KR102205865B1 - Adhesive biodegradable polyester resin derived from biomass and the method of manufacturing thereof - Google Patents

Abstract

The present invention relates to an adhesive biodegradable polyester resin derived from biomass and a method for preparing the same. Particularly, the present invention provides a biodegradable polyester resin having excellent adhesion and excellent surface energy, low-speed peel force, high-speed peel force, durability and water resistance. The adhesive biodegradable polyester resin uses 2,5-puran dicarboxylic acid and isocyanate derived from biomass in order to increase the adhesion, and has a number average molecular weight of 70,000 or more and a weight average molecular weight of 150,000 or more.

Description

Adhesive biodegradable polyester resin derived from biomass and the method of manufacturing thereof

The present invention relates to a biomass-induced adhesive biodegradable polyester resin and a method for manufacturing the same, and more particularly, to a biodegradable polyester resin having excellent adhesion with excellent surface energy, low-speed peeling force, high-speed peeling force, durability and water resistance. As an adhesive biodegradable polyester derived from biomass with excellent adhesion with a number average molecular weight of 70,000 or more and a weight average molecular weight of 150,000 or more by using biomass-derived 2,5-furandicarboxylic acid and isocyanate to increase adhesion, It relates to a resin and a method of manufacturing the same.

As the living environment improves, the number of disposable plastics is gradually increasing. Disposable plastics used in this way cause serious environmental pollution when disposed of in the natural environment.

Accordingly, in order to solve these problems, many studies are being conducted around the world to solve such serious environmental problems by manufacturing disposable products with biodegradable resins.

However, if an existing adhesive is used for a product made of biodegradable resin, the adhesive is not biodegradable, so even if the biodegradable resin product is biodegraded, the adhesive does not decompose and may cause secondary environmental pollution.

Therefore, environmental pollution can be solved by manufacturing a biodegradable disposable product that can be completely biodegradable by using a biodegradable adhesive in disposable products and products made of biodegradable resin.

More specifically, in general, acrylic-based adhesives that are not biodegradable are widely used as conventional adhesives, and in particular, biodegradable polyester resin research has been actively conducted in recent years for environmental protection such as preservation of the global environment.

However, disposable products used for plastics or resins adhered to plastics are non-biodegradable resins, and such non-degradable resins are adhered to products made of biodegradable, so disposable products with non-degradable adhesion to biodegradable resins cannot be completely degraded. , The disposable product to which the non-degradable resin is bonded is a situation that cannot fundamentally solve the environmental pollution, which is the original purpose, and rather may cause secondary environmental pollution.

In addition, as the adhesive biodegradable polyester resin is important in water resistance and durability, the problem of biodegradability was developed by developing an adhesive biodegradable polyester resin having an acid value of 0.5mg-KOH/g or less. Water resistance and durability can be solved.

In order to solve this conventional problem, adhesive biodegradable resins have been developed. In Korean Patent Registration 10-1696767 (registration date January 10, 2017), a lactic acid monomer is added to polylactic acid at a temperature of 130°C to 190°C. It is melt-mixed for a minute, but with respect to 100 parts by weight of the polylactic acid, the lactic acid monomer is mixed with 20 to 30 parts by weight, and with respect to 100 parts by weight of the polylactic acid, 5 to 20 parts by weight of rosin are further mixed, and , When the polylactic acid is amorphous, melt mixing may be performed at 140 to 160°C, and in the case of a crystalline form, a biodegradable pressure-sensitive adhesive manufacturing method is known, characterized in that melt mixing is performed at 170 to 190°C.

In addition, Korean Patent Registration No. 10-2050731 (registration date November 26, 2019) is a composition for a pressure-sensitive adhesive to which a biodegradable synthetic resin is added, and 100 parts by weight of an alkyl acrylate composed of 2-ethylhexyl acrylate and n-butyl acrylate Wow; 2 to 15 parts by weight of glycidyl methacrylate; 10 to 25 parts by weight of hydroxyalkyl acrylate; 15 to 35 parts by weight of acrylic acid; 10 to 22 parts by weight of a nonionic surfactant; 10 to 22 parts by weight of a UV curable resin; 110 to 220 parts by weight of an organic solvent; 10 to 50 parts by weight of a biodegradable synthetic resin composed of a protein extracted from any one of green algae, brown algae, and red algae; and, the biodegradable synthetic resin homogenizes the sea algae, and has a pH of 11 to 13 with an alkaline solution. A first step of first extracting the protein by processing so as to be; A second step of adding a weakly acidic solution to the material extracted in the first step to obtain a mixture of fibers and proteins; A third step of producing a synthetic resin chip by melting the mixture of fiber and protein at a temperature of 90°C to 95°C for 5-6 hours while melting; Produced through the process of the fourth step of pulverizing the synthetic resin chip to form a powder, and mixing and stirring the pressure-sensitive adhesive composition to which the biodegradable synthetic resin is added while heating at a temperature of 60°C to 70°C. A composition for a water-dissociable pressure-sensitive adhesive containing a biodegradable synthetic resin, characterized by preparing a composition, is known.

