KR20240007639A - A polyester resin and a method for manufacturing the same - Google Patents

Abstract

One aspect of the present invention provides a polyester resin including a soft segment and a hard segment, wherein the soft segment includes a dimer acid or an alkyl ester thereof, and a dibasic acid or an ester thereof, and a method for producing the same. do.

Description

Polyester resin and its manufacturing method {A POLYESTER RESIN AND A METHOD FOR MANUFACTURING THE SAME}

The present invention relates to polyester resin and its production method.

Adhesive materials such as adhesives, adhesives, sealants, coatings, and paints are used in various industrial fields such as civil engineering and construction, packaging, bookbinding, automobiles, electronics, precision, optical products, woodworking, plywood, textiles, and leather, as well as general household use. It is being used widely.

Recently, as environmental regulations such as volatile organic compound (VOC) emission regulations have been strengthened, eco-friendly products with relatively low emissions of volatile organic solvents, such as point/adhesives that are applied by melting with heat and so-called hot melt adhesives, are being widely used.

Hot melt adhesives are made of solids based on thermoplastic resins, either alone or mixed with other materials, and develop adhesiveness by heating and melting. They are evaluated as being reversible, economical, and eco-friendly.

These hot melt adhesives/adhesives are generally composed of a thermoplastic polymer such as an olefin-based copolymer as a base polymer and a tackifier and a viscosity regulator such as wax. Among olefin-based copolymers, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, or ethylene vinyl acetate have the advantage of excellent flexibility and low unit price, but their low polarity makes it difficult to sufficiently develop adhesiveness, especially, There is a problem with low adhesion to polyester-based substrates, which are widely applied to vehicle parts, etc., adversely affecting the completeness of vehicle assembly.

Low-melting point polyester-based resins, developed to improve adhesion to polyester-based substrates, are used as hot-melt binders to bond dissimilar fiber-based parts applied to mattresses, vehicle interior materials, etc.

Polyester refers to a polymer having an ester group (-COO-). In a broad sense, it is a component of a compound synthesized through a condensation reaction from a carboxyl group (-COOH) or an ester group (-COO-) and a hydroxy group (-OH). It can be understood as including all polymers with . While these polyesters generally have excellent mechanical strength and chemical resistance, they are prone to destruction due to deformation and are hydrophilic, so there is a problem of reduced hydrolysis stability.

In response to this, a method of copolymerizing a monomer capable of providing flexibility has been proposed, but there is a problem in that the crystallinity of the polymerized polyester-based copolymer and the resulting mechanical strength are reduced. In addition, a method of adding a hardener or the like to compensate for the reduced crystallinity has been proposed, but in this case, there is a problem that the formability is reduced due to hardening.

Meanwhile, since most polyester resins currently used are manufactured based on petroleum-based raw materials, there is a problem of adverse effects on the environment due to the use of fossil fuels. In response, Korean Patent No. 10-2032410 applies a polyester resin copolymerized with epoxidized vegetable oil-based monomers to achieve mechanical strength, flexibility, and adhesion, while at the same time reducing the risk of damage caused by polyester based on petroleum-based raw materials. Although it is disclosed that environmental problems can be solved, there is a problem in that as Young's modulus, tensile strength, and adhesiveness increase, the flexibility indicated by tensile elongation rapidly decreases, deepening the imbalance between each physical property.

The present invention is intended to solve the problems of the prior art described above, and the purpose of the present invention is to improve mechanical strength, flexibility, and adhesiveness in a balanced manner, while also solving environmental problems caused by polyester based on petroleum-based raw materials. To provide a polyester resin and a method for manufacturing the same.

One aspect of the present invention provides a polyester resin including a soft segment and a hard segment, wherein the soft segment includes a dimer acid or an alkyl ester thereof, and a dibasic acid or an ester thereof.

In one embodiment, the content of the soft segment in the polyester resin may be 45 to 68.5% by weight.

In one embodiment, the content of the dibasic acid or its ester in the polyester resin may be 1 to 20% by weight.

In one embodiment, the content of the dibasic acid or its ester in the soft segment may be 5 to 35% by weight.

In one embodiment, the dimer acid may be obtained from vegetable oil, animal oil, or a combination thereof.

