KR102438607B1 - Biodegradable polyester composite using solid dispersion of anhydrosugar alcohol and method for preparing the same, and molded article comprising the same - Google Patents

Abstract

The present invention relates to a biodegradable polyester composite, a method for producing the same, and a molded article comprising the same, and more specifically, to a matrix resin, which is a polyester resin in which anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol are copolymerized, and the A polyester composite comprising a nanomaterial dispersed in a matrix resin, a solid dispersion and anhydrosugar alcohol-alkylene obtained by introducing the nanomaterial (disperse) in an aqueous dispersion state into anhydrosugar alcohol (dispersion medium) during its manufacture By using glycol as a diol component, it exhibits significantly improved mechanical properties (eg, tensile strength, tensile modulus, and elongation, etc.) compared to the existing biodegradable polyester resin composite, and the nanomaterial is uniformly dispersed in the composite, resulting in a uniform It relates to a biodegradable polyester composite having physical properties, a method for manufacturing the same, and a molded article including the same.

Description

Biodegradable polyester composite using solid dispersion of anhydrosugar alcohol, manufacturing method thereof, and molded article comprising the same

The present invention relates to a biodegradable polyester composite, a method for producing the same, and a molded article comprising the same, and more specifically, to a matrix resin, which is a polyester resin in which anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol are copolymerized, and the A polyester composite comprising a nanomaterial dispersed in a matrix resin, a solid dispersion and anhydrosugar alcohol-alkylene obtained by introducing the nanomaterial (disperse) in an aqueous dispersion state into anhydrosugar alcohol (dispersion medium) during its manufacture By using glycol as a diol component, it exhibits significantly improved mechanical properties (eg, tensile strength, tensile modulus, and elongation, etc.) compared to the existing biodegradable polyester resin composite, and the nanomaterial is uniformly dispersed in the composite It relates to a biodegradable polyester composite having uniform physical properties, a method for manufacturing the same, and a molded article including the same.

Nanomaterials such as nanocellulose can be manufactured from biomass through various methods, and recently, many studies have been conducted to improve mechanical properties by adding it to polyurethane. However, due to the hydrophilicity of nanocellulose, most of the products are manufactured using water as a dispersion medium in an amount of about 1% by weight, so there is a limit to its application when manufacturing a composite material with a polymer resin.

In addition, when nano-cellulose is directly used in the form of solid crystals or powder without dispersing it in water, aggregation occurs between the nano-celluloses, and the physical properties of the polymer resin composite material produced therefrom are reduced. It has the disadvantage of becoming non-uniform.

Therefore, as a resin composite including a matrix resin and a nanomaterial dispersed therein, the nanomaterial is uniformly dispersed in the matrix resin while containing the nanomaterial in a higher content than in the prior art, so that physical properties (especially in comparison to the existing resin composite) , tensile strength) is requested to develop a resin composite with significantly improved.

An object of the present invention is to exhibit significantly improved mechanical properties (for example, tensile strength, tensile modulus and elongation, etc.) compared to conventional biodegradable polyester resin composites, and uniform physical properties because nanomaterials are uniformly dispersed in the composite It is to provide a biodegradable polyester composite having a method for producing the same, and a molded article comprising the same.

In order to solve the above technical problem, the present invention includes a matrix resin and a nanomaterial dispersed in the matrix resin, wherein the matrix resin is a solid dispersion of anhydrosugar alcohol in which the nanomaterial is dispersed and Anhydrosugar alcohol-a polyester resin that is a polymerization reaction product of a diol component and a dicarboxyl component containing an alkylene glycol, and the solid dispersion of the anhydrosugar alcohol is introduced into anhydrosugar alcohol in an aqueous dispersion state by introducing the nanomaterial It provides the obtained, biodegradable polyester composite.

