KR101844998B1 - Self-healing polyester and film prepared by using the same - Google Patents

Abstract

The present invention provides a self-heating polyester and a film prepared by using the same. The present invention is able to perform self-heating at the room temperature without additional heat process or light irradiation when being damaged, and has high solvent resistance and transparency, and excellent mechanical strength.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a self-restoring polyester and a film produced using the self-

The present invention relates to a self-restoring polyester capable of self-restoring at room temperature without any additional heat treatment or light irradiation, exhibiting excellent mechanical strength together with high solvent resistance, transparency and whiteness, ≪ / RTI >

Polymer materials having anti-scratch, anti-chip or anti-stone functions, specifically coating composition or film material for coating protection are used in various fields such as automobile, military, IT have.

For example, in automobiles, it is possible to prevent damage to the vehicle body surface or headlights by debris or sand during running of the vehicle, and is also necessary for aesthetic purposes. In military applications, helicopter blade surfaces can also be fatal to small scratches, so an anti-chip coating film or film is essential. For IT use, it is also necessary to use for protecting the display of smart phone or TV from external damage, and for preventing wing damage caused by ice on the surface of the drones.

For such an anti-chip coating or film, transparency and solvent resistance as well as abrasion resistance such as scratch resistance, anti-chip or anti-stone are required.

In the 2000s, anti-chip coating films or films were added that added functionality related to self-healing. The self-restoration function refers to a characteristic that when scratches occur on the surface of a coating film or a film, the film is restored to its original state without any heat treatment or light irradiation, and returns to its original state without scratches.

The self-restoration function can be classified as extrinsic-type or intrinsic-type according to its action mechanism. The mechanism by which a microcapsule contained in a coating film or a film is restored by a healing agent that is blown out by scratching is referred to as an exogenous type. This mechanism is a phenomenon that interfacial heterogeneity occurs at a restoration site, There is a problem that restoration by exhaustion is difficult. In order to overcome this problem, the intrinsic type is proposed in which a chemical bond of a coating or a film material itself introduces functional groups capable of reversibly covalent bonding by heat or light, . However, the endogenous type self-recoverable materials are mostly coated films or films that can recover the scratches only when an external stimulus such as heat treatment or light treatment is applied, and thus there is a need to apply an artificial external stimulus for self restoration.

In addition, in the case of the conventional self-restoring polymer material, the recovery speed at room temperature is slow and the restoring force is low, and it is not transparent, and the strength of the material is weak.

Accordingly, when a self-restoring coating film or a film is damaged, it is required to develop a self-restoring coating film or film that can self-recover at room temperature without any heat treatment or light irradiation, has high solvent resistance and transparency, and has excellent mechanical strength have.

The present invention provides a self-restoring polyester capable of self-restoring at room temperature without any additional heat treatment or light irradiation at the time of damage, exhibiting excellent mechanical strength together with high solvent resistance, transparency and whiteness, and a method for producing the same.

The present invention also provides a film produced using the polyester.

In order to solve the above problems, according to one embodiment of the present invention

(a) from more than 10 mol% to 35 mol% or less of recurring units derived from a tricarboxylic acid compound containing at least one hydroxyl group in the molecule;

(b) 30 to 70 mol% of recurring units derived from at least one compound selected from the group consisting of (b1) an alicyclic diol compound and (b2) an alicyclic dicarboxylic acid compound; And

(c) 10 to 40 mol% of recurring units derived from at least one compound of (c1) an aliphatic dicarboxylic acid compound and (c2) an aliphatic diol compound, wherein (b) and (c) Recoverable polyester that is not a repeating unit derived from a complex-oxide-based compound.

According to another embodiment of the present invention, there is provided a tricarboxylic acid-based compound comprising (a) from 10 mol% to 35 mol% of a tricarboxylic acid-based compound containing at least one hydroxyl group in a molecule; (b) 30 to 70 mol% of recurring units derived from at least one compound selected from the group consisting of (b1) an alicyclic diol compound and (b2) an alicyclic dicarboxylic acid compound; And (c) 10 to 40 mol% of a repeating unit derived from at least one compound selected from the group consisting of (c1) an aliphatic dicarboxylic acid compound and (c2) an aliphatic diol compound, (b) and (c) are not dicarboxylic acid compounds at the same time.

Still further, according to another embodiment of the present invention, there is provided a film produced using the self-restorable polyester.

The self-restorable polyester according to the present invention can self-recover at room temperature without any additional heat treatment or light irradiation, and exhibits excellent tensile strength along with high solvent resistance, transparency and whiteness. In addition, the polyester is a biomass-based material which is harmless, environmentally friendly, and can be processed by heat.

Accordingly, the polyester can be usefully used as a coating film or a film in a variety of fields requiring wear resistance, transparency and solvent resistance, such as scratch resistance, anti-chip, anti-stone, etc. for automobile, military use and IT.

Fig. 1 is a photograph of the polyester produced in Example 1-1 after its cleavage at room temperature. Fig.
2 shows the results of FT-IR spectroscopic observation of the polyesters prepared in Examples 1-1 to 1-3.
Fig. 3 is a photograph showing the formation of heat of the polyester produced in Example 1-1. Fig.
4 is a photograph of the self-restoration of the polyester film prepared in Example 2-1 at room temperature after the scratching.

Hereinafter, the present invention will be described in more detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

Also, as used in the specification of the present invention, the term " comprising " embodies certain features, areas, integers, steps, operations, elements and / or components, Or does not exclude the presence or addition of an ingredient.

Some of the terms used in the following specification can be defined as follows.

As used herein, a "polyester" is a synthetic polymer produced by polycondensation of one or more carboxylic acids with one or more diol compounds, including "copolyesters".

In the present specification, the term "repeating unit" means a unit structure having a functional group derived from a diol or a functional group derived from a carboxylic acid bonded through a carbonyloxy group.

