阅读说明：本技术 一种生物可降解共聚酯及其制备方法 (Biodegradable copolyester and preparation method thereof ) 是由 石燕山 安书怡 宋安 于 2020-08-11 设计创作，主要内容包括：本发明涉及高分子材料领域,具体的涉及到一种生物可降解共聚酯及其制备方法,其制备原料包括二元醇、烷氧基化支链醇、二元酸和钛酸酯；其中,所述烷氧基化支链醇的用量占所述可降解共聚酯的0.05～0.15wt％；其通过如下方法制备得到：(1)将二元醇、烷氧基化支链醇、二元酸和第一批钛酸酯加入到反应釜中进行酯化反应,1.5～4.5小时；(2)对上述酯化反应后的体系升温,抽真空进行预缩聚反应1.5～2.5小时；(3)在上述预缩聚反应结束后加入第二批钛酸酯和磷酸进行反应,然后抽真空进行缩聚反应,降温出料即得。通过烷氧基化显著提高甘油和三羟甲基丙烷的沸点,并且通过烷氧基单元的个数使可降解共聚酯保持足够的热稳定性。(The invention relates to the field of high polymer materials, in particular to biodegradable copolyester and a preparation method thereof, wherein the preparation raw materials comprise dihydric alcohol, alkoxylated branched alcohol, dibasic acid and titanate; wherein the amount of the alkoxylated branched alcohol accounts for 0.05-0.15 wt% of the degradable copolyester; the preparation method comprises the following steps: (1) adding dihydric alcohol, alkoxylated branched alcohol, dibasic acid and a first batch of titanate into a reaction kettle for esterification reaction for 1.5-4.5 hours; (2) heating the system after the esterification reaction, and vacuumizing for pre-polycondensation reaction for 1.5-2.5 hours; (3) and adding a second batch of titanate and phosphoric acid for reaction after the pre-polycondensation reaction is finished, then vacuumizing for polycondensation reaction, and cooling and discharging to obtain the catalyst. The boiling points of glycerin and trimethylolpropane are significantly increased by alkoxylation, and the degradable copolyester maintains sufficient thermal stability by the number of alkoxy units.)

1. A biodegradable copolyester is characterized in that the preparation raw materials comprise dihydric alcohol, alkoxylated branched alcohol, dibasic acid and titanate; wherein the amount of the alkoxylated branched alcohol accounts for 0.05-0.15 wt% of the degradable copolyester; the molar ratio of the dihydric alcohol to the dibasic acid is (1.5-2.5): 1.

2. the biodegradable copolyester of claim 1, wherein said alkoxylated branched alcohol is alkoxylated glycerin and/or alkoxylated trimethylolpropane.

3. The biodegradable copolyester of claim 1, wherein said alkoxylated branched alcohol is a compound of formula 1 and/or formula 2:

wherein R is₁、R₂、R₃Each independently is a hydrogen atom or a methyl group, and x, y and z are each a positive integer.

4. The biodegradable copolyester of claim 3, wherein x, y, and z in formula 1 and formula 2 are each independently not higher than 3.

5. The biodegradable copolyester of claim 1, wherein said dibasic acid is a mixture of aliphatic dibasic acid and aromatic dibasic acid.

6. The biodegradable copolyester of claim 5, wherein said aliphatic dibasic acid is 46-52 wt% of the molar amount of the dibasic acid.

7. The biodegradable copolyester of claim 6, wherein said aliphatic dibasic acid comprises adipic acid; the weight of the adipic acid is at least 80 wt% of the aliphatic dibasic acid.

8. The biodegradable copolyester of any one of claims 1 to 7, wherein the diol is an aliphatic diol; the content of butanediol in the aliphatic diol is at least not less than 90 wt%.

9. The method for preparing biodegradable copolyester according to any one of claims 1 to 8, characterized by comprising the following steps:

(1) adding dihydric alcohol, alkoxylated branched alcohol, dibasic acid and a first batch of titanate into a reaction kettle for esterification reaction for 1.5-4.5 hours;

(2) heating the system after the esterification reaction, and vacuumizing for pre-polycondensation reaction for 1.5-2.5 hours;

(3) and adding a second batch of titanate and phosphoric acid for reaction after the pre-polycondensation reaction is finished, then vacuumizing for polycondensation reaction, and cooling and discharging to obtain the catalyst.