In one embodiment, the dibasic acid is one selected from the group consisting of adipic acid, malonic acid, oxalic acid, succinic acid, glutaric acid, sebacic acid, undecanoic acid, itaconic acid, maleic acid, and combinations of two or more thereof. You can.

In one embodiment, the hard segment may include an aromatic dicarboxylic acid-based compound and a diol compound.

In one embodiment, the aromatic dicarboxylic acid-based compound may be one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 2,5-furane dicarboxylic acid, and combinations of two or more thereof.

In one embodiment, the diol compound is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexane It may be one selected from the group consisting of dimethanol, 2,2,4-trimethyl-1,3-pentanediol, and combinations of two or more thereof.

Another aspect of the present invention is a method for producing the polyester resin, wherein (a) a monomer containing a dimer acid or an alkyl ester thereof, a dibasic acid or an ester thereof, an aromatic dicarboxylic acid compound, and a diol compound is added to the reactor. Adding a mixture and a catalyst and reacting to obtain a first product; (b) reducing the pressure of the reactor to 10 to 50 mmHg to remove unreacted monomers from the first product to obtain a second product; and (c) reducing the pressure of the reactor to 1 mmHg or less and reacting the second product.

The polyester resin according to one aspect of the present invention includes a soft segment and a hard segment, and the soft segment includes a dimer acid or an alkyl ester thereof, and a dibasic acid or an ester thereof, thereby balancing mechanical strength, flexibility, and adhesiveness. It can be implemented effectively.

In addition, the method for producing a polyester resin according to another aspect of the present invention is to perform a primary reaction of a preset monomer mixture, obtain a primary product from which unreacted monomers are removed under reduced pressure conditions, and perform a secondary reaction thereof. The mechanical strength, flexibility, and adhesion of the polyester resin can be further improved.

The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

Hereinafter, the present invention will be described. However, the present invention may be implemented in various different forms and, therefore, is not limited to the embodiments described herein.

Throughout the specification, when a part is said to be “connected” to another part, this includes not only cases where it is “directly connected,” but also cases where it is “indirectly connected” with another member in between. . Additionally, when a part is said to “include” a certain component, this does not mean that other components are excluded, but that other components can be added, unless specifically stated to the contrary.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

polyester resin

One aspect of the present invention provides a polyester resin including a soft segment and a hard segment, wherein the soft segment includes a dimer acid or an alkyl ester thereof, and a dibasic acid or an ester thereof.

The polyester resin may be a copolymer composed of one or more monomers constituting the soft segment and one or more monomers constituting the hard segment.

The soft segment has low hardness and soft properties, so it contributes to the flexibility of the polyester resin, and the hard segment has relatively high hardness and hard properties, so the polyester resin and products containing it, for example, Can contribute to the mechanical strength and adhesion of hot melt adhesives/adhesives.

The content of the soft segment in the polyester resin may be 45 to 68.5% by weight. If the content of the soft segment is less than 45% by weight, the flexibility of the polyester resin and products containing it may be reduced, and if it is more than 68.5% by weight, mechanical strength and adhesiveness may be reduced.

The soft segment may include dimer acid or its alkyl ester, and dibasic acid or its ester.

The dimer acid or its alkyl ester may be obtained from vegetable oil (or waste vegetable oil) and/or animal oil (or waste animal oil), and the alkyl ester may be a C1 to C6 alkyl ester.

The vegetable oil may be soybean oil, safflower oil, rapeseed oil, olive oil, canola oil, safflower seed oil, sunflower oil, flax oil, corn oil, rice bran oil, palm oil, coconut oil, etc., and the animal fatty acid may be beef tallow, pork fat, fish oil, etc., but is limited thereto. That is not the case. In addition, the vegetable oil and/or the animal oil may qualitatively include lauric fatty acid, myristic fatty acid, palmitic fatty acid, stearic fatty acid, oleic fatty acid, linoleic fatty acid, linolenic fatty acid, etc. It is not limited to this.

That is, the dimer acid or its alkyl ester may be a dimer of saturated and/or unsaturated fatty acid obtained from the vegetable oil and/or the animal oil, or its ester. For example, the dimer acid may be a dimer acid produced by thermal polymerization of diene fatty acid in the vegetable oil, a non-conjugated dimer acid, or a mixture thereof.