In the present specification, "mol%" may be based on the total moles of the carboxylic acid-derived functional group or structure, the total moles of the diol-derived functional group or the structure, or the total moles of the repeating units. As an example, a polyester containing 30 mol% citric acid based on the total carboxylic acid may be prepared by reacting the polyester with 100 mol% of the total carboxylic acid-derived functional groups or structures of 30 mol% Quot; refers to containing a ric acid-derived functional group or structure.

Hereinafter, the present invention will be described in more detail.

The self-restorable polyester according to one embodiment of the present invention is a self-

(a) from more than 10 mol% to 35 mol% or less of recurring units derived from a tricarboxylic acid compound containing at least one hydroxyl group in the molecule;

(b) 30 to 70 mol% of recurring units derived from at least one compound selected from the group consisting of (b1) an alicyclic diol compound and (b2) an alicyclic dicarboxylic acid compound; And

(c) 10 to 40 mol% of recurring units derived from at least one compound of (c1) an aliphatic dicarboxylic acid compound and (c2) an aliphatic diol compound, wherein (b) and (c) Is not a repeating unit derived from a complex-acid compound.

Specifically, in the self-restorable polyester according to one embodiment of the present invention, the repeating unit derived from a tricarboxylic acid-based compound containing at least one hydroxy group in the molecule of the above-mentioned (a) Quot;), the polyesters can have a highly branched molecular structure by including three carboxyl groups, and as a result, the mechanical strength characteristics of the polyester can be improved. Further, a highly crosslinked structure can be formed by including a plurality of reactive end groups of a carboxy group and a hydroxy group. Particularly, the at least one hydroxyl group contained in the tricarboxylic acid compound does not participate in the polymerization process, and forms a hydrogen bond after the production of the film or the coating film to increase the self-recovery rate, Tensile strength and tensile strength after self-recovery can be increased.

In the present invention, the tricarboxylic acid-based compound containing at least one hydroxy group in the molecule includes a tricarboxylic acid, an ester thereof and a metal salt thereof containing at least one hydroxyl group in the molecule.

That is, the repeating unit of (a) may include at least one unit structure derived from an acid, ester or metal salt thereof containing at least one hydroxy group together with three carboxyl groups, and more specifically, C4 To C20 aliphatic tricarboxylic acid, an ester thereof or a metal salt-derived repeating unit, and more specifically may contain one or more repeating units derived from a compound of the following formula (1), an ester thereof or an alkali metal salt :

 [Chemical Formula 1]

In this formula,

X ₁ , X ₂ and X ₃ are each independently hydrogen, a hydroxy group, a C1 to C4 alkyl group, or a C1 to C4 hydroxyalkyl group,

a to d each independently represents an integer of 0 to 4,

e ₁ and e ₂ are each independently an integer of 0 to 2,

m and n are each independently an integer of 0 to 2,

Provided that e ₁ and e ₂ are simultaneously 0 or when m and n are simultaneously 0, X ₂ is a hydroxy group or a C1 to C4 hydroxyalkyl group.

In the present invention, the alkyl group is a C1 to C6 or C1 to C4 linear or branched alkyl group, and specific examples thereof include methyl, ethyl, isopropyl, t-butyl and the like, but are not limited thereto.

In the present invention, the hydroxyalkyl group is a functional group in which hydrogen in the alkyl group is substituted with a hydroxy group, and specific examples thereof include hydroxymethyl, hydroxyethyl and the like, but are not limited thereto.

More specifically, as the tricarboxylic acid-based compound, citric acid, isocitric acid, trimethyl citrate, triethyl citrate, tributyl citrate, isocitric acid trisodium salt or citric acid trisodium salt. The repeating unit (a) may include repeating units derived from any one or a mixture of two or more thereof.

The repeating unit (a) may be contained in an amount of more than 10 mol% to 35 mol% or less based on the total moles of the repeating units in the polyester. If the content of the repeating unit (a) is out of the above range and is not more than 10 mol%, or more than 35 mol%, it is difficult to obtain the self-restoring property. Considering the self-restoring property acquisition, tensile strength improving effect and film processability according to the control of the repeating unit content of the polyester (a) in the polyester, the repeating unit of (a) is preferably 10 mol% 35 mol%, and when the content is from 15 mol% to 30 mol%, the effect of improving tensile strength and tensile strength after self-restoration is more remarkable.

In the polyester, the repeating unit (b) includes repeating units derived from at least one compound selected from the group consisting of (b1) an alicyclic diol compound and (b2) an alicyclic dicarboxylic acid compound, Improves the self-restoration property by increasing the flexibility of the polymer chain. In the present invention, the alicyclic dicarboxylic acid-based compound includes an alicyclic dicarboxylic acid, an ester thereof and a metal salt thereof.

In the repeating unit (b), the repeating unit derived from the alicyclic diol compound (b1) specifically includes a repeating unit derived from a C3 to C20 alicyclic hydrocarbon compound containing two functional groups of a hydroxyl group and a hydroxyalkyl group , And the repeating unit derived from the alicyclic dicarboxylic acid compound (b2) is specifically a repeating unit derived from a C3 to C20 alicyclic hydrocarbon compound containing two functional groups of a carboxylic acid group and a carboxylalkyl ester group . ≪ / RTI >

More specifically, the repeating unit of the above (b) may include a repeating unit derived from a compound of the following formula (2)

(2)

Wherein Y ₁ and Y ₂ are each independently -OH, -R _a OH, -COOH or -COOR _b , R _a and R _b are each independently a C 1 to C 6 alkyl group,

p and q are each independently an integer of 0 to 6, and r is an integer of 0 to 4.

More specifically, as the alicyclic diol compound (b1), 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanediol , 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,2-cyclopentanediol, 1,3-cyclopentanedimethanol, or 1,2-cyclopentanedimethanol. The repeating unit of (b) may contain repeating units derived from any one or two or more of these.