However, the patents are not biodegradable polyester resins, but biodegradable resins, which cannot be used in general disposable products, and when acrylate resins are used, they are not completely biodegradable and thus cannot be commercialized.

In addition, in Korean Patent Registration 10-1433809 (registration date August 19, 2014), at least one selected from aliphatic dicarboxylic acids and acid anhydrides thereof 10 to 70% by weight, lactic acid 5 to 60% by weight, and neopentyl glycol , 2-methylpropanediol, 1,2-propanediol, 1,3-propanediol, ethylbutylpropanediol, and 10 to one or more aliphatic glycols selected from 2,2,4-trimethyl-1,3-pentanediol Biodegradable polyester compositions for solvent-type adhesives containing 50% by weight have been developed.

In addition, in Korean Patent Registration 10-2047147 (registration date November 14, 2019), at least, polyester obtained by polycondensing a dicarboxylic acid having a side chain and an aliphatic diol having 3 to 10 carbon atoms, and a polyester containing a crosslinking agent. A pressure-sensitive adhesive layer obtained by crosslinking a pressure-sensitive adhesive composition, wherein the polyester has a weight average molecular weight of 5000 to 60000, and a gel fraction of the pressure-sensitive adhesive layer is 74 to 98% by weight.

In addition, Korean Patent Laid-Open Publication No. 10-2019-0103416 (published date September 4, 2019) includes the following, a hot melt adhesive: lactic acid oligomer or polymer having a weight average molecular weight of about 1500 to about 3000, about 10 to about 20 weight %; About 40 to about 75 weight percent polylactide having a weight average molecular weight of about 10,000 to about 18,000; About 20 to about 35 weight percent polyester formed from the copolymerization of one or more diols and one or more dicarboxylic acids; And about 0.5 to about 5% by weight of a copolymer of vinyl acetate and mono-unsaturated short chain fatty acids, the fatty acids having 4 to 12 carbon atoms, where all weight percentages are known to be based on the total weight of the hot melt adhesive.

However, the above patents are biodegradable polyester resins having a high acid value without taking into account the characteristics of biodegradable polyester resins, which are not biodegradable when discarded in the natural environment, and have remarkable storage at room temperature and water resistance due to their high acid value. There was a problem that the product was not worth commercialization due to the remarkable decrease in physical properties.

[Patent Document 001] Korean Patent Registration 10-1696767 (Registration Date January 10, 2017) [Patent Document 002] Korean Patent Registration 10-2050731 (Registration Date November 26, 2019) [Patent Document 003] Korean Patent Registration 10-1433809 (Registration Date August 19, 2014) [Patent Document 004] Korean Patent Registration 10-2047147 (Registration Date November 14, 2019) [Patent Document 005] Korean Patent Publication 10-2019-0103416 (Publication date September 4, 2019)

Accordingly, the present invention solves the problem of the existing non-biodegradable adhesive resin, and solves the adhesive strength, water resistance, and durability, which are disadvantages of biodegradable resins, and is a biodegradable polyester resin composition with adhesive that is completely decomposed upon disposal in the natural environment, and The problem to be solved is to protect the natural environment by providing the manufacturing method.

In particular, the present invention is a biodegradable polyester resin with excellent surface energy, low-speed peeling force, high-speed peeling force, durability and water resistance excellent adhesion, and 2,5-furandicarboxylic acid and isocyanate derived from biomass to increase adhesion. It is an object to solve the problem of providing an adhesive biodegradable polyester resin derived from biomass having excellent adhesion with a number average molecular weight of 70,000 or more and a weight average molecular weight of 150,000 or more and a method of manufacturing the same.

The present invention to solve the above problem. A biodegradable polyester resin for adhesion that has excellent surface energy, peel strength, storage stability and durability, and has an acid value of 0.5mg-KOH/g or less, a weight average molecular weight of more than 150,000, and is dissolved in an organic solvent. To provide a polyester resin is used as a means of solving the problem.

In more detail, the present invention is a biodegradable adhesive polyester resin used in disposable products and plastic products made of biodegradable resin, as an aromatic dicarboxylic acid component derived from biomass used as a method for producing a polymer as follows [Chemical Formula 1] There are 2,5-furandicarboxylic acid, isophthalic acid, and the like, and are not limited to one type, and such aromatic dicarboxylic acid may be used as a single component or a mixture of two or more.

[Formula 1]

delete

delete

In addition, aliphatic (including cyclic aliphatic) dicarboxylic acids (or anhydrides) include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonandicarboxylic acid, 1,10 -Decanedicarboxylic acid and acid anhydrides thereof are included, but such aliphatic (including cyclic aliphatic) dicarboxylic acid or its acid anhydride may be used as a single component or a mixture of two or more.

As another preferred specific example, the aliphatic glycol used in the esterification reaction and the transesterification reaction includes ethylene glycol, 1,4-butanediol, 1,5-pentadiol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol may be used as a single component or a mixture of two or more.