According to another aspect of the present invention, the nanomaterial comprises a step of polymerizing a diol component and a dicarboxyl component comprising a solid dispersion of anhydrosugar alcohol dispersed therein and anhydrosugar alcohol-alkylene glycol, Here, the solid dispersion of the anhydrosugar alcohol is obtained by introducing the nanomaterial into the anhydrosugar alcohol in an aqueous dispersion state, a method for producing a biodegradable polyester composite is provided.

According to another aspect of the present invention, there is provided a molded article comprising the biodegradable polyester composite of the present invention.

The biodegradable polyester composite according to the present invention, compared to the existing biodegradable polyester resin composite, in particular, directly in the form of a solid crystal or powder without dispersing nano materials (eg, nano cellulose, etc.) in water, etc. Compared to the resin composite used, it exhibits significantly improved mechanical properties (eg, tensile strength, tensile modulus and elongation, etc.), and has uniform physical properties because the nanomaterial is uniformly dispersed in the composite.

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

The biodegradable polyester composite of the present invention includes a matrix resin and a nanomaterial dispersed in the matrix resin.

In the present invention, the "nano material" refers to an organic or inorganic material having a size (length or particle diameter) of sub-microns, that is, less than 1 micrometer (eg, 10-900 nm, or 10-500 nm). do.

As such a nanomaterial, a material satisfying the meaning of the above-mentioned nanomaterial, for example, nanocellulose, carbon nanofiber, carbon nanotube, iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium , zirconium, titanium, copper, silver, gold, platinum, kaolin, clay, talc, mica, silica, bentonite, dolomite, calcium silicate, magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, Aluminum sulfate, aluminum hydroxide, iron hydroxide, aluminum silicate, zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, silicon carbide, silicon nitride, boron nitride, barium titanate, diatomaceous earth , carbon black, rock wool, graphene, graphite, graphene oxide, azo compound, diazo compound, condensed azo compound, thioindigo compound, indanthrone compound, quinacrindone compound, anthraquinone compound, benzimi Dazolone-based compound, perylene-based compound, phthalocyanine-based compound, anthrapyridine-based compound, dioxazine-based compound, polyethylene resin, polypropylene resin, polyester resin, nylon resin, polyamide resin, aramid resin, urethane resin, polystyrene resin, poly One selected from lactic acid, cellulose acetate fiber, hemicellulose, lignin, chitin, chitosan, starch, or mixtures thereof may be used.

In one embodiment, the nanomaterial may be selected from nanocellulose, carbon nanofibers, carbon nanotubes, or a mixture thereof, but is not limited thereto.

In one embodiment, the nano-cellulose may be selected from nano-cellulose fibers, nano-cellulose crystals, or mixtures thereof.

In one embodiment, the carbon nanotubes may be selected from single-walled carbon nanotubes, multi-walled carbon nanotubes, or mixtures thereof.

In one embodiment, the content of the nanomaterial in the biodegradable polyester composite of the present invention, based on the total weight of the composite, 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.4% by weight or more, or 0.45 % or more, and also 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2.5 wt% or less, or 2 wt% or less or less, for example, may be 0.1 wt% to 10 wt%, more specifically 0.1 wt% to 5 wt%, and even more specifically 0.1 wt% to 3 wt%. If the content of the nanomaterial in the composite is lower than the above level, the improvement effect of mechanical strength such as tensile strength of the composite may be insignificant. , it may be difficult to obtain a polymer composite having uniform physical properties.

The matrix resin included in the biodegradable polyester composite of the present invention is a solid dispersion of anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol in which the nanomaterial is dispersed in a diol component and a dicarboxyl component It is a polyester resin which is a polymerization reaction product, and the solid dispersion of the anhydrosugar alcohol is obtained by introducing the nanomaterial in an aqueous dispersion state into anhydrosugar alcohol.

Anhydrosugar alcohol can be prepared by dehydrating a hydrogenated sugar derived from a natural product. Hydrogenated sugar (also referred to as “sugar alcohol”) refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5) ), and is classified into tetritol, pentitol, hexitol, and heptitol (with 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly effective substances.