C18-linolenic acid in the vegetable oil is converted into non-aromatic cyclic dimer acids such as acyclic dimer acid, monocyclic dimer acid and bicyclic dimer acid with 36 carbon atoms by thermal polymerization in the presence of a catalyst, and benzene. It can be converted to an aromatic dimer acid containing a ring. Since the vegetable oil contains saturated and/or unsaturated fatty acids, the dimer acid composition prepared from the vegetable oil includes not only C36 dimer acid derived from C18-linolenic acid, but also various cyclic (or cyclic) and acyclic (or non-cyclic) types with different chain lengths. cyclic) may include dimer acid.

Meanwhile, the dimer acid alkyl ester may be derived from the dimer acid, and may be synthesized by esterifying dimer acid raw materials purified from resources generated from the vegetable oil and/or the animal oil with alcohol in the presence of an acid catalyst.

The dibasic acid or its ester may constitute a soft segment of the polyester resin together with the dimer acid or its alkyl ester. Conventionally, dibasic acids or their esters are included as a component of compositions, i.e., mixtures, that make up paints, coatings, and coatings, and are used to control and improve the viscosity, adhesion, smoothness, processability, quick drying, etc. of the composition. , these compositions require an organic solvent as a medium for mixing and dispersing each component, and as a result, a large amount of volatile organic compounds (VOCs) are generated, which has the problem of worsening the surrounding environment.

In this regard, the dibasic acid or its ester is one monomer that makes up the polyester resin, that is, a polyester copolymer, and can be chemically combined with other monomers used together.

The polyester resin containing the dibasic acid or its ester can be obtained in a solid state, and this solid state can be used as a hot melt adhesive through appropriate processing when necessary.

The dibasic acid or its ester alleviates and solves the problems of polyester resins applied as conventional hot melt adhesives, specifically, the trade-off that exists between mechanical strength, flexibility, and adhesiveness, thereby balancing them with each other. It can be implemented and improved.

The content of the dibasic acid or its ester in the polyester resin may be 1 to 20% by weight, preferably 5 to 20% by weight, more preferably 10 to 20% by weight, and the dibasic acid in the soft segment The content of the base acid or its ester may be 5 to 35% by weight, preferably 10 to 35% by weight, and more preferably 15 to 35% by weight. If the content of the dibasic acid or its ester is less than the lower limit, the flexibility of the polyester resin and products containing it may be reduced, and if it is more than the upper limit, the balance between mechanical strength, flexibility, and adhesiveness may be disrupted.

The dibasic acid may be one selected from the group consisting of adipic acid, malonic acid, oxalic acid, succinic acid, glutaric acid, sebacic acid, undecanoic acid, itaconic acid, maleic acid, and combinations of two or more thereof, preferably , may be adipic acid, but is not limited thereto.

Meanwhile, the dibasic acid ester may be derived from the dibasic acid, and may be synthesized by esterifying the dibasic acid with an alcohol.

The hard segment may include an aromatic dicarboxylic acid compound and a diol compound as monomers.

The aromatic dicarboxylic acid compound is one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 2,5-furane dicarboxylic acid, and a combination of two or more thereof, or an ester and/or anhydride of each of these. It may be, but is not limited to this.

The content of the aromatic dicarboxylic acid-based compound in the polyester resin may be 1 to 25% by weight, preferably 4 to 20% by weight, and more preferably 5 to 15% by weight. If the content of the aromatic dicarboxylic acid-based compound in the polyester resin is less than 1% by weight, the mechanical strength and adhesiveness of the polyester resin and products containing it may be reduced, and if it is more than 25% by weight, flexibility may be reduced. there is.

The diol compound may be a C2-12 alkanol having two hydroxyl groups, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol , 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1, It may be one selected from the group consisting of 3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, and combinations of two or more of these, but is limited thereto. That is not the case.