Examples of the alicyclic dicarboxylic acid compound (b2) include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dimethylcyclohexane- 1,4-dicarboxylate, dimethylcyclohexane-1,3-dicarboxylate, dimethylcyclohexane-1,2-dicarboxylate, diethylcyclohexane-1,4-dicarboxylate, di 1,3-dicarboxylate, ethylcyclohexane-1,3-dicarboxylate, diethylcyclohexane-1,2-dicarboxylate, 1,3-cyclopentane dicarboxylic acid, 1,3-dicarboxylate, dimethylcyclopentane-1,2-dicarboxylate, diethylcyclopentane-1,3-dicarboxylate, or diethylcyclopentane-1,2-dicarboxylate And the repeating unit (b) may be a repeating unit derived from any one of them or a mixture of two or more thereof It may contain.

The repeating unit (b) may be contained in an amount of 30 to 70 mol% based on the total moles of the repeating units in the polyester. If it is contained in an amount of less than 30 mol% or more than 70 mol% outside the above range, it may be difficult to exhibit sufficient self-restitution property. Particularly, when it is less than 30 mol%, mechanical strength, particularly impact strength, If it exceeds the mol%, the film formability may be deteriorated. The repeating unit (b) may be contained in an amount of from 35 mol% to less than 65 mol% based on the total molar amount of the repeating units in the polyester, considering that the improvement effect according to the content control of the repeating unit (b) More specifically, in a content of 40 to 60 mol%, transparency, film processability and mechanical strength can be further improved.

In the polyester, the repeating unit (c) includes a repeating unit derived from at least one compound selected from the group consisting of (c1) an aliphatic dicarboxylic acid compound and (c2) an aliphatic diol compound, Thereby improving elongation and film processability. In the present invention, the aliphatic dicarboxylic acid-based compound includes an aliphatic dicarboxylic acid, an ester thereof and a metal salt thereof.

In the repeating unit (c), the aliphatic dicarboxylic acid-based compound-derived repeating unit (c1) is derived from a C3 to C20 aliphatic hydrocarbon-based compound containing two functional groups of a carboxylic acid group and a carboxyalkyl ester group And recurring units. More specifically, the aliphatic dicarboxylic acid-based compound may include succinic acid, glutaric acid, malonic acid, oxalic acid, Sebacic acid, adipic acid, fumaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, There may be mentioned brassilic acid, dodecanedioic acid, hexadecanedioic acid, itaconic acid, dimethyl succinate, dimethylacetamide, dimethylacetamide, Dimethyl glutarate, dimethyl malonate, dimethyl oxalate, sebacic acid dimethyl ester, dimethyl adipate, dimethyl fumarate, Pimelic acid dimethyl ester, suberic acid dimethyl ester, azelaic acid dimethyl ester, brassylic acid dimethyl ester, dimethyl (meth) acrylate, Dimethyldodecanedioate, hexadecanedioic acid dimethyl ester or dimethyl itaconate. The repeating unit of (c1) may be any one of them or And may contain two or more mixture-derived repeating units.

In the repeating unit (c), the repeating unit derived from the aliphatic diol compound (c2) specifically includes a repeating unit derived from a C2-C20 aliphatic hydrocarbon-based compound containing two functional groups of a hydroxyl group and a hydroxyalkyl group More specifically, examples of the aliphatic diol compound include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-propanediol, diethylene glycol, spiroglycol, polyethylene glycol, Propylene glycol, propylene glycol, 2-methyl-propanediol, 2,2-dimethyl-1,3-propanediol, Propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-butanediol, 2,3-butanediol, Pentanediol, 1,8-octanediol, 1,10-decanediol or 1,12-dodecanediol, and the repeating unit (c2) The And a repeating unit derived from any one or two or more of the mixture.

The repeating unit (c) may be contained in an amount of 10 to 40 mol% of the total repeating units of the polyester. When the content is out of the above range, it may be difficult to obtain a sufficient self-restoring force. Particularly when the content is less than 10 mol%, the effect of improving the elongation and film workability due to the inclusion of the repeating unit (c) is insignificant, There is a possibility that the mechanical strength is lowered. The recurring unit of (c) is more preferably contained in an amount of 13 to 38 mol%, more specifically 15 to 35 mol%, based on the repeating unit content of the polyester (c) As shown in FIG.

More specifically, when the repeating unit (c) contains (c1) a repeating unit derived from an aliphatic dicarboxylic acid-based compound, the repeating unit may be contained in an amount of 13 to 38 mol% May be contained in a molar ratio of 0.5 to 3.5 based on 1 mol of the repeating unit (a).

When the repeating unit (c) contains repeating units derived from the aliphatic diol compound (c2), the repeating units may be contained in an amount of 17 to 35 mol% in the total repeating units of the polyester. In a molar ratio of 0.5 to 3.5 with respect to 1 mole of the repeating unit (a).

The self-restorable polyester according to an embodiment of the present invention may further comprise a recurring unit derived from a disulfide compound represented by the following formula (3)

(3)

In the above formula, Z ₁ and Z ₂ each independently may be selected from the group consisting of a hydroxyl group, an amino group and a thiol group, and more specifically, a hydroxy group or an amino group, and more specifically, a hydroxy group.

Specific examples of the disulfide compound of Formula 3 include bis (4-hydroxyphenyl) disulfide, bis (4-aminophenyl) disulfide or bis (4-mercaptophenyl) disulfide, Two or more mixtures may be used.