10. The method of claim 9, wherein the weight ratio of the first titanate to the second titanate is 1: (0.3 to 1).

Technical Field

The invention relates to the field of high polymer materials, in particular to biodegradable copolyester and a preparation method thereof.

Background

The 'white pollution' refers to the pollution of the non-degradable plastic wastes to the environment at any time in or scattered around the urban and rural garbage. It mainly comprises plastic bags, plastic packages, disposable polypropylene fast food boxes, plastic tableware cups and trays, electric appliance filling foaming fillers, plastic beverage bottles, yogurt cups, ice cream peels and the like. In the face of increasingly serious white pollution, people hope to find a plastic substitute which can replace the performance of the existing plastic and does not cause white pollution, and degradable plastic is produced at the same time.

The degradable material comprises aliphatic-aromatic copolyester, aliphatic polyester and the like, wherein the aliphatic-aromatic copolyester has good comprehensive performance, can meet the requirement of biodegradation, has better mechanical property, receives more and more attention, and is the key point of development in the year, such as PBAT, PBST and other materials.

Polybutylene terephthalate-adipate (PBAT) is the final class of biodegradable copolyesters with various improvements in performance. CN201910846634.1 aromatic dicarboxylic acid and aliphatic dicarboxylic acid are added with epoxidized soybean oil after continuous esterification and are subjected to continuous pre-polycondensation, epoxy groups are grafted into polybutylene terephthalate adipate (PBAT) molecular chains through ester exchange in the pre-polycondensation process, and then the polycondensation is continuously performed under the condition of higher temperature, so that the molecular weight and the intrinsic viscosity reach target values.

In the process of synthesizing PBAT, n-butyl titanate is generally used as a catalyst, but the catalyst reacts with adipic acid, and the produced product shows severe red color. To change this color, color stabilization is usually added. Such as phosphorous-containing compounds including phosphorous acid, phosphoric acid, sodium dihydrogen phosphate, and the like.

CN201910388763.0 relates to a preparation method of branched biodegradable polyester. The preparation method comprises the steps of firstly carrying out esterification reaction on dihydric alcohol, a branching auxiliary agent, aromatic dibasic acid and aliphatic dibasic acid, adding a trifunctional aziridine group compound after the reaction is finished, and finally carrying out polycondensation to obtain the branched biodegradable polyester. The selected germanium catalyst is expensive in price.

The inventors of CN103649167A observed discoloration of the biodegradable aliphatic-aromatic copolyester product obtained in such a reaction, typically ranging in color from pink to red. This poses a problem: when discoloration is noticeable and cannot be easily overcome or masked with pigments, brighteners or fillers, the aesthetic appearance of the non-white polymer product becomes an obstacle to using the polymer for end uses. Polyhydroxy compounds such as sorbic acid are used as color stabilizers. After the polymer is synthesized, the polymer is added, the steps are complex, and the polymer is not easy to be mixed uniformly.

CN102007160A uses polyfunctional compounds as branching agents and phosphorus-containing compounds as color stabilizers. The branching agent and the color stabilizer were separately selected. The branching agent is a polyhydric alcohol or a polybasic acid such as glycerol, pentaerythritol, trimethylolpropane, pyromellitic anhydride, or the like. At the same time, a phosphorus-containing color stabilizer is required to be added. Glycerol and trimethylolpropane have relatively low boiling points and are relatively easily lost during the polymerization process.

Disclosure of Invention

In view of the above technical problems, a first aspect of the present invention provides a biodegradable copolyester, which is prepared from raw materials including dihydric alcohol, alkoxylated branched alcohol, dibasic acid and titanate; wherein the amount of the alkoxylated branched alcohol accounts for 0.05-0.15 wt% of the degradable copolyester; the molar ratio of the dihydric alcohol to the dibasic acid is (1.5-2.5): 1.

in a preferred embodiment of the present invention, the alkoxylated branched alcohol is alkoxylated glycerin and/or alkoxylated trimethylolpropane.

