Biodegradable adhesive composition

Abstract

The invention provides a biodegradable polyester polymer for an adhesive, which is prepared from a polyneopentyl sebacate oligomer, aiming at solving the problem that the existing polymer prepared by using a cancerogen isocyanate or using a polyhydric alcohol or adding a tackifier is non-biodegradable. The invention further provides the biodegradable polyester polymer for the adhesive, which is prepared from the polyneopentyl sebacate oligomer. The biodegradable polyester polymer has excellent solubility and storage stability, and the adhesive composition containing the biodegradable polyester polymer can exhibit excellent adhesive force and peel strength without adding an additional tackifier.

Description

TECHNICAL FIELD

[0001] The present application relates to a biodegradable polyester polymer for an adhesive and a biodegradable adhesive composition comprising the same. BACKGROUND

[0002] As a solution to environmental pollution caused by the use of plastics, a method of using a substitute material, paper, or a biodegradable polymer that decomposes under specific conditions is proposed, and research and development thereof are actively conducted.

[0003] Even in the case of an adhesive, the polyester resin used in the past does not decompose at the time of disposal, and thus, the above problems can be solved by replacing it with a biodegradable polyester resin that decomposes naturally. However, generally, as a purpose of improving adhesion, a tackifier such as rosin ester, terpene phenol, etc. added at the time of generally preparing an adhesive is difficult to biodegrade, thereby causing environmental pollution.

[0004] In addition, in the case of a conventional polyester adhesive using a polyol such as trimethylolpropane, in the case of dissolving it in a solvent to use, it has the following disadvantages: it is difficult to dissolve and disperse, it has insufficient stability to a solvent, and the softening point is high so that the adhesion is significantly reduced at room temperature or less, and it is difficult to recycle. In addition, an adhesive prepared by adding a large amount of isocyanate in order to increase the molecular weight and improve the adhesion is also difficult to recycle at the time of disposal in a natural environment, and cannot be decomposed in a natural environment, thereby causing environmental pollution.

[0005] Therefore, there is an urgent need to develop a biodegradable adhesive composition that has excellent solubility to a solvent and excellent adhesion even when a polymer is prepared without using isocyanate or a polyol and without including a tackifier. SUMMARY

[0006] TECHNICAL PROBLEM

[0007] To solve the problems of the prior art as described above, the present application aims to provide a biodegradable polyester polymer for an adhesive having excellent solubility to a solvent and storage stability, and a method of preparing the same.

[0008] Another object of the present application is to provide an adhesive composition including the biodegradable polyester polymer for an adhesive described above, which does not include a tackifier and also has significant adhesion.

[0009] TECHNICAL SOLUTION

[0010] The present inventors have continuously researched to solve the above problems in order to prepare a biodegradable polyester polymer having excellent solubility in a solvent and storage stability, and adhesion, and have found that a biodegradable polyester polymer prepared from a polymerizable composition including a polyneopentyl sebacate oligomer having a certain molecular weight has excellent solubility and storage stability, and shows remarkable adhesion and peeling strength without the addition of an additional tackifier, thereby completing the present invention.

[0011] The present invention provides a biodegradable polyester polymer prepared from a polymerizable composition including: (a) a dicarboxylic compound including an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or a mixture thereof, (b) an aliphatic diol compound, and (c) a polyneopentyl sebacate oligomer.

[0012] According to an embodiment of the present invention, the polyneopentyl sebacate oligomer can have a weight average molecular weight (Mw) of 2000 g / mol to 6000 g / mol.

[0013] According to an embodiment of the present invention, the polymerizable composition can include 0.1 weight percent to 10 weight percent of the polyneopentyl sebacate oligomer in the total weight of the polymerizable composition.

[0014] According to an embodiment of the present invention, the polymerizable composition can further include a multifunctional compound having 3 or more polymerization functional groups.

[0015] According to an embodiment of the present invention, the multifunctional compound can be included in 0.01 weight percent to 3 weight percent, relative to the total weight of the polymerizable composition.

[0016] According to an embodiment of the present invention, the aliphatic diol compound can include C 5-7 aliphatic diol compounds.

[0017] According to an embodiment of the present invention, the aliphatic diol compound can include 30 mole percent to 90 mole percent of neopentyl glycol and 10 mole percent to 70 mole percent of C 2-4 diol.

[0018] According to an embodiment of the present invention, the aliphatic dicarboxylic acid can be one or a combination of two or more selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, 1,9-nonane dicarboxylic acid, 1,10-decane dicarboxylic acid, and anhydride derivatives thereof.

[0019] According to an embodiment of the present invention, the aromatic dicarboxylic acid can be one or a combination of two or more selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid.