A polyester resin having the above composition can achieve balanced mechanical strength, flexibility, and adhesiveness. Specifically, the polyester resin may satisfy at least one, preferably all, of the following conditions (i) to (iv). (i) Young's modulus 5 to 20 MPa, preferably 6 to 15 MPa, more preferably 10 to 13 MPa; (ii) tensile strength of 3 to 10 MPa, preferably 5 to 10 MPa, more preferably 7 to 10 MPa; (iii) tensile elongation of 600 to 800%, preferably 620 to 750%, more preferably 640 to 750%; (iv) peel strength of 10 to 40 N/cm, preferably 15 to 30 N/cm , more preferably, 20 to 30 N/cm.

In addition, the number average molecular weight (Mn) of the polyester resin may be 5,000 to 40,000 g/mol, preferably 8,000 to 25,000 g/mol, more preferably 10,000 to 22,000 g/mol, and the weight average molecular weight (Mw) may be 20,000-100,000 g/mol, preferably 30,000-65,000 g/mol, more preferably 45,000-60,000 g/mol, and the softening point is 100-125°C, preferably 105-105°C. It may be 115°C.

Manufacturing method of polyester resin

Another aspect of the present invention is a method for producing the polyester resin, wherein (a) a monomer containing a dimer acid or an alkyl ester thereof, a dibasic acid or an ester thereof, an aromatic dicarboxylic acid compound, and a diol compound is added to the reactor. Adding a mixture and a catalyst and reacting to obtain a first product; (b) reducing the pressure of the reactor to 10 to 50 mmHg to remove unreacted monomers from the first product to obtain a second product; and (c) reducing the pressure of the reactor to 1 mmHg or less and reacting the second product.

In step (a), a monomer mixture including dimer acid or its alkyl ester, dibasic acid or ester, aromatic dicarboxylic acid compound, and diol compound and a catalyst can be added and then reacted to obtain the first product.

The types, ratios, effects, etc. of monomers required to produce the polyester resin, that is, the copolymer, are the same as described above.

The catalyst may be an alkali metal compound, a manganese compound, a cobalt compound, an aluminum compound, an antimony compound, a titanium compound, a zinc compound, a germanium compound, a tin compound, etc. Preferably, Ti(OBu) ₄ , Ti(Oi-Pr) ₄ , SnO(Bu) ₂ , Sb ₂ O ₃ , Zn(OAc) ₂ , Mn(OAc), etc., but is not limited thereto.

In step (a), the temperature of the reactor may be adjusted to a range of 150 to 300°C, preferably 150 to 200°C. If the temperature of the reactor is less than 150°C, the reaction rate may decrease and productivity may decrease, and if it exceeds 200°C, the esterification reaction may proceed rapidly, generating unnecessary by-products and/or increasing the molecular weight distribution (Mw/Mn). there is a problem.

In addition, the reaction in step (a) can be performed while maintaining nitrogen purge, and in particular, the purge rate is adjusted to 50 to 200 cc/min, preferably 80 to 150 cc/min to remove methanol, a by-product generated during the reaction. The first product can be obtained while removing the etc.

In step (b), the nitrogen purge is stopped, and the reactor is depressurized to 10 to 50 mmHg, preferably 15 to 30 mmHg, to remove unreacted monomers such as diol compounds in the first product to produce the second product. can be obtained. If the pressure of the reactor exceeds 50 mmHg, not only cannot the unreacted monomer be properly removed, but there is also a problem in that the subsequent step (c) is difficult to perform smoothly.

In step (c), the reactor may be further reduced to 1 mmHg or less and the second product may be reacted to obtain a polyester resin. The reaction in step (c) is a polycondensation reaction to increase the molecular weight of the second product obtained in step (b), and the temperature of the reactor is adjusted to 200 ℃ or more, preferably 240 to 300 ℃. You can.

That is, in step (c), the temperature of the reactor is increased compared to steps (a) and (b). In this case, when the temperature of the reactor is rapidly increased, the viscosity of the second product rapidly increases. Since polymer growth may occur non-uniformly, the temperature increase rate of the reactor can be adjusted to 1 to 5°C/min, preferably 2 to 2.5°C/min.

Hereinafter, embodiments of the present invention will be described in detail.