As a preferred embodiment of the present invention, the alkoxylated branched alcohol is a compound of formula 1 and/or formula 2:

formula 1:

formula 2:

wherein R is₁、R₂、R₃Each independently is a hydrogen atom or a methyl group, and x, y and z are each a positive integer.

In a preferred embodiment of the present invention, x, y, and z in formulas 1 and 2 are independently not higher than 3.

As a preferable technical scheme of the invention, the dibasic acid is a mixture of aliphatic dibasic acid and aromatic dibasic acid.

As a preferable technical scheme, the aliphatic dibasic acid accounts for 46-52 wt% of the molar amount of the dibasic acid.

As a preferred technical scheme of the invention, the aliphatic dibasic acid comprises adipic acid; the weight of the adipic acid is at least 80 wt% of the aliphatic dibasic acid.

As a preferred technical scheme of the invention, the dihydric alcohol is aliphatic dihydric alcohol; the content of butanediol in the aliphatic diol is at least not less than 90 wt%.

A second aspect of the present invention provides a method for preparing the biodegradable copolyester as described above, which comprises the following steps:

(1) adding dihydric alcohol, alkoxylated branched alcohol, dibasic acid and a first batch of titanate into a reaction kettle for esterification reaction for 1.5-4.5 hours;

(2) heating the system after the esterification reaction, and vacuumizing for pre-polycondensation reaction for 1.5-2.5 hours;

(3) and adding a second batch of titanate and phosphoric acid for reaction after the pre-polycondensation reaction is finished, then vacuumizing for polycondensation reaction, and cooling and discharging to obtain the catalyst.

As a preferable technical scheme of the invention, the weight ratio of the first batch of titanate to the second batch of titanate is 1: (0.3 to 1).

Has the advantages that: the invention provides a biodegradable polymer with excellent performance, which has good mechanical properties. The prior art uses glycerol or trimethylolpropane as branching agent, but the boiling point is low, and the glycerol or trimethylolpropane is easy to be drawn out of the reaction system along with butanediol in the polymerization process. It is also mentioned that branched polyether polyols are used as branching agents, but the polyether is added in a relatively large amount if the same branching effect is achieved, but the addition of a large amount of polyether leads to a reduction in the thermal stability of the aliphatic-aromatic copolyester. The invention adopts the alkoxylated glycerin or the alkoxylated trimethylolpropane, can obviously improve the boiling points of the glycerin and the trimethylolpropane, and can keep enough thermal stability through the number of alkoxy units.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

The words "preferred", "preferably", "further", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

The first aspect of the invention provides biodegradable copolyester, which is prepared from raw materials comprising dihydric alcohol, alkoxylated branched alcohol, dibasic acid and titanate; wherein the amount of the alkoxylated branched alcohol accounts for 0.05-0.15 wt% of the degradable copolyester; the molar ratio of the dihydric alcohol to the dibasic acid is (1.5-2.5): 1.

the alkoxylated branched alcohol in the invention is a compound obtained by modifying a polyol with a branched structure through alkoxylation. The polyol having a branched structure includes, but is not limited to, glycerin, ethylene glycol, pentaerythritol, trimethylolpropane, and the like.

In some embodiments, the alkoxylated branched alcohol is an alkoxylated glycerol and/or an alkoxylated trimethylolpropane.

The alkoxy groups in the alkoxylated glycerin and alkoxylated trimethylolpropane described herein include, but are not limited to, ethoxy, propoxy, butoxy, pentoxy, and the like. The number of the alkoxylation units in the molecular structure is not particularly limited, and can be adjusted according to the actual situation.

In some embodiments, the alkoxylated branched alcohol is a compound of formula 1 and/or formula 2:

formula 1:

formula 2:

wherein R is₁、R₂、R₃Each independently is a hydrogen atom or a methyl group, and x, y and z are each a positive integer.

In some preferred embodiments, x, y, and z in formulas 1 and 2 are each independently not higher than 3.

In some embodiments, the alkoxylated branched alcohol is selected from a mixture of one or more of ethoxylated glycerol, propoxylated glycerol, ethoxylated trimethylolpropane, propoxylated trimethylolpropane.