The repeating unit derived from the disulfide compound of Formula 3 improves the self-restoring property of the polyester and improves the tensile strength and the tensile strength after self-recovery of the polyester-containing film. The recurring unit derived from the disulfide compound of formula (3) may be contained in an amount of 1 to 10 mol%, more specifically 5 to 10 mol%, still more preferably 7 to 10 mol%, based on the total moles of repeating units in the polyester. ≪ / RTI >

(A) a tricarboxylic acid-based compound containing at least one hydroxyl group in the molecule in an amount of more than 10 molar% to 35 molar% or less; (b) 30 to 70 mol% of at least one compound selected from the group consisting of (b1) an alicyclic diol compound and (b2) an alicyclic dicarboxylic acid compound; And (c) 10 to 40 mol% of at least one compound selected from the group consisting of (c1) an aliphatic dicarboxylic acid-based compound and (c2) an aliphatic diol-based compound and then subjecting the mixture to a polymerization reaction. (B) and (c) are not dicarboxylic acid compounds at the same time, and when the polyester to be produced further comprises a structural unit derived from a disulfide compound, The above-mentioned disulfide-based compound may be added. According to another embodiment of the present invention, there is provided a method for producing the self-restorative polyester.

In the process for producing the self-restorable polyester, the polymerization reaction for the production of polyester is carried out in the same manner as in the case of the conventional polyester (a), except that the monomer materials of (a), (b) and (c) Can be carried out according to the polymerization method.

More specifically, the polyester may be obtained by mixing the monomer materials of (a), (b) and (c) described above in an amount satisfying the content range condition described above and performing an esterification reaction and / By subjecting the resulting low molecular weight polymer to a polycondensation reaction.

At this time, the kinds of the monomer materials and the amounts of the monomer materials (a), (b) and (c) are as described above for each repeating unit. Specifically, in the above mixing (a), (b) and (c), the mixing ratio of the carboxyl group-containing functional group and the hydroxyl group-containing functional group in the whole mixture (A), (b) and (c) may be mixed such that the molar ratio is 1: 0.95 to 1: 1.05. The carboxyl group-containing functional group includes a carboxyl group, an ester group thereof, and a metal base thereof, and the hydroxy group-containing functional group includes a hydroxy group and a hydroxyalkyl group.

(A), (b) and (c), the molar ratio of the carboxyl group and the hydroxyl group in the entire mixture is 1: 0.98 to 1: 1.02.

The esterification reaction or the ester exchange reaction may be carried out in an inert gas atmosphere such as nitrogen in order to suppress side reactions caused by oxygen. The esterification reaction or the ester exchange reaction may be carried out at a temperature of 120 to 200 DEG C and a pressure of 600 to 900 torr, Lt; 0 > C and a pressure of 700 to 800 torr. And can exhibit excellent esterification reaction efficiency when carried out under the above reaction conditions.

In order to increase the reaction efficiency in the esterification reaction, a stirring process using a conventional method may be performed together.

Then, when water as an adduct starts to emerge as a result of the esterification reaction, the reaction system is depressurized to 0.1 to 250 torr over 1 to 12 hours, and a polycondensation reaction is performed until water is not discharged. The polyester produced by such a polycondensation reaction can exhibit excellent mechanical properties, specifically, tensile strength characteristics and excellent solvent resistance.

The polyester produced according to the above-mentioned production method is a random copolymer in which repeating units derived from a disulfide compound are further randomly distributed together with the repeating units (a), (b) and (c).

The above-mentioned polyester exhibits a highly branched structure by using a tricarboxylic acid-based compound having at least one hydroxyl group as a monomer at the time of its production in a high content. Specifically, the polyester has a property that the content of carboxyl end groups is less than 100 Eq / ton, more specifically 10 to 90 Eq / ton, and the moldability is maintained without flowing at room temperature (25 캜 5 캜) .

In addition, the above-mentioned polyester has a better self-restoring force than a self-restoring polymer using hydrogen bonds in the prior art, and can be self-restored at room temperature (25 ± 5 ° C) without any heat treatment or light irradiation at the time of damage, There is no deterioration in mechanical properties. In addition, the polyester exhibits excellent tensile strength along with high solvent resistance, and exhibits remarkably excellent transparency and whiteness compared to the conventional self-restoring polymer.

In addition, the polyester is harmless, water-soluble, environmentally friendly, and free of aromatic groups, and is low in glass transition temperature, specifically 20 ° C or less, more specifically -20 ° C to 20 ° C Glass transition temperature.

In addition, although the polyester is a crosslinked polymer, it can be molded by heat, in particular injection molding by melting.

Accordingly, the polyester can be usefully used as a coating film, a sheet or the like in various fields requiring wear resistance, transparency and solvent resistance, such as scratch resistance, anti-chip, anti-stone, etc. for automobile, military use and IT. Accordingly, according to another embodiment of the present invention, there is provided a molded article manufactured using the above polyester, specifically, an injection-molded article, more specifically a film.

By including the polyester described above, the film can exhibit excellent transparency, solvent resistance, tensile strength characteristics, and self-restoring force.

Specifically, regarding the transparency, the film exhibits a transmittance of 88% or more, more specifically 90% or more when measured at a wavelength of 500 nm using a UV-Vis spectrophotometer.

The film had a tensile strength of 3 MPa or more, more specifically 3 to 20 MPa as measured by ASTM D638-Type V; An elongation of 50 to 500%, more specifically 80 to 400%; And a tensile modulus of 50 to 1200 MPa, more specifically 70 to 1000 MPa.

The film was exposed to a scratch of 10 to 50 占 퐉 in width for 2 hours at room temperature (25 占 占 폚), and the recovered width was observed with an optical microscope. When the restorative force is made a percentage, the restorative force is 85% or more, more specifically 90% or more. Further, when measuring the tensile strength in accordance with ASTM D638-Type V after recovery of the film, it shows an excellent recovery tensile strength of not less than 80%, more specifically not less than 85%, relative to the tensile strength before cutting.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided to further understand the present invention, and the present invention is not limited by the following examples.