[0020] According to an embodiment of the present application, the total weight of the above-mentioned dicarboxylic compound can include 50 to 100 weight percent of the above-mentioned aliphatic dicarboxylic acid.

[0021] According to an embodiment of the present application, the above-mentioned dicarboxylic compound and the above-mentioned aliphatic diol compound can have a molar ratio of 1:1 to 2.

[0022] According to an embodiment of the present application, the above-mentioned biodegradable polyester polymer can have a weight average molecular weight (Mw) of 60,000 to 150,000 g / mol.

[0023] According to an embodiment of the present application, the above-mentioned biodegradable polyester polymer can have a glass transition temperature of -40°C or less.

[0024] The present application can provide a biodegradable adhesive composition including the above-mentioned biodegradable polyester polymer.

[0025] The present application can provide a method of preparing a biodegradable polyester polymer, including: step (A) of preparing a polysebacic acid neopentyl ester oligomer by esterifying and polycondensing sebacic acid and an excess amount of neopentyl glycol; and step (B) of preparing a polyester polymer by esterifying and polycondensing a dicarboxylic compound, an aliphatic diol compound, and the above-mentioned polysebacic acid neopentyl ester oligomer.

[0026] According to an embodiment of the present application, in the above-mentioned step (A), the above-mentioned sebacic acid and neopentyl glycol can have a molar ratio of 1:1.1 to 1.5.

[0027] Effects of the Invention

[0028] The present application provides a biodegradable polyester polymer for an adhesive prepared using a polysebacic acid neopentyl ester oligomer, to solve the problem that existing polymers prepared using a carcinogenic isocyanate or using a polyol or adding a tackifier are not biodegradable. The above-mentioned biodegradable polyester polymer has excellent solubility and storage stability, and an adhesive composition including the same can exhibit excellent adhesion and peel strength without adding an additional tackifier. DETAILED DESCRIPTION

[0029] Hereinafter, the present application will be described in more detail by specific examples or embodiments including the accompanying drawings. However, the following specific examples or embodiments are only for a reference to explain the present application in detail, and the present application is not limited thereto, but can be realized in various forms.

[0030] Also, unless otherwise defined, 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 application belongs. The terminology used in the description is for the purpose of describing particular embodiments only and is not intended to be limiting of this application.

[0031] Also, as used in the specification and in the claims, the singular form "a", "an" and "the" include plural references unless the context clearly dictates otherwise.

[0032] Also, when referring to a part "comprising" a component, unless otherwise specifically noted, it refers to the possibility of also including other components, rather than excluding them.

[0033] The term "oligomer" of the present specification is a low molecular weight polymer polymerized from a monomer, and specifically refers to a polymer having a weight average molecular weight of 100 g / mol to 10,000 g / mol.

[0034] The present application can be better understood by the following examples, which are intended to illustrate the present application and not to limit the scope of protection defined by the claims.

[0035] Hereinafter, an embodiment of the present application will be described in more detail.

[0036] The present application provides a biodegradable polyester polymer prepared from a polymerizable composition, the polymerizable composition preparation comprising: (a) a dicarboxylic compound including an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or a mixture thereof, (b) an aliphatic diol compound, and (c) a polysebacic acid neopentyl glycol oligomer.

[0037] According to an embodiment of the present application, the aromatic dicarboxylic acid has a carbon number of 6 to 50, or 6 to 30, or 6 to 20, and as a non-limiting example, can be one or a combination of two or more selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid.

[0038] According to an embodiment of the present application, the aliphatic dicarboxylic acid has a carbon number of 2 to 30, or 2 to 20, or 2 to 15, or 2 to 12, and as a non-limiting example, can be one or a combination of two or more selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, 1,9-nonane dicarboxylic acid, 1,10-decane dicarboxylic acid, and anhydride derivatives thereof. The aliphatic dicarboxylic acid can be included in a total weight of 50 to 100 weight percent, or 75 to 100 weight percent, of the dicarboxylic compound.

[0039] According to an embodiment of the present application, the aliphatic diol compound can include C2-10 The aliphatic diol compound can be one or a combination of two or more selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,10-decanediol.

[0040] Specifically, the aliphatic diol compound can include C 5-7 The aliphatic diol compound can be one or a combination of two or more selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,10-decanediol. 5-7 The aliphatic diol compound can be one or a combination of two or more selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,10-decanediol.

[0041] According to an embodiment of the present application, the aliphatic diol compound can include C 5-7 The aliphatic diol compound can be one or a combination of two or more selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,10-decanediol. 2-4 The aliphatic diol compound can be one or a combination of two or more selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,10-decanediol. 5-7 The aliphatic diol compound can be one or a combination of two or more selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,10-decanediol. 2-4 The aliphatic diol compound can be one or a combination of two or more selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,10-decanediol.