In the present invention, the anhydrosugar alcohol may be mono-anhydrosugar alcohol, dianhydrosugar alcohol, or a mixture thereof, which is anhydrosugar by dehydrating hydrogenated sugar (eg, hexitol such as sorbitol, mannitol, iditol). It can be obtained in the process of preparing alcohol.

The monoanhydrosugar alcohol is an anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form having four hydroxyl groups in the molecule. The type of mono-anhydrosugar alcohol that can be used in the present invention is not particularly limited, but may preferably be mono-anhydrosugar hexitol, and more specifically, 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

The dianhydrosugar alcohol is an anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar, has a diol form with two hydroxyl groups in the molecule, and can be prepared using hexitol derived from starch. . Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, research on its manufacturing method has been conducted with a lot of interest from a long time ago. Among these dianhydrosugar alcohols, isosorbide prepared from sorbitol has the widest industrial application range at present. The type of dianhydrosugar alcohol that can be used in the present invention is not particularly limited, but may preferably be dianhydrosugar hexitol, and more specifically 1,4-3,6-dianhydrohexitol. The 1,4-3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof, more preferably isosorbide.

In one embodiment, the solid dispersion of the anhydrosugar alcohol is added to the anhydrosugar alcohol in an aqueous dispersion state of the nanomaterial (eg, a state in which the nanomaterial is dispersed in water at a concentration of 0.1 to 5% by weight) and uniformly It is a room temperature solid dispersion obtained by mixing and melting while removing moisture by applying a vacuum at a temperature higher than the melting point of anhydrosugar alcohol (for example, a temperature of 80° C. or higher), and then cooling the molten mixture to room temperature.

In one embodiment, the content of the nanomaterial introduced into the solid dispersion of the anhydrosugar alcohol is, based on the total weight of the solid dispersion, 0.2 wt% or more, 0.3 wt% or more, 0.4 wt% or more, 0.5 wt% % or more, 0.6 wt% or more, 0.7 wt% or more, 0.8 wt% or more, 0.9 wt% or more, or 1 wt% or more, and also 15 wt% or less, 14 wt% or less, 13 wt% or less, 12 wt% or less , may be 11 wt% or less or 10 wt% or less, for example, 0.2 wt% to 15 wt%, more specifically 0.5 wt% to 12 wt%, even more specifically 1 wt% % to 10% by weight.

The anhydrosugar alcohol-alkylene glycol is an adduct obtained by reacting an alkylene oxide with hydroxyl groups at both ends or one terminal (preferably both ends) of the anhydrosugar alcohol as described above.

In one embodiment, the alkylene oxide may be a linear or branched alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically, ethylene oxide, propylene oxide, or a combination thereof.

In one embodiment, the anhydrosugar alcohol-alkylene glycol may be a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R ¹ and R ² each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms, and m and n each independently represent an integer of 0 to 15, provided that m+n represents the integer of 1-30.

More specifically, in Formula 1, R ¹ and R ² each independently represent an ethylene group, a propylene group, or an isopropylene group, and more specifically, R ¹ and R ² are the same as each other, and m and n are Each independently represents an integer of 1 to 14, provided that m+n represents an integer of 2 to 15.

In one embodiment, as the anhydrosugar alcohol-alkylene glycol, the following isosorbide-propylene glycol, isosorbide-ethylene glycol, or a mixture thereof may be used.

[Isosorbide-Propylene Glycol]

In the above formula, a and b each independently represent an integer of 0 to 15, with the proviso that a+b is an integer of 1 to 30, and more specifically, a and b are each independently an integer of 1 to 14. with the proviso that a+b may be an integer from 2 to 15.

[Isosorbide-ethylene glycol]

In the above formula, c and d each independently represent an integer of 0 to 15, with the proviso that c+d may be an integer of 1 to 30, and more specifically, c and d are each independently an integer of 1 to 14 with the proviso that c + d may be an integer of 2 to 15.

The matrix resin included in the polyester composite of the present invention is a biodegradable polyester resin that is a polymerization reaction product of a diol component and a dicarboxyl component including a solid dispersion of such anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol. .