Example 1-1: Preparation of polyester

9.10 g (47.36 mmol) of citric acid (CA), 19.58 g (165.76 mmol) of succinic acid (SA) and 34.15 g (236.8 mmol) of 1,4-cyclohexanedimethanol (CHDM) were placed in a 100 ml two-necked flask equipped with a reflux condenser And then purged with nitrogen. The RPM was fixed at 50 by mechanical stirring, and the temperature in the flask was slowly raised to 160 DEG C to dissolve the mixture. The RPM was then raised to 150 and, when the water of the addition product started to emerge at 760 torr, the pressure was gradually reduced to 200 torr over 3 hours. After confirming that the water no longer appeared, the reaction was terminated to obtain a polyester.

Examples 1-2 to 1-10: Preparation of polyester

A polyester was produced in the same manner as in Example 1-1, except that the materials listed in Table 1 were used as base materials.

Comparative Example 1-1: Production of polyester

9.59 g (47.36 mmol) of citric acid (CA), 27.50 g (232.85 mmol) of succinic acid (SA) and 45.53 g (315.7 mmol) of 1,4-cyclohexane dimethanol (CHDM) were placed in a 100 ml two-necked flask equipped with a reflux condenser And then purged with nitrogen. The RPM was fixed at 50 by mechanical stirring, and the temperature in the flask was slowly raised to 160 DEG C to dissolve the mixture. The RPM was then raised to 150 and, when the water of the addition product started to emerge at 760 torr, the pressure was gradually reduced to 200 torr over 3 hours. After confirming that the water no longer appeared, the reaction was terminated to obtain a polyester.

Comparative Examples 1-2 to 1-12: Production of polyester

A polyester was produced in the same manner as in Example 1-1, except that the materials listed in Table 1 were used as base materials.

Monomer content (mol%) Feed molar ratio
(CA / CHDA / CHDM / SA / BD / SS) a b c d CA CHDA CHDM SA BD SS Example 1-1 10.5 0.0 52.6 36.8 0.0 0.0 0.4 / 0/2 / 1.4 / 0/0 Examples 1-2 18.2 0.0 54.5 27.3 0.0 0.0 0.67 / 0/2/1/0/0 Example 1-3 22.2 0.0 55.6 22.2 0.0 0.0 0.8 / 0/2 / 0.8 / 0/0 Examples 1-4 28.6 0.0 57.1 14.3 0.0 0.0 1/0/2 / 0.5 / 0/0 Examples 1-5 16.9 28.9 36.1 0.0 18.1 0.0 0.23 / 0.4 / 0.5 / 0 / 0.25 / 0 Examples 1-6 27.8 15.2 38.0 0.0 19.0 0.0 0.37 / 0.2 / 0.5 / 0 / 0.25 / 0 Examples 1-7 27.8 15.2 22.8 0.0 34.2 0.0 0.37 / 0.2 / 0.3 / 0 / 0.45 / 0 Examples 1-8 22.2 0.0 46.7 22.2 0.0 8.9 0.5 / 0 / 1.05 / 0.5 / 0 / 0.2 Examples 1-9 18.2 13 41.5 14.25 13.05 0 0.182 / 0.13 / 0.415 / 0.1425 / 0.1305 / 0 Example 1-10 25 18.75 21.25 0 26.0 9.0 0.25 / 0.1875 / 0.2125 / 0 / 0.26 / 0.09 Comparative Example 1-1 9.2 0.0 52.3 38.6 0.0 0.0 0.35 / 0/2 / 1.475 / 0/0 Comparative Example 1-2 7.8 0.0 51.9 40.3 0.0 0.0 0.3 / 0/2 / 1.55 / 0/0 Comparative Example 1-3 35.3 0.0 58.8 5.9 0.0 0.0 1.2 / 0/2 / 0.2 / 0/0 Comparative Example 1-4 40.0 0.0 40.0 0.0 20.0 0.0 0.5 / 0 / 0.5 / 0 / 0.25 / 0 Comparative Example 1-5 34.0 7.5 20.5 0 38 0.0 0.34 / 0.075 / 0.205 / 0 / 0.38 / 0 Comparative Example 1-6 27.8 15.2 7.6 0.0 49.4 0.0 0.37 / 0.2 / 0.1 / 0 / 0.65 / 0 Comparative Example 1-7 12.0 35 37 0 16 0.0 0.12 / 0.35 / 0.37 / 0 / 0.16 / 0 Comparative Example 1-8 18.0 27.5 12.5 0.0 42 0.0 0.18 / 0.275 / 0.125 / 0 / 0.42 / 0 Comparative Example 1-9 40.0 0.0 60.0 0.0 0.0 0.0 0.5 / 0 / 0.75 / 0/0/0 Comparative Example 1-10 18.2 0.0 0.0 27.3 54.5 0.0 0.67 / 0/0/1/2/0 Comparative Example 1-11 18.2
(PA) 0.0 54.5 27.3 0.0 0.0 0.67 (PA) /0/2/1.0/0/0 Comparative Example 1-12 27.8 15.2 38.0 0.0 19.0
(BDM) 0.0 0.37 / 0.2 / 0.5 / 0 / 0.25 (BDM) / 0 CA: citric acid
SA: succinic acid
CHDA: 1,4-cyclohexanedicarboxylic acid
CHDM: 1,4-cyclohexanedimethanol
BD: 1,4-butanediol
SS: Bis (4-hydroxyphenyl) disulfide
PA: 1,2,3-propanetricarboxylic acid
BDM: 1,4-Benzenedimethanol

Experimental Example  One: Of polyester  Property evaluation

The physical properties of the polyesters prepared in Examples 1-1 to 1-10 were measured by the following methods, and the results are shown in Table 2.

1) Glass transition temperature (Tg, 占 폚): Measured by DSCQ20 of TA Corporation. Specifically, 6 mg of the sample was scanned at a rate of 10 캜 / min from -10 캜 to 160 캜. At this time, since the degree of curing can be changed by heat, the glass transition temperature in the first heating scan was measured.

2) Carboxyl terminal group: Mettler Toledo G20 titration apparatus was used, and the polyester was dissolved using Chloroform: Phenol = 3: 2 (v / v), 0.02M KOH (in EtOH) And Bromo phenol Blue was used as an indicator.