[0042] According to an embodiment of the present application, the aliphatic diol compound can include neopentyl glycol and C 2-4 The aliphatic diol compound can be one or a combination of two or more selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,10-decanediol. 2-4 The aliphatic diol compound can be one or a combination of two or more selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,10-decanediol. 2-4 The aliphatic diol compound can be one or a combination of two or more selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-octanediol, 1,6-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,10-decanediol.

[0043] According to an embodiment of the present application, the molar ratio of the dicarboxylic compound and the aliphatic diol compound can be 1:1 to 2 or 1:1.25 to 1.5.

[0044] According to an embodiment of the present application, the polypentylene sebacate oligomer can be generally used or prepared by a known method, and a commercially available product can be purchased and used, and preferably, can be prepared by the preparation method of the polypentylene sebacate oligomer according to an embodiment of the present application.

[0045] According to an embodiment of the present application, the polyneopentyl sebacate oligomer can have a weight average molecular weight (Mw) of 2,000 g / mol to 10,000 g / mol, specifically, 2,000 g / mol to 8,000 g / mol, more specifically, 2,000 g / mol to 6,000 g / mol or 3,000 g / mol to 5,000 g / mol. In addition, the polydispersity index can be 1 to 5, preferably, 1 to 3, but is not limited thereto. The biodegradable polyester polymer prepared using the polyneopentyl sebacate oligomer satisfying the above-mentioned molecular weight range can exhibit more significant adhesion and peeling strength.

[0046] According to an embodiment of the present application, the polymeric composition can contain 0.1 wt% to 30 wt% of the polyneopentyl sebacate oligomer, specifically, 0.1 wt% to 10 wt% of the polyneopentyl sebacate oligomer, more specifically, 1 wt% to 3 wt% of the polyneopentyl sebacate oligomer, in the total weight of the polymeric composition. In the case of containing the above-mentioned content satisfying the above-mentioned range, when the biodegradable polyester polymer is prepared, the reactivity can be stabilized, and more excellent solubility, storage stability, and adhesion can be exhibited.

[0047] According to an embodiment of the present application, the polymeric composition can further contain a multi-functional compound containing 3 or more polymerization functional groups. The polymerization functional group can be any one or a combination of two or more selected from the group consisting of a carboxyl group, a hydroxyl group, and an amine group. Specifically, the multi-functional compound can be a C 2-10 or a C 2-7 carboxylic acid compound, as an example, can be any one or a combination of two or more selected from the group consisting of citric acid, tartaric acid, malic acid, and ascorbic acid. Preferably, the multi-functional compound can be malic acid. The multi-functional compound can be contained in an amount of 0.01 wt% to 3 wt% with respect to the total weight of the polymeric composition. In the case of containing the multi-functional compound in the above-mentioned range in the polymeric polymer, further improved solubility, storage stability, adhesion, and peeling strength can be achieved.

[0048] According to an embodiment of the present application, the biodegradable polyester polymer can be a branched polymer to achieve improved adhesion and peeling strength. As the biodegradable polyester polymer of an example is prepared from the polymeric composition containing the multi-functional compound, a branched polymer can be prepared, and thus, a biodegradable polyester polymer for an adhesive achieving improved physical properties can be prepared.

[0049] According to an embodiment of the present application, the weight average molecular weight (Mw) of the above-mentioned biodegradable polyester polymer can be 40,000 g / mol or more, or 60,000 g / mol or more, specifically, can be 60,000 g / mol to 150,000 g / mol, more specifically, can be 70,000 g / mol to 130,000 g / mol, or 80,000 g / mol to 120,000 g / mol.

[0050] According to an embodiment of the present application, the glass transition temperature of the above-mentioned biodegradable polyester polymer can be -0°C or less, or -10°C or less, or -20°C or less, or -30°C or less, or -40°C or less, specifically, can be -70°C to -40°C, more specifically, can be -60°C to -41°C.

[0051] The present application can provide a biodegradable adhesive composition comprising the above-mentioned biodegradable polyester polymer. The above-mentioned biodegradable adhesive composition can comprise a solvent and the above-mentioned biodegradable polyester polymer. The above-mentioned solvent can be used without limitation as long as it is a solvent that can dissolve the above-mentioned biodegradable polyester polymer, and, as an example, can be any one or a combination of two or more selected from the group consisting of toluene, coal tar volatile oil, ethyl acetate, methyl ethyl ketone, cyclohexanone, isopropyl alcohol, ethanol, and methanol.