As another preferred specific example, the weight part of the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid among the acid components used in the manufacturing process of the aliphatic/aromatic copolyester polymer of the present invention is preferably 55:45 to 45:55, in which case In order to have biodegradability, care must be taken since aromatics in the total acid component exceed 55 weight ratio, since it is not biodegradable.

In addition, by using a multifunctional crosslinking agent to maintain the adhesive strength of high viscosity, it is possible to control the adhesive properties of the adhesive, and it acts to improve the cohesiveness of the adhesive by reacting with carboxyl groups and hydroxyl groups.

An isocyanate-based compound may be used as the multifunctional crosslinking agent according to the present invention, and the isocyanate-based compound is not particularly limited, and for example, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone Diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, etc. are mentioned. These may be used alone or in combination of two or more.

As another preferred specific example, the catalyst introduced at the beginning or end of the esterification reaction, transesterification reaction, and condensation polymerization reaction may be used in the range of 0.01 to 0.8% by weight based on parts by weight of the total reactant.

As a specific example of such a catalyst, it is preferable to use one or a mixture of two or more selected from the group consisting of tetrabutyl titanate, trioctyl antimony oxide, tin oxide, calcium acetate, zinc acetate, tetrapropyl titanate, and the like.

As another preferred specific example, a stabilizer is additionally added at the beginning or end of the esterification reaction, transesterification reaction, and condensation polymerization reaction.

These stabilizers are used in the range of 0.05 to 0.4% by weight based on the total reaction and weight, and these stabilizers may be used alone or as a mixture of two or more types of phosphorous acid, trimethyl phosphate, and triphenyl phosphate.

In addition, the temperature range for performing the first esterification reaction and transesterification reaction is preferably maintained at 210 to 230°C, and the temperature at which the secondary esterification reaction and transesterification reaction is performed is suitably in the range of 220°C to 240°C. .

As another preferred specific example, it is preferable that the molar ratio of the acid component to the glycol added to the first and second esterification reactions is 1:1.15 to 1:1.5 mol.

As another preferred specific example, the condensation polymerization reaction temperature is preferably carried out for 130 minutes to 180 minutes under a vacuum degree of 0.01 to 2.0 Torr in a temperature range of 230 ℃ to 290 ℃.

Biodegradable resins currently available worldwide do not have an adhesive function. Accordingly, the present invention is adipic acid, sebacic acid, 1.10-dodecanedicarboxylic acid, isophthalic acid and the acid component in order to prepare a biodegradable polyester resin with excellent adhesion that can be used in a solvent or used in an extruder. Biodegradable polyester resin for adhesion that is selected from 2,5-furandicarboxylic acid and is easily dissolved in a solvent by using neopentyl glycol and/or ethylene glycol as glycol components and can be coded through an extruder. Was synthesized.

In another aspect, the present invention was prepared according to the manufacturing method described in the above-described aspect to prepare a biodegradable polyester resin for adhesion having excellent surface energy, peel strength, water resistance and durability.

The biodegradable polyester resin for adhesive prepared at this time has an acid value of 0.5mg-KOH/g or less, and a biodegradable polyester resin for adhesive having excellent water resistance and durability having a weight average molecular weight of 150,000 or more was developed.

The adhesive biodegradable polyester resin of the present invention is an adhesive polyester resin having excellent surface energy, peelability, water resistance and durability, and has an acid value of 0.5 mg-KOH/g or less. With a weight average molecular weight of 150,000 or more, it solves the water resistance and durability, which are the disadvantages of biodegradability, and at the same time, it is completely decomposed when disposed of in the natural environment, thereby providing excellent effects of protecting the natural environment.

The present invention is an aliphatic/aromatic copolyester resin, which has water resistance, excellent adhesion, and durability, and at the same time has natural biodegradability upon natural disposal, as an adhesive aliphatic/aromatic copolyester resin and a manufacturing method.The synthesis method is as follows.

Any one selected from aromatic dicarboxylic acids (or acid anhydrides thereof) containing aromatics in molecular structures such as 2,5-furandicarboxylic acid having aromatic dicarboxylic acid and isophthalic acid, neopentyl glycol and ethylene glycol, or It is carried out by reacting an aliphatic glycol containing one or more.

As a one-step synthesis method, the aromatic dicarboxylic acid component, glycol, catalyst, and stabilizer are first added, and the temperature is gradually raised to 210℃ to 230℃, and the theoretical amount of methanol is completely outflowed through the transesterification reaction. After adding dicarboxylic acid, the temperature was gradually increased to 230°C, and water was completely discharged through the esterification reaction, and then the reaction was terminated. At this time, the weight ratio of the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid among the total acid components is preferably 55:45 to 45:55.

When the amount is more than 55% by weight of the acid component of the aromatic dicarboxylic acid, the biodegradability is remarkably low, and the biodegradable resin for adhesion to be obtained by the present invention cannot be obtained. In addition, if the acid component is 45% by weight or less of the aromatic dicarboxylic acid, heat resistance may be deteriorated.