Example 1

A thermometer, stirrer, distiller, and nitrogen pipe were installed in a four-neck reactor, and dimer acid derived from vegetable oil was esterified with methanol under an acid catalyst to produce dimer acid methyl ester (DAME, 0.4 mol, 228 g) and dimethyl isophthalic acid ( DMI, 0.2 mol, 38.8 g), dibasic acid ester based on adipic acid (DBE, 0.2 mol, 31.7 g), 1,4-butanediol (BDO, 1.2 mol, 108.14 g) and dibutyltin oxide (DBTO) , 20 mmol, 0.4 g) was added to the reactor. The temperature of the reactor was raised to 100°C and nitrogen was purged at a rate of 100 cc/min. During the nitrogen purge, the temperature of the reactor was raised to 180°C, reaction was performed for 5 hours, and the water produced was removed.

Nitrogen purge was stopped, the temperature of the reactor was maintained at 180°C, and the pressure was reduced to 15-30 mmHg to remove unreacted 1,4-butanediol for 5 hours.

When the removal of unreacted 1,4-butanediol was completed, the temperature of the reactor was raised to 250°C, the pressure was reduced to 1 mmHg or less, and reaction was performed for 8 hours to prepare a polyester resin.

Example 2

Dimeric acid methyl ester (DAME, 0.4 mol, 228 g), dimethyl isophthalic acid (DMI, 0.1 mol, 19.4 g), and adipic acid were synthesized by esterifying dimer acid derived from vegetable oil with methanol under an acid catalyst in a four-neck reactor. Except that dibasic acid ester (DBE, 0.3 mol, 47.6 g), 1,4-butanediol (BDO, 1.2 mol, 108.14 g) and dibutyltin oxide (DBTO, 20 mmol, 0.4 g) were added. , a polyester resin was prepared in the same manner as Example 1.

Example 3

Dimeric acid methyl ester (DAME, 0.4 mol, 228 g), dimethyl isophthalic acid (DMI, 0.3 mol, 58.3 g), and adipic acid were synthesized by esterifying dimer acid derived from vegetable oil with methanol under an acid catalyst in a four-neck reactor. Except that dibasic acid ester (DBE, 0.1 mol, 15.9 g), 1,4-butanediol (BDO, 1.2 mol, 108.14 g), and dibutyltin oxide (DBTO, 20 mmol, 0.4 g) were added. , a polyester resin was prepared in the same manner as Example 1.

Example 4

Dimeric acid methyl ester (DAME, 0.24 mol, 136.8 g), dimethyl isophthalic acid (DMI, 0.28 mol, 54.4 g), and adip were synthesized by esterifying dimer acid derived from vegetable oil with methanol under an acid catalyst in a four-neck reactor. Excluding the addition of acid-based dibasic acid ester (DBE, 0.28 mol, 44.4 g), 1,4-butanediol (BDO, 1.2 mol, 108.14 g), and dibutyltin oxide (DBTO, 20 mmol, 0.4 g) In this case, a polyester resin was prepared in the same manner as in Example 1 above.

Example 5

Dimeric acid methyl ester (DAME, 0.24 mol, 136.8 g), dimethyl isophthalic acid (DMI, 0.14 mol, 27.2 g), and adip were synthesized by esterifying dimer acid derived from vegetable oil with methanol under an acid catalyst in a four-neck reactor. Excluding the addition of acid-based dibasic acid ester (DBE, 0.42 mol, 66.6 g), 1,4-butanediol (BDO, 1.2 mol, 108.14 g), and dibutyltin oxide (DBTO, 20 mmol, 0.4 g) In this case, a polyester resin was prepared in the same manner as in Example 1 above.

Comparative Example 1

Dimeric acid methyl ester (DAME, 0.8 mol, 456 g), 1,4-butanediol (BDO, 1.2 mol, 108.14 g), synthesized by esterifying vegetable oil-derived dimer acid with methanol under an acid catalyst in a four-neck reactor. A polyester resin was prepared in the same manner as Example 1, except that dibutyltin oxide (DBTO, 20 mmol, 0.4 g) was added.