[0052] The above-mentioned biodegradable polyester polymer can be contained in an amount of 1% by weight to 99% by weight, or 20% by weight to 80% by weight, or 20% by weight to 60% by weight, with respect to the total weight of the biodegradable adhesive composition, but is not limited thereto, and can be easily adjusted according to viscosity.

[0053] According to an embodiment of the present application, the above-mentioned biodegradable adhesive composition can not comprise a conventional tackifier, a polyurethane resin, a polyamide resin, a terpene phenol resin, a rosin ester resin, and the like. The adhesive composition comprising the biodegradable polyester polymer of the present application has the advantage that excellent adhesion, peeling strength, and biodegradability are achieved without the above-mentioned additives, and is environmentally friendly.

[0054] According to an embodiment of the present application, the viscosity of the above-mentioned biodegradable adhesive composition can be 10,000 cP or less, or 10 cP to 8,000 cP, or 50 cP to 5,000 cP, but is not limited thereto. The above-mentioned viscosity can be easily adjusted according to the viscosity suitable for the intended use.

[0055] According to an embodiment of the present application, the above-mentioned biodegradable adhesive composition can be applied to a suitable object, and the method of application can be selected from gravure coating, spraying, reverse coating, die coating, and dipping, without being limited thereto, as long as it is a generally used method.

[0056] Hereinafter, a method of preparing a biodegradable polyester polymer according to an embodiment of the present application will be described in more detail.

[0057] The present application can provide a method of preparing a biodegradable polyester polymer, which includes, as a method of lowering a glass transition temperature, a step (A) of preparing a poly(neopentyl sebacate) oligomer by esterifying sebacic acid and an excess amount of neopentyl glycol and then polycondensing the same; and

[0058] a step (B) of preparing a polyester polymer by reacting a dicarboxylic compound, an aliphatic diol compound, and the poly(neopentyl sebacate) oligomer.

[0059] The above-mentioned step (A) can include a step (A-1) of preparing a precursor by esterifying sebacic acid and an excess amount of neopentyl glycol, and a step (A-2) of preparing a poly(neopentyl sebacate) oligomer by polycondensing the precursor.

[0060] Specifically, in the above-mentioned step (A-1), the mole ratio of the sebacic acid and the neopentyl glycol can satisfy 1:1.0 to 3.0, preferably, 1:1.1 to 2.0, more preferably, 1:1.1 to 1.5, and the esterification reaction can be performed at a reaction temperature of 200°C to 250°C, preferably, 200°C to 230°C, using a tin catalyst such as tin oxide or a titanium catalyst such as tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, and butyl isopropyl titanate. The content of the catalyst can be 0.00001 parts by weight to 1 part by weight or 0.0001 parts by weight to 0.15 parts by weight, with respect to 100 parts by weight of the total amount of the above-mentioned succinic acid and the neopentyl glycol, and is not limited thereto as long as it does not inhibit the properties to be achieved in the present application. The precursor of the poly(neopentyl sebacate) oligomer can be prepared through the above-mentioned esterification reaction.

[0061] Further, in the above-mentioned step (A-1), the polycondensation of the precursor to prepare the poly(neopentyl sebacate) oligomer can be performed at a reaction temperature of 200°C to 260°C, preferably, 220°C to 240°C, and a vacuum condition of 0.5 Torr to 1 Torr. The polycondensation time can be 1 minute to 60 minutes, preferably, 2 minutes to 30 minutes, and the poly(neopentyl sebacate) oligomer satisfying the above-mentioned molecular weight range can be prepared in the case where the above-mentioned range is satisfied. The biodegradable polyester polymer including the same can ensure improved adhesion strength and transparency.

[0062] Further, in the above esterification reaction and polycondensation step, a stabilizer can be added in addition to the catalyst, and as non-limiting examples, phosphorous acid, trimethyl phosphate, and triphenyl phosphate, etc. can be used, but are not limited thereto. The content of the above stabilizer can be 0.000001 parts by weight to 1 part by weight or 0.000005 parts by weight to 0.1 parts by weight, with respect to 100 parts by weight of the above total of sebacic acid and neopentyl glycol, and is not limited thereto, as long as the properties to be achieved in the present application are not inhibited.

[0063] In the above step (A), as the excess of the above neopentyl glycol is added, the terminal of the above polyneopentyl sebacate oligomer can have a hydroxyl group, and particularly, in the case where the above sebacic acid and neopentyl glycol are within the above molar ratio range, the prepared polyneopentyl sebacate oligomer can preferably satisfy the above molecular weight range.