In the present invention, in preparing the aliphatic/aromatic copolyester resin, the molar ratio of dicarboxylic acid and glycol is added in a molar ratio of 1:1.15 to 1:1.5.

At this time, if the glycol is less than 1.15 mol. There is a problem in that the reaction speed may be lowered and the color is deteriorated. In addition, if it is more than 1.15 moles of glycol, the manufacturing cost increases and the price competitiveness decreases.

In the first step synthesis, the esterification reaction is also reacted by gradually increasing the temperature to 210°C to 230°C during the transesterification reaction.

At this time, when the reaction temperature is below 210°C, it takes a long time to drain the theoretical amount of water. In addition, if the temperature is above 230℃, thermal decomposition may occur, resulting in deterioration of properties.

In this way, after the esterification reaction or the esder exchange reaction is completed, the reaction temperature is gradually maintained at 240℃ to 290℃ in order to start the condensation polymerization reaction, which is a secondary reaction. If the condensation polymerization temperature is less than 240℃, the reaction speed becomes slow and the When the polymerization temperature is over 290°C, there is a risk of thermal decomposition.

Meanwhile, in the first step in the present invention, a catalyst and a stabilizer are added at the beginning of the esderification reaction, the esder exchange reaction, or the condensation polymerization reaction in the second step.

At this time, the amount of the catalyst added is 0.01 to 0.8 parts by weight based on the weight of the total composition. At this time, if the amount of the catalyst used is less than 0,03 parts by weight, the esterification reaction and the transesterification reaction cannot be performed smoothly, and the reaction time may take a long time and the color may deteriorate during condensation polymerization.

In addition, when the amount of the catalyst is 0.8 parts by weight or more, the reaction rate is fast, but the molecular weight distribution is large, which may cause a factor to deteriorate the physical properties.

In addition, it is preferable to add 0.02 to 0.4 parts by weight of the stabilizer, and at this time, when the amount of the stabilizer is less than 0.02 parts by weight, a factor that significantly lowers the color may occur, and when the amount of the stabilizer is 0.4 parts by weight or more, the reaction rate is significantly lowered.

Finally, in the condensation polymerization reaction, isocyanate, which is a multifunctional crosslinking agent, is added when the isocyanate compound, which is a multifunctional crosslinking agent, has a weight average molecular weight according to the condensation time. At this time, when the weight average molecular weight is between 20,000 and 30,000, isocyanate relative to the total weight part It is preferable to add 0.1 to 0.8 parts by weight.

If less than 0.1 parts by weight of isocyanate is added, there may be a limit to raising a sufficient weight average molecular weight, and if more than 0.8 parts by weight of isocyanate is added, there is a high possibility of gelation.

A biodegradable polyester resin for adhesion was developed that can be used by dissolving the prepared biodegradable polyester resin for adhesion in a solvent and that can be used without a solvent through a coating extruder.

The pressure-sensitive adhesive composition of the present invention may further include addition of a crosslinking catalyst, a tackifier resin, a curing agent, an ultraviolet stabilizer, an antioxidant, a colorant, a filler, an antifoaming agent, a surfactant, a plasticizer, and the like known in the art, if necessary.

In addition, in the present invention, the adhesive formed auxiliary film comprising the pressure-sensitive adhesive composition is currently commercially available biodegradable resins such as polylactide, polybutylene succinate, polybutylcoadipate terebutalate, and polybutylenecoadipate stone. It is a film produced by using either one or a mixture as a sinate.

The auxiliary film thickness is not particularly limited and may be, for example, 10 to 500 μm, and preferably 10 to 80 μm.

In the protective film of the present invention, since the adhesive layer has a surface energy of 40 dyne/cm or less, it can have an appropriate adhesive strength during low-speed peeling and high-speed peeling, especially for the protective film with antifouling treatment on the surface. Even when exposed, there is no lifting phenomenon, so it has excellent durability, so it can protect the protective film from external impact and contamination.

Hereinafter, in order to help a more detailed understanding of the present invention, the following [Example 1] to [Example 10] were carried out as examples of the present invention, while [Example 11] was referred to as [Comparative Example 1] and [Example 12]. Was compared with [Comparative Example 2] and [Example 13] with [Comparative Example 3], and was carried out as shown in [Table 1] to [Table 2].

After adding 0.45 mol of 2,5-furandicarboxylic acid and 1.5 mol of ethylene glycol to a 500 ml round bottom flask, gradually increasing the temperature and adding 0.052 g of catalyst detrabutyl titanate when the internal temperature reached 80°C, and the temperature was 280°C. When the temperature is gradually increased to 230°C, after the transesterification reaction proceeds and methanol is completely leaked, 0.55 mol of sebacic acid and 0.04 g of tetrabutyl titanate are added to raise the temperature to 230°C. After adding 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate, condensation polymerization was carried out while gradually increasing the temperature to 250°C.
At this time, when the condensation time reached 100 minutes, the condensation polymerization reaction was performed while adding 0.2 g of hexamethylene diisocyanate in a vacuum state in a round bottom flask.