In one embodiment, the dicarboxyl component may be selected from an aliphatic dicarboxyl compound, an aromatic dicarboxyl compound, or a combination thereof.

In one embodiment, the aliphatic dicarboxyl compound may be selected from aliphatic dicarboxylic acids having 4 to 14 carbon atoms or esters thereof.

More specifically, the aliphatic dicarboxyl compound is adipic acid or its ester, cyclohexanedicarboxylic acid or its ester, sebacic acid or its ester, isodecylsuccinic acid or its ester, maleic acid or its ester, fumaric acid or its ester ester, succinic acid or its ester, glutaric acid or its ester, azelaic acid or its ester, itaconic acid or its ester, glutamic acid or its ester, 2,5-furandicarboxylic acid or its ester, tetrahydrofuran-2, 5-dicarboxylic acid or its ester, tetrahydrofuran-3,5-dicarboxylic acid or its ester, undecanedioic acid or its ester, dodecanedioic acid or its ester, tridecanedioic acid or its ester, tetradecanedioic acid Or it may be selected from the group consisting of esters thereof, and combinations thereof. The ester compound of the aliphatic dicarboxylic acid may be a monoester compound, a diester compound, or a mixture thereof, and more specifically, a diester compound. For example, the diester compound of the aliphatic dicarboxylic acid may be dimethyl adipate, diethyl adipate, dimethyl succinate or diethyl succinate.

More specifically, the aliphatic dicarboxyl compound may include adipic acid or an ester thereof.

In one embodiment, the aromatic dicarboxyl compound may be selected from aromatic dicarboxylic acids having 8 to 16 carbon atoms or esters thereof.

More specifically, the aromatic dicarboxyl compound is phthalic acid or its ester, terephthalic acid or its ester, isophthalic acid or its ester, 1,5-naphthalenedicarboxylic acid or its ester, 2,6-naphthalenedicarboxylic acid or It may be selected from the group consisting of esters thereof, diphenic acid or esters thereof, p-phenylene diacetic acid or esters thereof, o-phenylene diacetic acid or esters thereof, and combinations thereof. The ester compound of the aromatic dicarboxylic acid may be a monoester compound, a diester compound, or a mixture thereof, and more specifically, a diester compound. For example, the ester compound of the aromatic dicarboxylic acid may be dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate or diethyl isophthalate.

In one embodiment, the diol component may further include an additional diol component in addition to the solid dispersion of the anhydrosugar alcohol and the anhydrosugar alcohol-alkylene glycol.

In one embodiment, the additional diol component may be a diol component represented by the following Chemical Formula 2:

[Formula 2]

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; a linear alkylene group having 1 to 15 carbon atoms; a branched alkylene group having 3 to 15 carbon atoms; or a cyclic alkylene group having 3 to 15 carbon atoms, wherein the arylene group, linear alkylene group, branched alkylene group and cyclic alkylene group are each a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, a nitro group, or It may be unsubstituted or substituted with a carboxyl group.

In one embodiment, in Formula 2, the halogen atom may be F, Cl or Br, and the alkyl group is an alkyl group having 1 to 20 carbon atoms (more specifically, an alkyl group having 1 to 13 carbon atoms, for example, methyl, ethyl , propyl or butyl), and the cycloalkyl group may be a cycloalkyl group having 3 to 10 carbon atoms (more specifically, a cycloalkyl group having 3 to 6 carbon atoms), and the alkenyl group is an alkenyl group having 2 to 20 carbon atoms (more Specifically, it may be an alkenyl group having 2 to 13 carbon atoms), and the alkoxy group is an alkoxy group having 1 to 20 carbon atoms (more specifically, an alkoxy group having 1 to 13 carbon atoms, for example, methoxy, ethoxy, propoxy or butoxy), and the aryl group may be an aryl group having 6 to 30 carbon atoms (more specifically, an aryl group having 6 to 20 carbon atoms, for example, a phenyl group, tolyl group, xylenyl group, or naphthyl group). have.