[0064] The above step (B) of preparing a polyester polymer by reacting a dicarboxylic compound, an aliphatic diol compound, and the above polyneopentyl sebacate oligomer can include: step (B-1) of preparing a precursor by reacting a polymerizable composition including a dicarboxylic compound, an aliphatic diol compound, and the above polyneopentyl sebacate oligomer; and step (B-2) of polycondensing the above precursor to prepare a biodegradable polyester polymer.

[0065] The specific description of the dicarboxylic compound, the aliphatic diol compound, and the polyneopentyl sebacate oligomer of the above step (B-1) and the examples of the compounds are the same as the above description.

[0066] As a specific embodiment, in the above step (B-1), the above reaction can be an esterification reaction, an ester exchange reaction, or a mixed reaction thereof. Specifically, the above reaction can be an esterification reaction. In the above step (B-1), a polymerizable composition including an aromatic dicarboxylic acid, an aliphatic diol compound, and a catalyst is first added to a dicarboxylic compound, and an esterification reaction is performed by performing a primary reaction at a temperature of 180°C to 280°C, and then, a polymerizable composition including an aliphatic carboxylic acid and a catalyst is added, and an esterification reaction is performed as a secondary reaction at a temperature of 180°C to 260°C.

[0067] In the above step (B-1), the above catalyst can use one or a combination of two or more selected from the group consisting of antimony oxide, tin oxide and the like tin-based catalysts, and tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, and butyl isopropyl titanate and the like titanium-based catalysts, and the content of the above catalyst can be 0.00001 to 1 parts by weight or 0.0001 to 0.15 parts by weight per 100 parts by weight of the total of the above dicarboxylic compound and the aliphatic diol compound, and is not limited thereto as long as the physical properties to be achieved in the present application are not inhibited.

[0068] As a specific other embodiment, the aliphatic carboxylic acid, the aliphatic diol compound, and the catalyst are first charged, and the esterification reaction is performed by a primary reaction at a temperature of 180 to 280°C, and then the aliphatic carboxylic acid and the catalyst are charged, and the esterification reaction is performed as a secondary reaction at a temperature of 180 to 260°C. The specific examples of the above catalyst and the content are the same as described above.

[0069] The above polyneopentyl sebacate oligomer can be charged to the above polymerizable composition to be polymerized in the above step (B-1) of the primary reaction or the secondary reaction. The content of the polyneopentyl sebacate oligomer can be 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 1 to 5 parts by weight per 100 parts by weight of the total of the above dicarboxylic compound and the aliphatic diol compound.

[0070] In the above step (B-2) of preparing a polyester polymer by polycondensation of the above precursor, the reaction can be performed at a reaction temperature of 200 to 280°C, and preferably at a reaction temperature of 220 to 270°C, in the presence of the above catalyst. The content of the above catalyst can be 0.00001 to 1 parts by weight or 0.0001 to 0.5 parts by weight per 100 parts by weight of the total of the above dicarboxylic compound and the aliphatic diol compound, and is not limited thereto as long as the physical properties to be achieved in the present application are not inhibited.

[0071] As another embodiment, the polyneopentyl sebacate oligomer can also be charged in step (B-2) instead of being charged in the above step (B-1).

[0072] In the above esterification reaction or polycondensation step, a stabilizer can be added in addition to the catalyst, and as non-limiting examples, phosphorous acid, trimethyl phosphate, and triphenyl phosphate, etc. can be used, but are not limited thereto. The content of the above stabilizer can be 0.000001 parts by weight to 1 part by weight or 0.000005 parts by weight to 0.1 part by weight, relative to 100 parts by weight of the total of the above dicarboxyl compound and the aliphatic diol compound, and is not limited thereto, as long as the properties to be achieved in the present application are not inhibited.

[0073] Hereinafter, the present application will be described in more detail according to Examples and Comparative Examples. However, the following Examples and Comparative Examples are merely one example for describing the present application in more detail, and the present application is not limited to the following Examples and Comparative Examples.

[0074] Property measurement method

[0075] 1) Molecular weight [g / mol]: A sample specimen was prepared by dissolving 1 weight percent of the oligomer or polymer in THF, and the weight average molecular weight (Mw) was measured using gel permeation chromatography (GPC, Waters 2690 model HPLC / RI detector (Detector)). PS was used as a standard specimen, and the measurement was performed by setting the flow rate to 1.0 mL / min and the column temperature to 40.0°C.

[0076] 2) Glass transition temperature (Tg) [°C]: The measurement was performed using a differential scanning calorimeter (DSC) by increasing the temperature at a rate of 10°C per minute from -50°C to 100°C.