The copolyester resin thus obtained had a condensation polymerization reaction time of 153 minutes, an acid value of 0.27 mg-KOH/g, and a weight average molecular weight of 167,000 to prepare a biodegradable adhesive copolyester resin.

After adding 0.45 moles of 2,5-furandicarboxylic acid, 0.05 moles of isophthalic acid, and 1.5 moles of ethylene glycol to a 500 ml round-bottom flask, gradually increase the temperature and add 0.052 g of catalyst detrabutyl titanate when the internal temperature reaches 80°C. Then, if the temperature is gradually raised to 280℃, the transesterification reaction proceeds and methanol is completely outflowed, and then 0.5 mol of adipic acid and 0.04 g of tetrabutyl titanate catalyst are added to raise the temperature to 230℃, and the esterification reaction proceeds. While water was completely discharged, 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate were added, and the condensation polymerization was carried out while gradually increasing the temperature to 250°C.
At this time, when the condensation time reached 100 minutes, the condensation polymerization reaction was carried out while adding 0.2 g of diphenylmethane diisocyanate to the round bottom flask in a vacuum state.

The copolyester resin thus obtained was prepared for a biodegradable adhesive copolyester resin having a condensation polymerization reaction time of 160 minutes, an acid value of 0.6 mg-KOH/g, and a weight average molecular weight of 170,000.

0.55 mol of 2,5-furandicarboxylic acid, 1.0 mol of ethylene glycol, and 0.5 mol of neopentyl glycol were added to a 500 ml round bottom flask, and then gradually heated up and the internal temperature reached 80°C. Catalyst detrabutyl titanate 0.052 g When the temperature is gradually increased to 280°C by introducing the transesterification reaction, the methanol is completely outflowed while the transesterification reaction proceeds, and then 0.45 mol of succinic acid and 0.04 g of the catalyst tetrabutyl titanate are added and the temperature is raised to 230°C again to proceed with the esterification reaction. While water was completely discharged, 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate were added, and the condensation polymerization was carried out while gradually increasing the temperature to 250°C.
At this time, when the condensation time reached 100 minutes, the condensation polymerization reaction was carried out while adding 0.2 g of tolyene diisocyanate to the round bottom flask in a vacuum state.

The copolyester resin thus obtained was prepared for a biodegradable adhesive copolyester resin having a condensation polymerization reaction time of 157 minutes, an acid value of 0.7 mg-KOH/g, and a weight average molecular weight of 169,000.

0.5 mol of 2,5-furandicarboxylic acid, 0.7 mol of ethylene glycol and 0.8 mol of neopentyl glycol were added to a 500 ml round-bottom flask, and then gradually heated up, and 0.052 g of tetrabutyl titanate catalyst was added when the internal temperature reached 80°C. When the temperature is gradually raised to 280°C, the transesterification reaction proceeds and methanol is completely outflowed, and 0.5 mol of succinic acid and 0.04 g of catalyst detrabutyl titanate are added to raise the temperature to 230°C. After completely draining water, 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate were added, and the condensation polymerization was carried out while gradually increasing the temperature to 250°C.
At this time, when the condensation time reached 100 minutes, the condensation polymerization reaction proceeded while adding 0.25 g of hexamethylene diisocyanate in a vacuum state in a round bottom flask.

The copolyester resin thus obtained had a condensation polymerization reaction time of 173 minutes, an acid value of 0.89 mg-KOH/g, and a weight average molecular weight of 178,000 to prepare a biodegradable adhesive copolyester resin.

Add 0.47 mol of 2,5-furandicarboxylic acid, 1.2 mol of ethylene glycol, and 0.3 mol of neopentyl glycol to a 500 ml round bottom flask, then gradually increase the temperature and add 0.052 g of tetrabutyl titanate catalyst when the internal temperature reaches 80°C. When the temperature is gradually raised to 280°C, the transesterification reaction proceeds and methanol is completely outflowed, and then 0.53 mol of 1,10-decanedicarboxylic acid and 0.04 g of catalyst detrabutyl titanate are added to raise the temperature to 230°C. When the temperature was raised, water was completely discharged while the esterification reaction proceeded, and then 0.07 g of the catalyst antimony trioxide and 0.027 g of the stabilizer triphenyl phosphate were added, and the condensation polymerization was carried out while gradually increasing the temperature to 250°C.
At this time, when the condensation time reached 100 minutes, the condensation polymerization reaction was carried out while adding 0.3 g of hexamethylene diisocyanate to the round bottom flask in a vacuum state.

The copolyester resin thus obtained was prepared for a biodegradable adhesive copolyester resin having a condensation polymerization reaction time of 168 minutes, an acid value of 0.52 mg-KOH/g, and a weight average molecular weight of 154,000.