Preferably, the alkoxylated branched alcohol structure contains less than or equal to 9 alkoxylated units per molecule.

The dihydric alcohol of the present invention has a molecular structure containing two hydroxyl groups, and the kind of the dihydric alcohol is not particularly limited in the present invention, and any one or more combinations of the following kinds may be selected, for example: diols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, heptanediol, octanediol, alkane (9 to 22) diols, 3-methyl-1, 5-pentanediol, alkane-1, 2-diols (C17 to 20), 1, 3-or 1, 4-cyclohexanedimethanol, 1, 4-cyclohexanediol, hydrogenated bisphenol A, 1, 4-dihydroxy-2-butene, 2, 6-dimethyl-1-octene-3, 8-diol, bisphenol A and the like.

In some embodiments, the glycol is an aliphatic glycol; the content of butanediol in the aliphatic diol is at least not less than 80 wt%.

Preferably, the content of butanediol in the aliphatic diol is at least not lower than 90 wt%.

More preferably, the aliphatic diol is butanediol.

The dibasic acid used in the present invention is well known to those skilled in the art, and the carboxylic acid having two carboxyl groups in its structure may be any of various dibasic acids well known to those skilled in the art, and the kind of the dibasic acid is not particularly limited.

In some embodiments, the diacid is a mixture of an aliphatic diacid and an aromatic diacid.

Further, the aliphatic dibasic acid accounts for 40-60 wt% of the molar weight of the dibasic acid.

Preferably, the aliphatic dibasic acid accounts for 46-52 wt% of the molar weight of the dibasic acid.

The kind of the aliphatic dibasic acid in the present invention is not particularly limited, and various aliphatic dibasic acids known to those skilled in the art can be selected, and examples include, but are not limited to: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, methylcyclohexanedioic acid, ethylcyclohexanedicarboxylic acid, cyclopentanedioic acid, and the like, and the above components may be used alone or mixed in any proportion.

In some embodiments, the aliphatic dibasic acid comprises adipic acid; the weight of the adipic acid is at least 60 wt% of the aliphatic dibasic acid.

Preferably, the weight of the adipic acid is at least 80 wt% of the aliphatic dibasic acid.

Further preferably, the weight of the adipic acid is at least 90 wt% of the aliphatic dibasic acid.

The aromatic dibasic acid used in the present invention is not particularly limited, and various aromatic dibasic acids known to those skilled in the art can be used, and examples thereof include: terephthalic acid, phthalic acid or isophthalic acid, methyl-substituted phthalic acid, ethyl-substituted phthalic acid, halogen-substituted phthalic acid, hydroxy-substituted phthalic acid, naphthalenedicarboxylic acid, substituted naphthalenedicarboxylic acid, and the like.

Preferably, the aromatic dibasic acid is terephthalic acid.

In the process of preparing branched copolyester by using conventional components of glycerin, trimethylolpropane and the like as branching agents, the boiling point of the branching agents is low, so that the reaction degree is low, and the comprehensive performance of the copolyester is not obviously improved. In the process of completing the present invention, the applicant finds that the boiling points of the components can be significantly increased after the glycerol and the trimethylolpropane are subjected to alkoxylation modification, so that the components can fully participate in the preparation process of the copolyester, and the mechanical properties of the copolyester can be significantly improved by using a trace amount. Meanwhile, due to the higher functionality, the alkoxylated glycerin and the alkoxylated trimethylolpropane are easy to dehydrate to form a three-dimensional crosslinking network structure with a certain branched chain or crosslinking degree in the dibasic acid esterification reaction and the subsequent polycondensation process, so that the response speed and the response capacity of the copolyester material to external stress are improved, the copolyester material can absorb more external energy without being broken, and the mechanical strength of the copolyester is improved. In addition, the applicant has unexpectedly found that the thermal stability of the copolyester can be significantly improved by the alkoxylated glycerin and the alkoxylated trimethylolpropane, so that the copolyester can still maintain excellent comprehensive performance under high-temperature and high-humidity environments and can be normally used. It is probably because the formation of the structure-type crosslinked structure by the reaction of the above-mentioned components having multiple functionalities contributes to improvement of cohesive energy density of polymer segments, makes arrangement between molecular chain structures denser, and requires more energy to cause migration, rotation, or other physicochemical reactions of the segments under the stimulation of heat or the like, thereby enabling stable existence at a certain temperature.