In one embodiment, in Formula 2, X is a substituted or unsubstituted bisphenol (eg, bisphenol A, bisphenol F or bisphenol TMC, etc.), a substituted or unsubstituted resorcinol, a substituted or unsubstituted hydroquinone (eg, For example, hydroquinone, 2-nitro hydroquinone, 2-sulfonyl hydroquinone, etc.), substituted or unsubstituted biphenol, substituted or unsubstituted naphthalenediol, or arylene which may be derived from substituted or unsubstituted diphenylphenol It may be a group, for example, it may be represented by the following Chemical Formulas 2a to 2h.

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

[Formula 2f]

[Formula 2g]

[Formula 2h]

In one embodiment, in Formula 2, X may be an alkylene group that may be derived from substituted or unsubstituted ethylene glycol, substituted or unsubstituted propylene glycol, or substituted or unsubstituted butanediol, for example, It may be an ethylene group, a propylene group, or a butylene group.

In one embodiment, in Formula 2, X is a cycloalkylene group which may be derived from a substituted or unsubstituted cyclohexane diol, a substituted or unsubstituted cyclohexane dimethanol, or a substituted or unsubstituted tetramethylcyclobutane diol. and, for example, may be represented by the following Chemical Formulas 2i to 2k.

[Formula 2i]

[Formula 2j]

[Formula 2k]

In one embodiment, the diol component represented by Formula 2 may be an aromatic diol, an aliphatic diol, an anhydrosugar alcohol and an alicyclic diol other than an anhydrosugar alcohol-alkylene glycol, or a mixture thereof, preferably an aliphatic diol (especially an aliphatic diol derived from biomass).

Examples of the aromatic diol include bisphenol (eg, bisphenol A, bisphenol F, bisphenol which is unsubstituted or substituted with a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, a nitro group or a carboxyl group). TMC, etc.), resorcinol, hydroquinone, biphenol, naphthalene diol, or a mixture thereof may be used, preferably substituted with a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, a nitro group or a carboxyl group Bisphenol A, optionally or unsubstituted, may be used.

The aliphatic diol is, for example, an aliphatic diol having 2 to 15 carbon atoms, which is unsubstituted or substituted with a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, a nitro group or a carboxyl group, more specifically, an aliphatic diol having 2 carbon atoms. to 10 aliphatic diols, for example, ethylene glycol, diethylene glycol, triethylene glycol, propane diol (1,2-propane diol and 1,3-propane diol, etc.), butane diol (1,2- butanediol, 1,3-butanediol and 1,4-butanediol, etc.), pentanediol (1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol and 1,5-pentanediol, etc.) ), hexanediol (1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol and 1,6-hexanediol, etc.), neopentyl glycol, 2,2- dimethyl-1,3-propane diol, 2-ethyl-2-t-butyl-1,3-propane diol, 2,2,4-trimethyl-1,6-hexane diol, or a mixture thereof, more specifically may be butanediol.

The alicyclic diol other than the anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol includes, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, a nitro group or a carboxyl group unsubstituted or substituted. , cyclohexane diol (1,2-cyclohexane diol, 1,3-cyclohexane diol and 1,4-cyclohexane diol, etc.), cyclohexane dimethanol (1,2-cyclohexane dimethanol, 1,3-cyclo hexane dimethanol and 1,4-cyclohexane dimethanol), tetramethylcyclobutane diol, tricyclodecanedimethanol, adamantanediol, or a mixture thereof, and more specifically, cyclohexane diol.

In one embodiment, the biodegradable polyester resin may include a repeating unit derived from a dicarboxyl component; And a biodegradable polyester resin comprising a repeating unit derived from a diol component, wherein the dicarboxyl component is 30 to 70 mol% of an aliphatic dicarboxyl compound based on 100 mol% of the total of the dicarboxyl component; and 30 to 70 mol% of an aromatic dicarboxyl compound, wherein the aliphatic dicarboxyl component includes adipic acid or an ester thereof, and the diol component is anhydrosugar alcohol based on 100 mol% of the total of the diol component. 0.1 to 23 mol% and 0.1 to 30 mol% of anhydrosugar alcohol-alkylene glycol, the total content of anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol is 5 to 53 mole %.