[0077] 3) Solubility and storage stability: An adhesive composition was prepared by stirring 50 weight percent of the biodegradable polyester polymer, 30 weight percent of toluene, and 20 weight percent of methyl ethyl ketone for 10 minutes, and the solubility was evaluated by observing the state of the composition immediately after stirring. In addition, after the composition was left to stand for 1 month under normal temperature conditions, the storage stability was evaluated by observing the change in the composition. The evaluation criteria are as follows. Here, precipitation can mean the precipitation of solid precipitates such as gels, which are not liquid, in the composition.

[0078] Excellent: No precipitation

[0079] Good: Precipitation of 10 v% or less of the composition

[0080] Inadequate: Precipitation of more than 10 v% and less than 25 v% of the composition

[0081] Poor: Precipitation of more than 25 v% of the composition

[0082] 4) Peeling strength: The adhesive composition containing 50 weight percent of the biodegradable polyester polymer in toluene was applied on A4 paper at a thickness of about 50 μm, and after drying for 1 hour, the other A4 paper was overlaid in such a manner that no air bubbles were generated, and constant pressing was performed using a 2 kg roller. During peeling of the two A4 papers at a certain speed, the peeling strength was evaluated.

[0083] Strong: The two A4 papers were not peeled, and were torn

[0084] Medium: The two A4 papers were peeled with difficulty to such a degree that they were not torn

[0085] Weak: The two A4 papers were easily peeled

[0086] 5) Normal temperature adhesion: The adhesive composition containing 50 weight percent of the biodegradable polyester polymer in toluene was applied on A4 paper at a thickness of about 50 μm, and dried for 1 hour under normal temperature conditions. The tackiness of the adhesive surface was evaluated by hand (not tacky) 1 to 10 (very tacky), and is shown in Table 2 below. The greater the tackiness, the normal temperature adhesion was evaluated as excellent.

[0087] Preparation Example 1: Preparation of polyneopentyl sebacate oligomer

[0088] After 202.25 g (1 mol) of sebacic acid, 130.2 g (1.25 mol) of neopentyl glycol, and 0.031 g of tin oxide were put into a 500 ml round bottom flask, the temperature was gradually increased to 200 to 210°C to perform an esterification reaction. After water was completely drained, 0.015 g of a stabilizer, phosphorous acid, was put in, and while the temperature was gradually increased to 230°C, a condensation was performed for 5 minutes under a vacuum of 1 torr. After the reaction was completed, the polyneopentyl sebacate oligomer of Preparation Example 1 was finally obtained. The weight average molecular weight of the above oligomer, which was measured using GPC, was 4100 g / mol.

[0089] Preparation Example 2: Preparation of polyneopentyl sebacate polymer

[0090] In the condensation step of Preparation Example 1 above, except that the condensation was performed for 90 minutes at a temperature of 230°C under a vacuum of less than 1 torr, it was performed in the same manner as Preparation Example 1, and thus the polyneopentyl sebacate polymer of Preparation Example 2 was obtained. The weight average molecular weight of the above polymer was 42080 g / mol.

[0091] Preparation of biodegradable polyester polymer

[0092] Example 1

[0093] In a 500 ml round bottom flask, 8.31 g (0.05 mol) of terephthalic acid and 8.31 g (0.05 mol) of isophthalic acid (dicarboxylic compounds), 72.90 g (0.7 mol) of neopentyl glycol, 18.02 g (0.2 mol) of 1,4-butanediol, 12.41 g (0.2 mol) of ethylene glycol, and 22.83 g (0.3 mol) of propylene glycol (aliphatic diol compounds), and 0.003 g of catalyst tetrabutyl titanate were charged, and the temperature was gradually increased to 220°C while maintaining a pressure of 1 kgf / cm 2 After the theoretical amount of water was completely distilled off, 121.35 g (0.6 mol) of sebacic acid, 21.92 g (0.15 mol) of adipic acid, and 17.71 g (0.15 mol) of succinic acid (dicarboxylic compounds), 0.1 g of malic acid, 6 g of the polysebacic acid neopentyl ester oligomer (polyfunctional compound) of Preparation Example 1 described above, 0.003 g of antimony oxide, 0.032 g of tetrabutyl titanate, and 0.02 g of the stabilizer triphenyl phosphate were charged, and the esterification reaction (second) was performed at a temperature of 220°C under normal pressure. After the water was completely distilled off, 0.004 g of tin oxide and 0.002 g of the stabilizer trimethyl phosphate were charged, and after stirring for 10 minutes, the reaction was performed under low vacuum for 30 minutes, and then under a high vacuum of 0.5 Torr at 240°C for 140 minutes. After the reaction was completed, the biodegradable polyester polymer of Example 1 was finally obtained.

