bond between a dicarboxylic acid residue and a diol residue, which is characterized by containing the following formula (1) R1 RJ tn. (1) R2 Here R1! ^ 2 and R3 can be the same or different, showing a hydrogen atom or a Ci ~ C6 alkyl group, and R4 shows a Ci ~ C6 alkyl group. Aryl or c7 ~ Ch aralkyl, out of 2, 3 or 4, and η is a number from 3 to 250, the polyoxyalkylene propylene glycol residue is shown as the following formula (2) —Q— (cH2 · * .(2) Here, ρ is 2, 3, or 4. The alkanediol residue and the terephthalic acid residue are shown, and contain at least one selected from the following formula (3) The additional residues of the ether diol residues, isophthalic acid residues, and aliphatic dicarboxylic acid residues shown are grouped as -53- 200528505 (2) (i) In the case of ether glycol residues, the dicarboxylic acid residues are mainly composed of the terephthalic acid residues mentioned above, and 10 to 30 mol% of the total glycol residues are composed of ether glycol residues' ( ii) when it contains only isophthalic acid residues, aliphatic dicarboxylic acid residues, or combinations thereof, 60 to 85 mol% of the total dicarboxylic acid residues are the terephthalic acid residues, and 40 ~ 15 mol% is composed of an isophthalic acid residue, an aliphatic dicarboxylic acid residue, or a combination thereof, and (iii) contains an isophthalic acid residue and an aliphatic dicarboxylic acid residue When any of these combinations are combined with ether diol residues, 60 to 90 mole% of the total dicarboxylic acid residues are the terephthalic acid residues, and 40 to 10 mole% of the residues are from A phthalic acid residue, an aliphatic dicarboxylic acid residue, or a combination thereof, and 0.5 to 25 mol% of the total diol residue is formed from an ether diol residue. 2. The aromatic polyester according to item 1 of the scope of the patent application, wherein the polyoxyalkylene propylene glycol residue is a polyoxyalkylene propylene glycol having a weight average molecular weight of 300 to 2500. 3. The aromatic polyester according to item 1 of the application, wherein the polyoxyalkylene propylene glycol residue is a polyoxyethylene propylene glycol residue. 4. The aromatic polyester according to item 1 of the application, wherein the alkanediol residue is derived from ethylene glycol. 5. The aromatic polyester according to item 1 of the scope of the patent application, wherein the polyoxyalkylene propylene glycol residue is 0.1 to 6.0 mol% of the total glycol residue. 6. The aromatic polyester according to the first patent application range, in which the alkanediol residue is 70 to 99.9% by mole of the total diol residue. -54- 200528505 (3) 7 * The aromatic polyester according to claim 1, wherein the ether glycol residue is an isosorbide residue and the aliphatic dicarboxylic acid residue is a succinic acid residue. 8. The aromatic polyester of item 1 in the scope of the patent application, wherein the total diol residue is formed from a polyoxyalkylene propylene glycol residue, an alkanediol residue, and the ether glycol residue; As for the total diol residue, the polyoxyalkylene propylene glycol residue is 0.25 to 5.0 moles. / 〇, alkanediol residue is 75 ~ 94.75 mole%; the above ether monool residue is 10 ~ 24.75 mole%; the above polyoxyalkylene glycerol residue is derived from polyoxidation Ethylene propylene glycol, the above glycol residues are derived from ethylene glycol, and the above ether glycol residues are derived from isosorbide; the dicarboxylic acid residues are mainly formed from terephthalic acid residues, and the whole As for the dicarboxylic acid residue, the terephthalic acid residue is 91 to 100 mol%. 9 · The aromatic polyester according to item 1 of the scope of patent application, wherein the total diol residues are formed from polyoxyalkylene propylene glycol residues and alkanediol residues; in terms of all diol residues, polyoxidation The alkylene propylene glycol residue is 0.25 to 50 mole%, and the alkylene glycol residue is 95.0 to 99.75 mole%; the above polyoxyalkylene glycerol residue is derived from polyoxyethylene glycol, and The above diol residues are derived from ethylene glycol, and the dicarboxylic acid residues are formed from a terephthalic acid residue and an isophthalic acid residue, an aliphatic dicarboxylic acid residue, or a combination thereof. As for the dicarboxylic acid residue, the terephthalic acid residue is 70 to 80 moles. / 〇, and the isophthalic acid residue, the aliphatic dicarboxylic acid residue or a combination thereof accounts for 20 to 30 mol%, and the aliphatic dicarboxylic acid residue is a succinic acid residue. 