However, applicants have found that the thermal stability and mechanical properties of the copolyester are not improved by modification to increase the molecular weight of glycerol or trimethylolpropane. When applicants used glycerine polyether-26 polymerized from glycerine and ethylene oxide in place of the alkoxylated glycerine/alkoxylated trimethylolpropane in the present system, it was found that the thermal stability of the copolyester was not improved, the melt index change when heat treated at 80 degrees celsius at 80% humidity for 200 hours was even higher and the thermal stability was even worse than the copolyester with (alkoxylated) glycerine. Probably because the glycerol ether has insufficient functionality on one hand, a better body type crosslinking structure is formed in the reaction process, and the cohesive energy density of the polymer is improved. On the other hand, due to the introduction of the long-chain-segment polyether structure, the flexibility of the polymer chain segment is improved, the activation energy of the polymer chain segment is reduced, and the polymer can move and migrate at a lower temperature, so that the conformation is changed under the stimulation of lower stress or heat and the like, the larger physical and chemical property change is caused, and the normal use of the material is influenced.

A second aspect of the present invention provides a method for preparing the biodegradable copolyester as described above, which comprises the following steps:

(1) adding dihydric alcohol, alkoxylated branched alcohol, dibasic acid and a first batch of titanate into a reaction kettle for esterification reaction for 1.5-4.5 hours;

(2) heating the system after the esterification reaction, and vacuumizing for pre-polycondensation reaction for 1.5-2.5 hours;

(3) and adding a second batch of titanate and phosphoric acid for reaction after the pre-polycondensation reaction is finished, then vacuumizing for polycondensation reaction, and cooling and discharging to obtain the catalyst.

In some embodiments, the first and second titanate are present in a weight ratio of 1: (0.3 to 1).

The titanate is a compound obtained by reacting titanium tetrachloride and an alcohol compound in a nitrogen atmosphere, the reaction can be carried out in an organic solvent, gas released in the reaction process can be absorbed by alkali liquor, and the titanate is obtained by discharging. The alkyl chain length and the alkyl chain structure in the titanate structure are adjusted by selecting specific alcohol compounds.

In some embodiments, the first and second titanate esters are tetrabutyl titanate and/or tetraisopropyl titanate, respectively.

In the preparation process of the biodegradable copolyester, part of titanate is added in the esterification process of dihydric alcohol, dibasic acid and alkoxylated branched alcohol in the first step, and then the rest titanate is added in the final polycondensation stage in the third step to further catalyze the condensation polymerization of the prepolymer. The specific operation and control parameters of the esterification reaction, the pre-polycondensation reaction and the final polycondensation reaction in the steps 1, 2 and 3 are not particularly limited in the present invention, and the related parameters can be regulated and controlled according to the methods known to those skilled in the art. Wherein the temperature of the branching reaction in the first step is generally controlled within the range of 200-250 ℃, the temperature of the pre-polycondensation reaction and the final polycondensation reaction in the second step and the third step is controlled within the range of 230-250 ℃, and the reaction is carried out by controlling the vacuum degree below 200Pa in the final polycondensation reaction process.

In some preferred embodiments, the method for preparing the biodegradable copolyester comprises the following steps:

(1) adding dihydric alcohol, alkoxylated branched alcohol, dibasic acid and a first batch of titanate into a reaction kettle, and carrying out esterification reaction for 1.5-4.5 hours at 200-240 ℃ under the nitrogen atmosphere;

(2) heating the system after the esterification reaction to 240-250 ℃, vacuumizing to below 15kPa, and carrying out a pre-polycondensation reaction for 1.5-2.5 hours;

(3) and adding a second batch of titanate (the rest titanate) and phosphoric acid after the pre-polycondensation reaction is finished, vacuumizing to 50-200 Pa, reacting for 1.5-3.0 hours, and then cooling and discharging to obtain the catalyst. Wherein the discharging can be carried out in the conventional modes of melt extrusion granulation, drying and the like.