[COOH] terminal capacity
(Eq / ton) Tg
(° C) Example 1-1 72.5 6 Examples 1-2 85.5 8 Example 1-3 72.5 12 Examples 1-4 62.8 14 Examples 1-5 58.5 -6 Examples 1-6 72.9 -2 Examples 1-7 48.2 -12 Examples 1-8 35.5 18 Examples 1-9 82.3 8 Example 1-10 34.0 20 Comparative Example 1-1 68.9 0 Comparative Example 1-2 75.8 -2 Comparative Example 1-3 82.5 18 Comparative Example 1-4 77.2 17 Comparative Example 1-5 48.9 -15 Comparative Example 1-6 45.2 -22 Comparative Example 1-7 53.5 22 Comparative Example 1-8 58.8 -10 Comparative Example 1-9 52.5 20 Comparative Example 1-10 42.5 -18 Comparative Example 1-11 82.5 8 Comparative Example 1-12 55.8 25

Experimental Example  2: Of polyester Self-resilience  evaluation

After the polyester produced in Example 1-1 was cut with a knife, the polyester was exposed at room temperature (25 ± 5 ° C) for 48 hours to observe recombination. The results are shown in Fig.

As shown in FIG. 1, it can be confirmed that the cut polyester completely recombined without a separate heat treatment or light irradiation.

Experimental Example  3: polyester  analysis

Fourier-transform infrared spectroscopy (FT-IR) was performed on the polyesters prepared in Examples 1-1 to 1-3, and the results are shown in FIG.

Specifically, the FT-IR analysis using a Nicolet iS10 spectrometer was measured as the sensitivity of 4cm ^-1 to 650 cm ^-1 to 4000 cm ^-1, wherein, using the attenuated total reflectance (ATR) techniques for the measurement of polyester Respectively.

As a result of the analysis, stretching by the hydroxyl group (OH) of the citric acid was observed at 3488 cm ^-1 . Further, at 2922 cm ^-1 and 2854 cm ^-1 Sp ³ CH stretch, 1728 C = O stretch of the ester in cm ^-1, and 1161 cm ^- was observed, respectively the CO stretch of the ester in ^1).

Experimental Example 4: Moldability evaluation of polyester

The polyester produced in Example 1-1 was subjected to heat treatment after compression to evaluate the thermoformability and recyclability, and the results are shown in FIG.

Specifically, the polyester prepared in Example 1-1 was finely cut and then hot-pressed in a hot-press apparatus at a temperature of 160 ° C for 3 hours under a pressure of 3000 psi.

As shown in FIG. 3, the polyester produced in Example 1-1 exhibited thermoplasticity capable of thermoforming in spite of being a crosslinked polymer, and it was also confirmed that it was also possible to recycle after molding have.

Example 2-1: Production of film

The polyester polymerized in Example 1-1 was finely cut and then charged into a polytetrafluoroethylene (PTFE) mold (100 mm * 70 mm * 2.5 mm). The mold was placed in a hot-press apparatus and pressed at 3000 psi under the hot-press conditions shown in Table 3 to produce a film.

Examples 2-2 to 2-10 and Comparative Examples 2-1 to 2-12: Film production

Except that the polyesters prepared in Examples 1-2 to 1-10 and Comparative Examples 1-1 to 1-12 were used in place of the polyesters prepared in Example 1-1 and Hot The film was produced in the same manner as in Example 1-1 except that the film was pressed under the -press condition.

Polyester type Hot-press condition Example 2-1 Example 1-1 160 ° C / 3 hours Example 2-2 Examples 1-2 160 ° C / 3 hours Example 2-3 Example 1-3 160 ° C / 3 hours Examples 2-4 Examples 1-4 160 ° C / 3 hours Example 2-5 Examples 1-5 160 ° C / 3 hours Examples 2-6 Examples 1-6 160 ° C / 3 hours Examples 2-7 Examples 1-7 160 ° C / 3 hours Examples 2-8 Examples 1-8 160 ° C / 3 hours Examples 2-9 Examples 1-9 160 ° C / 3 hours Examples 2-10 Example 1-10 160 ° C / 3 hours Comparative Example 2-1 Comparative Example 1-1 160 ° C / 3 hours Comparative Example 2-2 Comparative Example 1-2 160 ° C / 3 hours Comparative Example 2-3 Comparative Example 1-3 200 ° C / 3 hours Comparative Example 2-4 Comparative Example 1-4 200 ° C / 3 hours Comparative Example 2-5 Comparative Example 1-5 160 ° C / 3 hours Comparative Example 2-6 Comparative Example 1-6 160 ° C / 3 hours Comparative Example 2-7 Comparative Example 1-7 160 ° C / 3 hours Comparative Example 2-8 Comparative Example 1-8 160 ° C / 3 hours Comparative Example 2-9 Comparative Example 1-9 200 ° C / 3 hours Comparative Example 2-10 Comparative Example 1-10 160 ° C / 3 hours Comparative Example 2-11 Comparative Example 1-11 160 ° C / 3 hours Comparative Examples 2-12 Comparative Example 1-12 160 ° C / 3 hours

Experimental Example  5: polyester  Evaluation of physical properties of film

The physical properties of the polyesters prepared in Examples 2-1 to 2-10 and Comparative Examples 2-1 to 2-12 were measured by the following methods, and the results are shown in Tables 4 and 5 and FIG. 4 .

1) Carboxyl terminal group: Mettler Torredo G20 titration apparatus was used and the polyester was dissolved using Chloroform: Phenol = 3: 2 (v / v), 0.02 M KOH (in EtOH) And Bromo phenol blue was used as an indicator.

2) Glass transition temperature (Tg, 占 폚): Measured by DSCQ20 from TA Corporation. Specifically, 6 mg of the sample was scanned at a rate of 10 캜 / min from -10 캜 to 160 캜. At this time, since the degree of curing can be changed by heat, the glass transition temperature in the first heating scan was measured.