10. The aromatic polyester according to item 1 of the scope of patent application, wherein the total glycol residues are polyoxyalkylene propylene glycol residues, alkanediol residues, and the above-55-200528505 (4) ether glycol residues With respect to the total diol residue, the polyoxyalkylene propylene glycol residue is 0.25 to 5.0 mol%, the diol residue is 75.0 to 94.75 mol%, and the ether diol residue is 5.0 ~ 25.0 Moore. /. And the above polyoxyalkylene propylene glycol residue is derived from polyoxyethylene propylene glycol, the above diol residue is derived from ethylene glycol, and the above ether diol residue is derived from isosorbide; all / dicarboxylic acid The residue is formed by a terephthalic acid residue and an isophthalic acid residue, an aliphatic dicarboxylic acid residue, or a combination thereof. For the dicarboxylic acid residue, the terephthalic acid residue is accounted for 60 to 90 mol%, and isophthalic acid residues, aliphatic diφcarboxylic acid residues, or a combination thereof accounts for 10 to 40 mol%, and the aliphatic dicarboxylic acid residue is succinic acid Residues. 11. The aromatic polyester according to item 1 of the patent application, whose reduction viscosity is in the range of 0.5 to 2 dl / g. 12. If the aromatic polyester in item 1 of the patent application has a glass transition temperature in the range of 0 to 75 ° C. 13. For the aromatic polyester in the scope of patent application No. 1, its glass transition temperature is 20 ~ 75. (: Those in the scope. Φ 14. If the aromatic polyester in item 1 of the scope of patent application has a melting point in the range of 150 to 25 kt. 15. If the aromatic polyester in item 1 of the scope of patent application has a melting point of 1 in the range of 80 ~ 240 ° C ° " 1 ··· Aromatic polyester composition 'characterized in that it is composed of 1000 parts by weight of the aromatic polyester as in the scope of the first patent application, 23 ~ 39 parts by weight At least one selected from the group consisting of poly (oxyalkylene) ethylene glycol and at least one side of which is a terminally blocked derivative, and 4.3 to 2 10 parts by weight of at least one selected from cellulose and its derivative of -56- 200528505 (5) hydroxyl group 17 · —A film characterized by being made of an aromatic polyester as described in item 1 of the scope of patent application. 1 8 · A film as claimed in item 17 of the scope of patent application, in which the aromatic polyester is Those whose melting point is in the range of 1 80 ~ 240 ° C. 1 9 · As for the film of item 17 in the scope of patent application, in which the glass transition temperature of the aromatic polyester is in the range of 20 ~ 75 ° C. 2 0. If applied The film in the scope of the patent No. 17 is a film for agricultural and horticultural purposes or a film for food packaging. 2 1 -A kind of laminated paper, which is characterized by laminating a film as described in item 17 of the patent application to paper. 2 2 ·-A kind of fiber, which is characterized by aromatic as described in item 1 of the patent application. Made of polyester. 2 3. If the fiber of the scope of patent application No. 22, where the melting point of aromatic polyvinegar is in the range of 180 ~ 24 ° C. 24. If the fiber of scope of the patent application, No. 22, Among them, the aromatic polyester has a glass transition temperature of 20 ~ 7 5 t: range. 2 5 · —A kind of cloth, non-woven fabric or net, which is characterized by being made of fibers such as 22 in the scope of patent application. 26. If the net of the scope of the patent application is No. 25, it is a civil net or plant production net. 2 7 · If the cloth of the scope of the patent application No. 25 is a non-woven fabric, it is civil sheet or civil material. In the form of a bag. 28 · —A photodegradable molded product characterized by being made of an aromatic polyester such as the one described in Patent Application No. 200528505 (6). -58- 200528505 Qi Wu ···································· ·················································, if there is a chemical formula, please disclose the Inventive chemical formula: None-4-