To increase the viscosity of the product, high active ingredients may also be added for further chain extension or crosslinking. The cross-linking agent and the chain extender used in the cross-linking or chain extension process are not particularly limited, and various high-activity components known to those skilled in the art can be selected, such as epoxy monomers such as epoxy glycidyl ether, isocyanate monomers such as isofluorodione diisocyanate, high-activity acyl chloride monomers such as sebacoyl chloride, and the like. The chain extension and crosslinking processes and methods are not particularly limited in the present invention, and the polycondensation product may be mixed and stirred and then fed into a tackifying kettle, and the chain extender or the crosslinking agent and other components are added for tackifying, and the specific reaction parameters, such as reaction temperature and vacuum degree, are determined according to the specific conditions.

In addition, on the premise of not affecting the comprehensive performance of the biodegradable copolyester containing the amide group, other auxiliary agents can be added into the biodegradable copolyester containing the amide group, and the auxiliary agents can be selected from various components well known to those skilled in the art, such as flame retardants, antioxidants, ultraviolet absorbers, dispersants, antibacterial agents, pigments, delustering agents, heat stabilizers, weather-resistant agents, plasticizers, antistatic agents, anti-coloring agents and the like.

The flame retardant is not particularly limited, and there may be mentioned: guanidine phosphate, ammonium phosphate, melamine phosphate, triphenyl phosphate, tris (2, 3-dichloropropyl) phosphate, ammonium polyphosphate, phosphate, tricresyl phosphate, trichloroethyl phosphoric acid, and the like.

The antioxidant is not particularly limited, and there may be mentioned: and antioxidants such as phosphorus compounds including copper compounds, organic or inorganic halogen compounds, hindered phenols, hindered amines, hydrazines, sulfur compounds, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, and magnesium hypophosphite. The ultraviolet absorber is not particularly limited, and there may be mentioned: benzotriazole-based ultraviolet absorbers such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-butylphenyl) benzotriazole, 2- (2-hydroxy-5-octylphenyl) benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, and 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole; benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone.

The antibacterial agent is not particularly limited, and there may be mentioned: silver ion antibacterial agents, zinc oxide, copper oxide, ammonium dihydrogen phosphate, lithium carbonate, acylaniline, imidazoles, thiazoles, isothiazolone derivatives, quaternary ammonium salts, biguanidine, phenolic formic acid, sorbic acid, organic iodine, nitrile, thiocyanide, copper agents, trihalogenated allyl compounds, organic nitrogen-sulfur compounds, chitin, mustard, castor oil, horseradish and the like.

The heat stabilizer is not particularly limited, and there may be mentioned: the heat stabilizer includes basic lead salts, metal soaps, organotin compounds, organic compounds and polyols, composite stabilizers, and the like.

The antifungal agent is not particularly limited, and there may be mentioned: pentachlorophenol, sodium pentachlorophenol, pentachlorophenol laurate, salicylanilide, copper 8-hydroxyquinoline, bis (tri-N-butyltin) oxide, bis (tributyltin) sulfide, tributyltin acetate, tributyltin chloride, tributyltin fumarate, tributyltin fluoride, N- (trichloromethylthio) phthalimide, N- (trichloromethylthio) -4-cyclohexene-1, 2-dicarboximide, 5, 6-dichlorobenzoxazolinone, N- (fluorodichloromethylthio) phthalimide, and the like.

The antistatic agent is not particularly limited, and there may be mentioned: stearamidopropyl dimethyl- β -hydroxyethylammonium nitrate, (3-lauramidopropyl) trimethylammonium methyl sulfate, N-bis (2-hydroxyethyl) -N- (3 '-dodecyloxy-2' -hydroxypropyl) methyl ammonium sulfate, N- (3-dodecyloxy-2-hydroxypropyl) ethanolamine, trishydroxyethyl methylammonium methyl sulfate, stearamidopropyl dimethyl- β -hydroxyethylammonium dihydrogen phosphate, alkyl phosphate diethanolamine salts, and the like.

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.