More specifically, the content of the aliphatic dicarboxyl compound contained in the dicarboxyl component of the biodegradable polyester resin is 30 mol% or more, 35 mol% or more, 40 mol% or more, based on 100 mol% of the total of the dicarboxyl component. mol% or more, 45 mol% or more, or 50 mol% or more, 70 mol% or less, 65 mol% or less, 60 mol% or less, 55 mol% or less, or 50 mol% or less, for example 30 to 70 mol% %, 40 to 65 mol% or 50 to 60 mol%. When the content of the aliphatic dicarboxyl compound is out of the above range, the glass transition temperature of the biodegradable polyester resin may be lowered, and heat resistance may be poor.

In addition, the content of the aromatic dicarboxyl compound included in the dicarboxyl component is 30 mol% or more, 35 mol% or more, 40 mol% or more, 45 mol% or more, based on 100 mol% of the total amount of the dicarboxyl component. or 50 mol % or more, 70 mol % or less, 65 mol % or less, 60 mol % or less, 55 mol % or less, or 50 mol % or less, for example 30 to 70 mol %, 40 to 65 mol % or It may be 50 to 60 mol%. When the content of the aromatic dicarboxyl compound is out of the above range, the biodegradability of the polyester resin may decrease, and mechanical properties (eg, elongation) may deteriorate.

In one embodiment, the anhydrosugar alcohol in the biodegradable polyester resin of the present invention improves heat resistance by increasing the glass transition temperature, and disrupts the structural regularity of molecular chains in the resin to further improve biodegradability.

In one embodiment, the content of anhydrosugar alcohol included as a repeating unit in the biodegradable polyester resin is 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, 3 mol% or more, based on 100 mol% of the total diol component. , 5 mol% or more, 8 mol% or more, 10 mol% or more, or 12 mol% or more, and 23 mol% or less, 20 mol% or less, 19 mol% or less, 18 mol% or less, 15 mol% or less, 12 mol% or less % or less, 10 mol% or less, or 8 mol% or less, for example 0.1 to 23 mol%, 0.1 to 20 mol%, 0.5 to 20 mol%, or 0.5 to 19 mol%. When the content of anhydrosugar alcohol is less than the above level, the effect of improving the heat resistance and biodegradability of the resin may be insignificant, and when the content exceeds the above level, the reactivity is low and the reaction rate is significantly slowed, and thus a high molecular weight resin cannot be prepared, The color of the resin may deteriorate, and mechanical properties may deteriorate.

In one embodiment, the anhydrosugar alcohol-alkylene glycol in the biodegradable polyester resin of the present invention can improve the color value, improve mechanical properties, and disturb the structural regularity of molecular chains in the resin to biodegradability can be further improved.

In one embodiment, the content of anhydrosugar alcohol-alkylene glycol contained as a repeating unit in the biodegradable polyester resin is 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, based on 100 mol% of the total diol component, 3 mol % or more, 4 mol % or more, 5 mol % or more, 8 mol % or more, 10 mol % or more, 15 mol % or more, or 20 mol % or more, and 30 mol % or less, 28 mol % or less, 25 mol % or more or less, 22 mol% or less, 20 mol% or less, 16 mol% or less, 15 mol% or less, 12 mol% or less, or 10 mol% or less, for example 0.1 to 30 mol%, 3 to 30 mol% or 4 to 28 mol%. When the content of anhydrosugar alcohol-alkylene glycol is less than the above level, the effect of improving the color value, mechanical properties and biodegradability of the resin may be insignificant. slow, and thus a high molecular weight resin cannot be produced, and the color of the resin may be deteriorated and heat resistance may be poor.