[0094] Example 2

[0095] In a 500 ml round bottom flask, 161.80 g (0.8 mol) of sebacic acid and 23.62 g (0.2 mol) of succinic acid (dicarboxylic compounds), 93.73 g (0.9 mol) of neopentyl glycol, 22.53 g (0.25 mol) of 1,4-butanediol, 6.21 g (0.1 mol) of ethylene glycol, and 11.41 g (0.15 mol) of propylene glycol (aliphatic diol compounds), 0.3 g of malic acid, 4 g of the polysebacic acid neopentyl ester oligomer (polyfunctional compound) of Preparation Example 1 described above, and 0.003 g of tetrabutyl titanate were charged, and the esterification reaction was performed by gradually increasing the temperature to 220°C under normal pressure. After the theoretical amount of water was completely distilled off, 0.003 g of antimony oxide, 0.002 g of tetrabutyl titanate, and 0.0015 g of the stabilizer phosphorous acid were charged, and after stirring for 10 minutes, the temperature was gradually increased to 245°C, and the reaction was performed under low vacuum for 30 minutes, and then under a high vacuum of 0.6 Torr for 130 minutes. After the reaction was completed, the biodegradable polyester polymer of Example 2 was finally obtained.

[0096] Example 3

[0097] Except that 16.61 g (0.1 mol) of isophthalic acid (dicarboxylic compound), 93.73 g (0.9 mol) of neopentyl glycol, 22.53 g (0.25 mol) of 1,4-butanediol, 6.21 g (0.1 mol) of ethylene glycol, and 11.41 g (0.15 mol) of propylene glycol (aliphatic diol compound) were charged in the primary esterification reaction of Example 1 above, and 161.80 g (0.8 mol) of sebacic acid and 14.61 g (0.1 mol) of adipic acid (dicarboxylic compound) were charged in the secondary esterification reaction, the reaction was carried out in the same manner as in Example 1, except that 4 g of the polyneopentyl glycol sebacate oligomer of Preparation Example 1 above was added, to obtain the biodegradable polyester polymer of Example 3.

[0098] Example 4

[0099] Except that 24.92 g (0.15 mol) of isophthalic acid (dicarboxylic compound), 83.32 g (0.8 mol) of neopentyl glycol, 9.01 g (0.1 mol) of 1,4-butanediol, and 45.65 g (0.6 mol) of propylene glycol (aliphatic diol compound) were charged in the primary esterification reaction of Example 1 above, and 171.91 g (0.85 mol) of sebacic acid (dicarboxylic compound) was charged in the secondary esterification reaction, the reaction was carried out in the same manner as in Example 1, except that 4 g of the polyneopentyl glycol sebacate oligomer of Preparation Example 1 above was added, to obtain the biodegradable polyester polymer of Example 4.

[0100] Example 5

[0101] Except that 16.61 g (0.1 mol) of terephthalic acid and 2.49 g (0.015 mol) of isophthalic acid (dicarboxylic compound), 93.73 g (0.9 mol) of neopentyl glycol, 6.21 g (0.1 mol) of ethylene glycol, and 30.44 g (0.4 mol) of propylene glycol (aliphatic diol compound) were charged in the primary esterification reaction of Example 1 above, and 171.91 g (0.85 mol) of sebacic acid (dicarboxylic compound) and 0.15 g of the multifunctional compound malic acid were charged in the secondary esterification reaction, the reaction was carried out in the same manner as in Example 1, except that 4 g of the polyneopentyl glycol sebacate oligomer of Preparation Example 1 above was added, to obtain the biodegradable polyester polymer of Example 5.

[0102] Example 6

[0103] Example 6 was obtained by the same manner as in Example 1 except that, in addition to 16.61 g (0.1 mol) of terephthalic acid and 16.61 g (0.1 mol) of isophthalic acid (dicarboxylic compounds), 62.49 g (0.6 mol) of neopentyl glycol, in the first esterification reaction, 121.35 g (0.8 mol) of sebacic acid, 14.61 g (0.1 mol) of adipic acid, 11.81 g (0.1 mol) of succinic acid (dicarboxylic compounds), 0.2 g of the polyfunctional compound malic acid, 5 g of the polysebacic acid neopentyl ester oligomer of Preparation Example 1, and 0.2 g of the polyfunctional compound malic acid were charged in the second esterification reaction.

[0104] Comparative Example 1

[0105] Example 1 was performed in the same manner as in Example 1 except that the polysebacic acid neopentyl ester oligomer of Preparation Example 1 was not charged.

[0106] Comparative Example 2

[0107] Comparative Example 2 was obtained by the same manner as in Example 1 except that, in the first and second esterification reactions of Example 1, trimethylolpropane was charged in the same molar amount as neopentyl glycol instead of neopentyl glycol.