Comparative Example 2

Dimeric acid methyl ester (DAME, 0.4 mol, 228 g), dimethyl isophthalic acid (DMI, 0.4 mol, 77.7 g), 1,4 synthesized by esterifying dimer acid derived from vegetable oil with methanol under an acid catalyst in a four-neck reactor. -A polyester resin was prepared in the same manner as in Example 1, except that butanediol (BDO, 1.2 mol, 108.14 g) and dibutyltin oxide (DBTO, 20 mmol, 0.4 g) were added.

Comparative Example 3

Dimeric acid methyl ester (DAME, 0.4 mol, 228 g), dimethyl isophthalic acid (DMI, 0.2 mol, 38.8 g), and adipic acid were synthesized by esterifying dimer acid derived from vegetable oil with methanol under an acid catalyst in a four-neck reactor. Except that dibasic acid ester (DBE, 0.6 mol, 95.1 g), 1,4-butanediol (BDO, 1.2 mol, 108.14 g), and dibutyltin oxide (DBTO, 20 mmol, 0.4 g) were added. , a polyester resin was prepared in the same manner as Example 1.

Comparative Example 4

Dimeric acid methyl ester (DAME, 0.079 mol, 45 g), dimethyl terephthalic acid (DMT, 0.076 mol, 14.81 g), and 1,4-synthesized by esterifying dimer acid derived from vegetable oil with methanol under an acid catalyst in a four-neck reactor. In the same manner as Example 1, except that butanediol (BDO, 0.229 mol, 20.62 g), epoxidized soybean oil (ESBO, 4.02 g), and dibutyltin oxide (DBTO, 95 mmol, 1.9 g) were added. A polyester resin was prepared.

The temperature of the reactor was raised to 100°C and nitrogen was purged at a rate of 100 cc/min. During the nitrogen purge, the temperature of the reactor was raised to 180°C, reaction was performed for 5 hours, and the water produced was removed.

The temperature of the reactor was raised to 250°C, the pressure was reduced to 1 mmHg or less, and reaction was performed for 8 hours to prepare a polyester resin.

Comparative Example 5

Dimeric acid methyl ester (DAME, 0.044 mol, 25 g), dimethyl terephthalic acid (DMT, 0.046 mol, 9.06 g), and dimethyl isophthalic acid were synthesized by esterifying dimer acid derived from vegetable oil with methanol under an acid catalyst in a four-neck reactor. (DMI, 0.049 mol, 9.6 g), 1,4-butanediol (BDO, 0.212 mol, 19.09 g), epoxidized soybean oil (ESBO, 4.43 g), and dibutyltin oxide (DBTO, 52.5 mmol, 1.05 g). A polyester resin was prepared in the same manner as in Comparative Example 4, except that .

Comparative Example 6

Dimeric acid methyl ester (DAME, 0.032 mol, 18 g), dimethyl terephthalic acid (DMT, 0.08 mol, 15.7 g), and dimethyl isophthalic acid were synthesized by esterifying dimer acid derived from vegetable oil with methanol under an acid catalyst in a four-neck reactor. Comparative example above, except that (DMI, 0.041mol, 8g), 1,4-butanediol (BDO, 0.229mol, 20.62g), and dibutyltin oxide (DBTO, 38.5mmol, 0.77g) were added. Polyester resin was prepared in the same manner as in 4.

Composition (unit: weight %) of the reactant (monomer mixture) according to the above examples and comparative examples, molecular weight measured through room temperature GPC (Gel Permeation Chromatography) of the polyester resin, and thermogravimetric analysis (TGA) The softening points measured are shown in Tables 1 and 2 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 soft
segment DAME 56.1 56.6 55.6 52.4 40.4 39.2 DBE 7.8 11.8 3.9 10.2 19.7 6.4 ESBO 0.0 0.0 0.0 0.0 0.0 0.0 hard
segment DMI 9.5 4.8 14.2 12.5 8.0 23.4 DMT 0.0 0.0 0.0 0.0 0.0 0.0 BDO 26.6 26.8 26.4 24.9 31.9 31.0 Weight average molecular weight
(Mw, kg/mol) 53.5 57.4 47.8 46.5 50.9 49.3 Number average molecular weight
(Mn, kg/mol) 19.8 20.5 18.4 20.2 21.2 19.7 Molecular weight distribution
(Mw/Mn) 2.70 2.80 2.60 2.30 2.40 2.50 Yeonhwa branch
(℃) 105 103 105 115 113 121