0.52 mol of 2,5-furandicarboxylic acid, 0.03 mol of isophthalic acid, and 1.5 mol of ethylene glycol were added to a 500 ml round-bottom flask, and then gradually heated up, and 0.052 g of tetrabutyl titanate catalyst was added when the internal temperature reached 80°C. If the temperature is gradually raised to 280°C, the transesterification reaction proceeds and methanol is completely outflowed, and then 0.45 mol of sebacic acid and 0.04 g of catalyst detrabutyl titanate are added to raise the temperature to 230°C. After completely draining water, 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate were added, and the condensation polymerization was carried out while gradually increasing the temperature to 250°C.
At this time, when the condensation time reached 100 minutes, the condensation polymerization reaction proceeded while adding 0.27 g of hexamethylene diisocyanate in a vacuum state in a round bottom flask.

The copolyester resin thus obtained was prepared for a biodegradable adhesive copolyester resin having a condensation polymerization reaction time of 172 minutes, an acid value of 0.63 mg-KOH/g, and a weight average molecular weight of 164,000.

Add 0.45 mol of 2,5-furandicarboxylic acid, 1.3 mol of ethylene glycol, and 0.2 mol of neopentyl glycol to a 500 ml round bottom flask, and then gradually increase the temperature and add 0.052 g of tetrabutyl titanate catalyst when the inner temperature reaches 80°C. Then, if the temperature is gradually raised to 280℃, the transesterification reaction proceeds and methanol is completely outflowed, and then 0.55 mol of sebacic acid and 0.04 g of catalyst detrabutyl titanate are added and the temperature is raised to 230℃ again to proceed with the esterification reaction. While water was completely discharged, 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate were added, and the condensation polymerization was carried out while gradually increasing the temperature to 250°C.
At this time, when the condensation time reached 100 minutes, the condensation polymerization reaction proceeded while adding 0.35 g of hexamethylene diisocyanate to the round bottom flask in a vacuum state.

The copolyester resin thus obtained was prepared for a biodegradable adhesive copolyester resin having a condensation polymerization reaction time of 160 minutes, an acid value of 0.91 mg-KOH/g, and a weight average molecular weight of 189,000.

Add 0.45 mol of 2,5-furandicarboxylic acid, 1.0 mol of ethylene glycol, and 0.5 mol of neopentyl glycol to a 500 ml round bottom flask, then gradually increase the temperature and add 0.052 g of tetrabutyl titanate catalyst when the internal temperature reaches 80°C. If the temperature is gradually increased to 280°C, the esterification reaction proceeds and methanol is completely outflowed, and then 0.55 mol of adipic acid and 0.04 g of catalyst detrabutyl titanate are added to increase the temperature to 230°C. During the process, after the water was completely discharged, 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate were added, and the condensation polymerization was performed while gradually increasing the temperature to 250°C.
At this time, when the condensation time reached 100 minutes, the condensation polymerization reaction proceeded while adding 0.22 g of hexamethylene diisocyanate in a vacuum state in a round bottom flask.

The copolyester resin thus obtained was prepared for a biodegradable adhesive copolyester resin having a condensation polymerization reaction time of 155 minutes, an acid value of 0.59 mg-KOH/g, and a weight average molecular weight of 159,000.

0.52 mol of 2,5-furandicarboxylic acid, 1.4 mol of ethylene glycol, and 0.1 mol of neopentyl glycol were added to a 500 ml round-bottom flask, and then gradually heated up, and 0.052 g of tetrabutyl titanate catalyst was added when the inner temperature reached 80°C. Then, if the temperature is gradually increased to 280℃, the transesterification reaction proceeds and methanol is completely outflowed, and then 0.48 mol of sebacic acid and 0.04 g of catalyst detrabutyl titanate are added to increase the temperature to 230℃ again to proceed with the esterification reaction. While water was completely discharged, 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate were added, and the condensation polymerization was carried out while gradually increasing the temperature to 250°C.
At this time, when the condensation time reached 100 minutes, the condensation polymerization reaction proceeded while adding 0.31 g of hexamethylene diisocyanate to the round bottom flask in a vacuum state.

The copolyester resin thus obtained was prepared for a biodegradable adhesive copolyester resin having a condensation polymerization reaction time of 167 minutes, an acid value of 0.79 mg-KOH/g, and a weight average molecular weight of 171,000.

After adding 0.4 mol of 2,5-furandicarboxylic acid, 0.05 mol of isophthalic acid, and 1.5 mol of ethylene glycol to a 500 ml round bottom flask, gradually increasing the temperature and adding 0.052 g of tetrabutyl titanate catalyst when the internal temperature reached 80°C. If the temperature is gradually raised to 280°C, the transesterification reaction proceeds and methanol is completely outflowed, and then 0.55 mol of 1,10-decanedicarboxylic acid and 0.04 g of catalyst detrabutyl titanate are added to raise the temperature to 230°C. When the esterification reaction proceeded, water completely flowed out, 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate were added, and condensation polymerization was performed while gradually raising the temperature to 250°C.
At this time, when the condensation time reached 100 minutes, the condensation polymerization reaction proceeded while adding 0.35 g of hexamethylene diisocyanate to the round bottom flask in a vacuum state.