[0108] Comparative Example 3

[0109] Example 1 was performed in the same manner as in Example 1 except that the polysebacic acid neopentyl ester oligomer of Preparation Example 1 was not charged.

[0110] The components and physical properties of Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 1 and Table 2 below.

[0111] Table 1

[0112]

[0113]

[0114] Table 2

[0115]

[0116] As shown in Tables 1 and 2 above, it was confirmed that in the case where the polyneopentyl glycol sebacate oligomer of Preparation Example 1 was used to prepare a biodegradable polyester polymer, a biodegradable adhesive composition having a glass transition temperature of -40 or less and excellent peeling strength and room temperature adhesion could be prepared even without including an additional tackifier. Further, it was confirmed from Comparative Example 1 and Examples 6 and 7 that, in the case where a diol was included instead of a polyol, particularly, in the case where neopentyl glycol was 50 mol% or more relative to the total number of moles of aliphatic diol compounds, more excellent solubility and storage stability were shown. Furthermore, it was confirmed from the additional examples that, in the case where a small amount of malic acid was not included as a functional group compound, poorer peeling strength and room temperature adhesion were shown compared to the case where it was included, and thus, in the case where a multi-functional group compound was included, an effect of improving adhesion and peeling strength was exhibited.

[0117] As described above, the present application is explained by specific matters, limited examples and drawings, and the above-described contents are provided only to help more fully understand the present application, and the present application is not limited to the above-described examples, and a person having ordinary skill in the art to which the present application pertains can make various modifications and changes from these descriptions.

[0118] Therefore, the idea of the present application should not be limited to the explained examples, and the scope of the invention described below and all modifications equivalent or equivalent to the scope of the invention should be considered to belong to the category of the idea of the partial invention.

Claims

1. A biodegradable polyester polymer, characterized in that The biodegradable polyester polymer is prepared from a polymerizable composition comprising: (a) a dicarboxyl compound including an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or a mixture thereof, (b) an aliphatic diol compound and (c) a polyneopentyl sebacate oligomer.

2. The biodegradable polyester polymer according to claim 1, characterized in that The weight average molecular weight Mw of the polyneopentyl sebacate oligomer is 2000 g / mol to 6000 g / mol.

3. The biodegradable polyester polymer according to claim 1, characterized in that The total weight of the polymerizable composition comprises 0.1 to 10 weight percent of the polyneopentyl sebacate oligomer.

4. The biodegradable polyester polymer according to claim 1, characterized in that The polymerizable composition further includes a polyfunctional compound having three or more polymerizable functional groups.

5. The biodegradable polyester polymer according to claim 4, characterized in that The polyfunctional compound is contained in an amount of 0.01 to 3 weight percent relative to the total weight of the polymerizable composition.

6. The biodegradable polyester polymer according to claim 1, wherein The above-mentioned aliphatic diol compound contains C 5-7 aliphatic diol compounds.

7. The biodegradable polyester polymer according to claim 1, characterized in that The aliphatic diol compound comprises 30 mol% to 90 mol% of neopentyl glycol and 10 mol% to 70 mol% of C 2-4 diol.

8. The biodegradable polyester polymer according to claim 1, wherein The aliphatic dicarboxylic acid is one or a combination of two or more selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid and anhydride derivatives thereof.

9. The biodegradable polyester polymer according to claim 1, wherein The aromatic dicarboxylic acid is one or a combination of two or more selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid.

10. The biodegradable polyester polymer according to claim 1, characterized in that The total weight of the dicarboxyl compound comprises 50 weight percent to 100 weight percent of the aliphatic dicarboxylic acid.

11. The biodegradable polyester polymer according to claim 1, wherein The molar ratio of the dicarboxyl compound to the aliphatic diol compound is 1:1-2.

12. The biodegradable polyester polymer according to claim 1, wherein The weight average molecular weight Mw is 60,000 g / mol to 150,000 g / mol.

13. The biodegradable polyester polymer according to claim 1, wherein The glass transition temperature is below -40°C.

14. A biodegradable adhesive composition, characterized in that: The method comprises a biodegradable polyester polymer selected from any one of claims 1 to 13.

15. A method for preparing a biodegradable polyester polymer, characterized in that: include: Step (A) of esterifying sebacic acid and an excess of neopentyl glycol and then subjecting them to polycondensation to prepare polyneopentyl sebacate oligomer; In step (B), a dicarboxyl compound, an aliphatic diol compound and the polyneopentyl sebacate oligomer are subjected to esterification and transesterification and then polycondensed to prepare a polyester polymer.

16. The method for preparing a biodegradable polyester polymer according to claim 15, wherein: In the above step (A), the molar ratio of sebacic acid to neopentyl glycol is 1:1.1-1.5.

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