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 soft
segment DAME 80.8 55.1 48.5 53.3 37.2 26.3 DBE 0.0 0.0 20.2 0.0 0.0 0.0 ESBO 0.0 0.0 0.0 4.8 6.6 9.1 hard
segment DMI 0.0 18.8 8.3 0.0 14.3 11.7 DMT 0.0 0.0 0.0 17.5 13.5 22.9 BDO 19.2 26.1 23.0 24.4 28.4 30.1 Weight average molecular weight
(Mw, kg/mol) 51.9 46.3 52.4 56.4 41.5 38.5 Number average molecular weight
(Mn, kg/mol) 17.9 18.5 21.6 19.6 15.2 14.8 Molecular weight distribution
(Mw/Mn) 2.90 2.50 2.43 2.80 2.70 2.60 Yeonhwa branch
(℃) 87 105 112 104 120 119

Experiment example

In order to confirm the mechanical strength, flexibility, and adhesiveness of the polyester resin, the Young's modulus, tensile strength, tensile elongation, and peel strength of the polyester resin according to the above Examples and Comparative Examples were measured and are shown in Table 3 below.

division Young's modulus
(MPa) tensile strength
(MPa) tensile elongation
(%) Peel strength
(N/cm) Example 1 9.2 6.2 670 17.1 Example 2 8.2 5.3 690 11.5 Example 3 5.7 3.2 660 10.5 Example 4 12.5 9.7 640 20.4 Example 5 11.3 8.5 630 28.5 Example 6 6.9 4.2 610 18.1 Comparative Example 1 5.5 3.1 700 5.7 Comparative Example 2 3.3 3.1 640 8.7 Comparative Example 3 4.8 4.4 680 21.7 Comparative Example 4 8.5 5.3 640 9.0 Comparative Example 5 9.6 7.8 580 24.3 Comparative Example 6 11.8 9.5 450 19.1

The description of the present invention described above is for illustrative purposes, and those skilled in the art will understand that the present invention can be easily modified into other specific forms without changing the technical idea or essential features of the present invention. will be. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as unitary may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims described below, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present invention.

Claims (7)

In the polyester resin containing soft segments and hard segments,
The soft segment is,
Contains dimer acid or its alkyl ester, and dibasic acid ester,
The content of the soft segment in the polyester resin is 45 to 68.5% by weight,
The content of the dibasic acid ester in the polyester resin is 5 to 20% by weight,
The hard segment includes an aromatic dicarboxylic acid compound and a diol compound,
The content of the aromatic dicarboxylic acid compound in the polyester resin is 4 to 15% by weight,
The Young's modulus of the polyester resin is 6 to 15 MPa, the tensile strength is 5 to 10 MPa, and the peel strength is 10 to 40 N/cm,
Polyester resin. According to paragraph 1,
The content of the dibasic acid ester in the soft segment is 5 to 35% by weight,
Polyester resin. According to paragraph 1,
The dimer acid is obtained from vegetable oil, animal oil, or a combination thereof,
Polyester resin. According to paragraph 1,
The dibasic acid ester is derived from one selected from the group consisting of adipic acid, malonic acid, oxalic acid, succinic acid, glutaric acid, sebacic acid, undecanoic acid, itaconic acid, maleic acid, and combinations of two or more of these.
Polyester resin. According to paragraph 1,
The aromatic dicarboxylic acid-based compound is one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 2,5-furane dicarboxylic acid, and combinations of two or more of these,
Polyester resin. According to paragraph 1,
The diol compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2 , 4-trimethyl-1,3-pentanediol and a combination of two or more thereof,
Polyester resin. In the method for producing the polyester resin according to any one of claims 1 to 6,
(a) adding a monomer mixture including dimer acid or its alkyl ester, dibasic acid ester, aromatic dicarboxylic acid compound, and diol compound to the reactor, and a catalyst, followed by reaction to obtain a first product;
(b) reducing the pressure of the reactor to 10 to 50 mmHg to remove unreacted monomers from the first product to obtain a second product; and
(c) depressurizing the reactor to 1 mmHg or less and reacting the second product; comprising,
Method for producing polyester resin.