*The copolyester resin thus obtained was prepared for a biodegradable adhesive copolyester resin having a condensation polymerization reaction time of 175 minutes, an acid value of 0.81 mg-KOH/g, and a weight average molecular weight of 180,000.

After adding 0.45 moles of 2,5-furandicarboxylic acid and 1.5 moles of ethylene glycol to a 500 ml round bottom flask, gradually increasing the temperature and adding 0.052 g of tetrabutyl titanate catalyst to 280°C when the internal temperature reaches 80°C. When the temperature is gradually raised, the transesterification reaction proceeds and methanol completely flows out, and then 0.55 mol of sebacic acid and 0.04 g of catalyst detrabutyl titanate are added to raise the temperature to 230°C. After adding 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate, condensation polymerization was carried out while gradually increasing the temperature to 250°C.

The copolyester resin thus obtained was prepared for a biodegradable adhesive copolyester resin having a condensation polymerization reaction time of 170 minutes, an acid value of 2.7 mg-KOH/g, and a weight average molecular weight of 110,000.

After adding 0.45 moles of 2,5-furandicarboxylic acid, 0.05 moles of isophthalic acid, and 1.5 moles of ethylene glycol to a 500 ml round-bottom flask, gradually increase the temperature and add 0.052 g of tetrabutyl titanate catalyst when the internal temperature reaches 80°C. If the temperature is gradually raised to 280℃, the transesterification reaction proceeds and methanol is completely outflowed, and then 0.5 mol of adipic acid and 0.04 g of catalyst detrabutyl titanate are added, and the temperature is raised to 230℃ again to proceed with the esterification reaction. While water was completely discharged, 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate were added, and the condensation polymerization was carried out while gradually increasing the temperature to 250°C.

The copolyester resin thus obtained had a condensation polymerization reaction time of 169 minutes, an acid value of 3.1 mg-KOH/g, and a weight average molecular weight of 98,000 to prepare a biodegradable adhesive copolyester resin.

0.55 mol of 2,5-furandicarboxylic acid, 1.0 mol of ethylene glycol, and 0.5 mol of neopentyl glycol were added to a 500 ml round-bottom flask, and then gradually heated up, and 0.052 g of tetrabutyl titanate catalyst was added when the internal temperature reached 80°C. If the temperature is gradually increased to 280°C, the transesterification reaction proceeds and methanol is completely outflowed, and then 0.45 mol of adipic acid and 0.04 g of catalyst detrabutyl titanate are added to increase the temperature to 230°C. During the process, after the water was completely discharged, 0.07 g of catalyst antimony trioxide and 0.027 g of stabilizer triphenyl phosphate were added, and the condensation polymerization was performed while gradually increasing the temperature to 250°C.

The copolyester resin thus obtained was prepared for a biodegradable adhesive copolyester resin having a condensation polymerization reaction time of 170 minutes, an acid value of 3.3 mg-KOH/g, and a weight average molecular weight of 100,000.

division Example Example Example Example Example Example Example One 2 3 4 5 6 7 2,5-furandicarboxylic acid mole 0.45 0.45 0.55 0.5 0.47 0.52 0.45 Isophthalic acid mole 0.05 0.03 Adipic acid mole 0.5 Succinic acid mole 0.45 0.5 1,10-decanedicarboxylic acid mole 0.53 Sebacic acid mole 0.55 0.45 0.55 Ethylene glycol mole 1.5 1.5 1.0 0.7 1.2 1.5 1.3 Neopentyl glycol mole 0.5 0.8 0.3 0.2 Hexamethylene diisocyanate g 0.2 0.25 0.3 0.27 0.35 Diphenylmethane diisocyanate g 0.2 Tolylene diisocyanate g 0.2 Weight average molecular weight 167,000 170,000 169,000 178,000 154,000 164,000 189,000 Acid mg-KOH/g 0.27 0.6 0.7 0.89 0.52 0.63 0.91 Condensation time minute 153 160 157 173 168 172 160

division Example Example Example Example Example Example 8 9 10 11 12 13 2,5-furandicarboxylic acid mole 0.45 0.52 0.4 0.45 0.45 0.55 Isophthalic acid mole 0.05 0.05 Adipic acid mole 0.55 0.5 0.45 Succinic acid mole 1,10-decanedicarboxylic acid mole 0.55 Sebacic acid mole 0.48 0.55 Ethylene glycol mole 1.0 1.4 1.5 1.5 1.5 1.0 Neopentyl glycol mole 0.5 0.1 0.5 Hexamethylene diisocyanate g 0.22 0.31 0.35 × × × Diphenylmethane diisocyanate g Tolylene diisocyanate g Weight average molecular weight 159,000 171,000 180,000 110,000 98,000 100,000 Acid mg-KOH/g 0.59 0.79 0.81 2.7 3.1 3.3 Condensation time minute 155 167 175 170 169 170

The copolyester resin prepared in [Examples 1] to [Example 10] and [Example 11] to [Example 13] was applied to one side of a biaxially stretched polylactide film having a thickness of 80 µm and 15 µm. It was applied and dried to form a uniform adhesive layer. The release film was laminated on the adhesive layer and aged for 3 days at a constant temperature of 40°C. The surface energy measurement, the low-speed peel force measurement, the high-speed peel force measurement, and durability evaluation are shown in Table 3 as follows.