3) Permeability (%): The transmittance of the film was measured at a wavelength of 500 nm using a UV-Vis spectrophotometer.

4) Solvent resistance: The film was rubbed with a cloth moistened with isopropyl alcohol (IPA) and observed.

◎: When there is almost no part coming out

B: When a portion with a high haze is generated

X: When the shape of the film is lost

5) Tensile strength (MPa), elongation (%), tensile modulus (MPa): Measured with ASTM D638-Type V with Intstron 5966 instrument. A load cell of 10 KN was measured at a crosshead speed of 50 mm / min at 18 ° C and an average value of 5 measurements in the form of a dog of 26.34 mm * 3.18 mm * 2.50 mm was taken.

6) Self-restoring force (%): The film was subjected to scratch damage of 10 to 50 탆 in width, exposed for 2 hours at room temperature (25 짹 5 캜), and the recovered width was observed with an optical microscope. As a reference.

7) Tensile Strength (Mpa) and Tensile Strength Recovery Rate (%) after Cut Recovery: The specimen prepared by the method of 5) was cut in half using a cutter knife and then joined again. After 24 hours at room temperature, The tensile strength was measured in the same manner and the tensile strength recovery rate was calculated from the ratio of the tensile strength after cutting to the strength of the tensile strength before cutting.

[COOH] terminal capacity
(Eq / ton) Tg
(° C) Permeability
(%) Solvent resistance
(IPA) The tensile strength
(MPa) Elongation
(%) Tensile modulus
(MPa) Self-resilience
(%) Tensile strength after cutting recovery (MPa) Tensile strength recovery rate
(%) Example 2-1 69.1 8 94 ◎ 3.1 385 70 99.5 2.9 94 Example 2-2 66.8 10 95 ◎ 3.5 349 90 99.5 3.3 94 Example 2-3 68.2 14 94 ◎ 9.3 315 181 92.5 8.4 90 Examples 2-4 60.1 16 96 ◎ 17.3 69.9 961 90.6 15.2 88 Example 2-5 53.2 -4 92 ◎ 3.6 352 250 93.2 3.3 92 Examples 2-6 65.5 0 94 ◎ 12.5 302 152 91.2 10.8 86 Examples 2-7 46.8 -10 93 ◎ 10.8 368 80 94.5 9.8 91 Examples 2-8 32.8 20 92 ◎ 18.5 95.3 498 98.5 17.2 93 Examples 2-9 76.3 10 95 ◎ 3.6 375 90 99.0 3.4 94 Examples 2-10 33.5 22 93 ◎ 12.5 110 680 91.5 11.0 88

[COOH] terminal capacity
(Eq / ton) Tg
(° C) Permeability
(%) Solvent resistance
(IPA) The tensile strength
(MPa) Elongation
(%) Tensile modulus
(MPa) Self-resilience
(%) Tensile strength after cutting recovery (MPa) Tensile strength recovery rate
(%) Comparative Example 2-1 65.3 2 95 X 1.6 52.5 14.5 - (clamping force X) - (clamping force X) - Comparative Example 2-2 72.4 0 95 X 1.5 48.5 15.5 - (clamping force X) -
(Mold clamping force X) - Comparative Example 2-3 80.9 19 88 △ 1.8 25.1 150 15.2 -
(Rejoining X) - Comparative Example 2-4 76.1 19 87 △ 1.7 20.2 140 14.8 -
(Rejoining X) - Comparative Example 2-5 46.7 -13 93 △ 3.8 15.2 120 35.8 -
(Rejoining X) - Comparative Example 2-6 42.9 -20 95 X 1.4 45.8 12.6 -
(Mold clamping force X) -
(Mold clamping force X) - Comparative Example 2-7 50.9 24 92 △ 6.8 550 85.6 25.2 -
(Rejoining X) - Comparative Example 2-8 56.5 -8 92 X 2.5 780 19.5 -
(Mold clamping force X) -
(Mold clamping force X) - Comparative Example 2-9 49.6 22 93 X 2.5 21.2 350 26.2 1.9 15 Comparative Example 2-10 41.5 -16 93 X 1.2 40.6 12.5 -
(Mold clamping force X) -
(Mold clamping force X) - Comparative Example 2-11 77.6 10 95 △ 0.89 1080 21.3 10.5 0.19 21 Comparative Examples 2-12 55.1 25 85 △ 2.8 35.8 150 21.5 0.43 15

4 is an optical microscope photograph of the polyester film prepared in Example 2-1, wherein self-restoration was observed at room temperature (26.9 ° C) after the scratching.

As shown in Table 4 and FIG. 4, the polyester films of Examples 2-1 to 2-10 showed excellent self-restoring force and tensile strength recovery as well as good solvent resistance and high transmittance. Specifically, the polyester films of Examples 2-1 to 2-10 had a tensile strength of 3 MPa or more due to the hydrogen bonding of a hydroxy group in the repeating unit derived from the citric acid in the polyester, and the polyester film had a scratch- Within 2 hours, self - restoration rate of 85% or more was achieved and the tensile strength after cutting recovery was more than 85% of the tensile strength before cutting.

On the other hand, as shown in Table 5, in Comparative Example 2-1 in which the content of the hydroxyl group-containing tricarboxylic acid compound (a) in the production of polyester was less than 10 mol%, and the aliphatic diol or aliphatic dicarboxylic acid (c) The polyester film of Comparative Example 2-2, which was used in an excessively high content of the complex-based compound, exhibited greatly deteriorated solvent resistance, and the film formed at room temperature melted in a few hours after the film formation was weak. It was impossible to proceed. Such lowering of solvent resistance and lowering of self-restorability were also observed in the films of Comparative Examples 2-6, 2-8, and 2-10 in which the compound (c) was used in excess in the production of polyester.