(1) surface energy measurement

The transition film of the prepared biodegradable protective film was removed, and the surface energy of the adhesive layer was measured using a contact angle meter (DSA100. Kruss).

(2) Low-speed peel force measurement

Each of the prepared protective films was removed from the release film and bonded to the surface of the high antifouling low-reflection protective film using a 2 kg roller, and then aged at 25° C. 50% to prepare a sample.

(3) High-speed peel force measurement

High-speed peeling force was measured using a high-speed peeling tester at a 180° angle and a speed of 30m/min.

(4) Durability evaluation

Each sample was stored in an oven at 60° C. and an oven at 60° C./90% for 3 days, and then the durability was evaluated by checking whether a lifting phenomenon of the protective film occurred.

<Evaluation criteria>

○: No peeling and lifting phenomenon

△: Slight peeling and lifting

X: Peeling and lifting phenomenon occurs

division Surface energy Low speed peeling force High speed peeling force durability dyne/cm gf/25mm gf/25mm 60℃ 60℃/90% Example 1 37.4 2.8 40 ○ ○ Example 2 36.7 2.7 39 ○ ○ Example 3 35.6 2.9 41 ○ ○ Example 4 42.2 2.4 42 ○ ○ Example 5 40.4 2.1 46 ○ ○ Example 6 42.5 2.3 44 ○ ○ Example 7 39.3 2.2 51 ○ ○ Example 8 38.2 2.4 43 ○ ○ Example 9 37.6 2.5 45 ○ ○ Example 10 30.4 2.3 50 ○ ○ Example 11 50.1 1.1 22 × × Example 12 52.3 1.2 21 △ × Example 13 56.4 1.0 24 △ ×

As shown in [Table 3] above, the biodegradable adhesive resin has almost similar physical properties to the non-degradable adhesive resin used in the past, and the reaction was made while increasing the viscosity by adding isocyanate during the reaction, and without adding isocyanate. It can be seen that there is a huge difference in physical properties from the reaction.

The above description is merely illustrative of the technical idea of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications and variations without departing from the essential characteristics of the present invention. Accordingly, the embodiments and/or drawings disclosed in the present invention are not intended to limit the technical idea of the present invention, but to explain the technical idea, and the scope of the technical idea of the present invention is not limited by these embodiments and/or drawings. . The scope of protection of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent thereto should be interpreted as being included in the scope of the present invention.

Claims (10)

An acid component having an aromatic dicarboxylic acid derived from biomass and an aliphatic dicarboxylic acid in a weight part ratio of 55:45 to 45:55; A glycol component mixed with one or two of ethylene glycol and neopentyl glycol; And a crosslinking agent; as a biodegradable polyester resin prepared by esterification and condensation polymerization,
The aromatic dicarboxylic acid is 2,5-furandicarboxylic acid,
The aliphatic dicarboxylic acid is adipic acid, succinic acid, sebacic acid or 1,10-decanedicarboxylic acid,
The molar ratio of the acidic component to glycol is 1: 1.15 to 1: 1.5 mol,
The crosslinking agent is one or two or more isocyanate compounds selected from tolylene diisocyanate, hexamethylene diisocyanate, and tetramethylxylene diisocyanate, and the amount added is 0.1 to 0.8 parts by weight based on 100 parts by weight of all components,
The ethylene glycol is 100 to 50 parts by weight based on 100 parts by weight of the total glycol component,
An adhesive biodegradable polyester resin derived from biomass, characterized in that the acid value is less than 0.5mg-KOH/g and the weight average molecular weight is more than 150,000
delete delete The method of claim 1,
Biomass-derived adhesive biodegradable polyester resin, characterized in that the aromatic dicarboxylic acid further contains isophthalic acid
delete delete delete delete The method of claim 1,
In the esterification and condensation polymerization reaction, one or two or more catalysts selected from the group consisting of tetrabutyl titanate, trioctyl antimony oxide, tin oxide, calcium acetate, zinc acetate, tetrapropyl titanate, etc. Biomass-derived adhesive biodegradable polyester resin, characterized in that it is used in the range of 0.01 to 0.8% by weight based on parts
The method of claim 1,
In the esterification and condensation polymerization reaction, phosphorous acid, trimethyl phosphate, triphenyl phosphate alone or two or more stabilizers are used in the range of 0.05 to 0.4% by weight based on the total weight of the reactants. Castle polyester resin