In addition, in the case of the polyester film of Comparative Example 2-3 in which the compound of (a) was used in excess and the content of the compound of (c) was less than 10 mol%, the self-restoring force was low, , The transmittance was greatly decreased. The polyester film of Comparative Example 2-4, in which the compounds of (b) and (c) were used in the optimum amount range but the compound of (a) was used in a larger amount than that of Comparative Example 2-3, And showed lower mechanical properties and self-restoring force than Comparative Example 2-3, and did not recover the rejoining after cutting. In addition, the film of Comparative Example 2-4 exhibited greatly reduced transmittance as in Comparative Example 2-3.

In the case of the polyester film of Comparative Example 2-9 in which the compounds (a) and (b) are used in an optimum amount in the production of the polyester but the compound (c) is not used, As compared with the films of Examples 2-1 to 2-10 showing the bonding, the self-restoring force and the recovery rate of tensile strength after cutting were greatly lowered, and the elongation was greatly reduced.

In the case of the polyester film of Comparative Example 2-5 in which the compounds (a) and (c) were used in an optimum amount in the production of polyester but the compound of (b) was used in an amount of less than 30 mol% And the polyester film of Comparative Example 2-7 in which the compound of (b) was used in an amount exceeding 70 mol% exhibited a low self-restoring force, and remanent bonding did not occur after the cutting. Suggesting that there is a minimum and maximum content of alicyclic repeat units that express self-restoring forces.

In addition, the polyester film of Comparative Example 2-11 had an effect of hydrogen bonding due to the use of 1,2,3-propanetricarboxylic acid (PA) having no hydroxy group in the citric acid in the production of polyester The tensile strength was also low, the self-restoring force was not excellent, and the tensile strength after cutting recovery was also very low.

In addition, the film of Comparative Example 2-12 including a polyester prepared by using an aromatic diol in place of an aliphatic dicarboxylic acid or a diol also exhibited low self-restoring force and tensile strength after cutting recovery.

Further, the whiteness of the polyester films of Examples 2-1 to 2-10 was observed.

The whiteness index was measured using a spectrophotometer (Spectrophotometer SE2000, JAPAN, Denshoku) according to ASTM D 1925. Halogen lamps were used as the light source of the spectrophotometer, and the standard deviation of DELTA E * Was less than 0.05.

As a result, the colorimetric b * exponents of the polyester foils of Examples 2-1 to 2-10 all showed a whiteness of 5 or less.

Claims (10)

(a) from more than 10 mol% to 35 mol% or less of recurring units derived from a tricarboxylic acid compound containing at least one hydroxyl group in the molecule;
(b) 30 to 70 mol% of recurring units derived from at least one compound selected from the group consisting of (b1) an alicyclic diol compound and (b2) an alicyclic dicarboxylic acid compound; And
(c) 10 to 40 mol% of recurring units derived from at least one compound of (c1) an aliphatic dicarboxylic acid-based compound and (c2) an aliphatic diol-based compound,
(B) and (c) are not the repeating units derived from the dicarboxylic acid compound at the same time,
The repeating unit derived from a tricarboxylic acid compound containing at least one hydroxy group in the molecule of the above (a) may be obtained by reacting a repeating unit derived from at least one compound selected from the group consisting of a compound represented by the following formula (1), an ester thereof and a metal salt thereof Self-restituting polyesters, including:
[Chemical Formula 1]

In this formula,
X ₁ , X ₂ and X ₃ are each independently hydrogen, a hydroxy group, a C1 to C4 alkyl group, or a C1 to C4 hydroxyalkyl group,
a to d each independently represents an integer of 0 to 4,
e ₁ and e ₂ are each independently an integer of 0 to 2,
m and n are each independently an integer of 0 to 2,
If the end e ₁ and e _2, or at the same time, 0, or m and n are 0 at the same time, X ₂ is a hydroxy alkyl group of the hydroxy group, or a C1 to C4.
delete The method according to claim 1,
The repeating unit of (b) comprises a repeating unit derived from a compound of the following formula (2)
(2)

In this formula,
Y ₁ and Y ₂ are each independently -OH, -R _a OH, -COOH or -COOR _b , R _a and R _b are each independently a C 1 to C 6 alkyl group,
p and q are each independently an integer of 0 to 6,
r is an integer of 0 to 4;
The method according to claim 1,
The aliphatic dicarboxylic acid-based compound (c1) is a C3 to C20 aliphatic hydrocarbon-based compound containing two functional groups of a carboxylic acid group and a carboxyalkyl ester group.
The method according to claim 1,
The aliphatic diol compound (c2) is a C2-C20 aliphatic hydrocarbon-based compound containing two functional groups of a hydroxyl group and a hydroxyalkyl group.
The method according to claim 1,
Self-restoring polyester further comprising a recurring unit derived from a disulfide compound represented by the following formula (3):
(3)

In the above formula, Z ₁ and Z ₂ are each independently selected from the group consisting of a hydroxyl group, an amino group, and a thiol group.
The method according to claim 1,
A self-restoring polyester having a carboxyl end group content of less than 100 Eq / ton.
(a) from 10 mol% to 35 mol% of a tricarboxylic acid-based compound containing at least one hydroxyl group in the molecule; (b) 30 to 70 mol% of at least one compound selected from the group consisting of (b1) an alicyclic diol compound and (b2) an alicyclic dicarboxylic acid compound; And (c) 10 to 40 mol% of at least one compound selected from the group consisting of (c1) aliphatic dicarboxylic acid compounds and (c2) aliphatic diol compounds,
The method of producing a self-restoring polyester according to claim 1, wherein (b) and (c) are not simultaneously a dicarboxylic acid compound.
9. The method of claim 8,
The molar ratio of the carboxyl group-containing functional group and the hydroxyl group-containing functional group in the whole mixture is preferably from 1: 0.95 to 1 (1), more preferably from 1: : 1.05. ≪ / RTI >
A film produced using the self-restoring polyester according to claim 1.

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