In one embodiment, the total content of anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol included as a repeating unit in the biodegradable polyester resin is 5 mol% or more, 8 mol% or more, based on 100 mol% of the total diol component, 10 mol % or more, 12 mol % or more, 15 mol % or more, 20 mol % or more, 25 mol % or more, 28 mol % or more, or 30 mol % or more, and 53 mol % or less, 50 mol % or less, 47 mol % or less, 45 mol% or less, 40 mol% or less, 35 mol% or less, 31 mol% or less, 30 mol% or less, 28 mol% or less, 25 mol% or less, or 20 mol% or less, for example 5 to 53 mol% or less mol%, 5-50 mol%, 5-47 mol%, 8-45 mol% or 10-40 mol%. If the total content of anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol is less than the above level, the effect of improving the biodegradability of the resin may be insignificant. It is difficult to reach the molecular weight of the resin, and the color and heat resistance of the resin may be deteriorated.

In one embodiment, when an additional diol component (eg, aliphatic diol) is included in addition to anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol as a repeating unit in the biodegradable polyester resin, the content is 100 diol components in total. 47 mol% or more, 50 mol% or more, 53 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, or 70 mol% or more, 95 mol% or less, 90 mol% or more, based on mol% or less, 88 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, or 70 mol% or less, for example, 47 to 95 mol%, 50 to 95 mol%, 53 to 95 mol%, 55 to 92 mole % or 60 to 90 mole %. By using an additional diol component (for example, an aliphatic diol, specifically an aliphatic diol derived from biomass) other than the anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol at the above level, the heat resistance of the biodegradable polyester resin is improved. While maintaining excellent and improving the content of biomass-derived components, it is easy to apply to eco-friendly products, and in particular, mechanical properties (eg, elongation, etc.) can be further improved.

In one embodiment, the intrinsic viscosity (IV) of the biodegradable polyester composite according to the present invention may be greater than 0.8, 0.85 or more, or 0.9 or more, and may be less than 1.3, 1.25 or less, or 1.2 or less, for example, more than 0.8 to 1.3. less than, 0.85 to 1.25 or 0.9 to 1.2. The intrinsic viscosity (IV) is a 0.5 wt% solution by dissolving the biodegradable polyester complex in a mixture of phenol and tetrachloroethane (weight ratio = 50:50), and then measuring at 35 ° C using an Uberod viscometer. can

In one embodiment, the biodegradable polyester composite according to the present invention has a low intrinsic viscosity change rate and excellent heat resistance. Intrinsic viscosity change rate, for example, after preparing a biodegradable polyester composite in the form of a pellet, 1 g of the biodegradable polyester composite pellet is placed on an aluminum plate, left in an oven at 65 ° C. for 72 hours, then taken out again and heat history at room temperature After removing the intrinsic viscosity may be measured to calculate the rate of change compared to the initial intrinsic viscosity, and the rate of change in intrinsic viscosity of the biodegradable polyester composite of the present invention may be less than 30%, preferably less than 20%. The lower the rate of change in intrinsic viscosity of the biodegradable polyester composite means less denaturation by heat, that is, better heat resistance.

In one embodiment, the biodegradable polyester composite according to the present invention has excellent mechanical properties due to high elongation. The elongation of the biodegradable polyester resin may be measured, for example, according to ASTM D638.

In one embodiment, the biodegradable polyester composite of the present invention has excellent color and less yellowing. In order to confirm the superiority of the color of the biodegradable polyester composite, for example, the Color-b value can be measured using ZE 6000 of Nippon denshoku, and the lower the measured color-b value, the lower the occurrence of yellowing. Less, meaning that the color is excellent.

In one embodiment, if the reaction molar ratio of the diol component to the dicarboxyl component (the total number of moles of the diol component/the total number of moles of the dicarboxyl component) is less than 1, the unreacted dicarboxyl component remains during the polymerization reaction and is biodegradable. There is a fear that the mechanical properties and color of the sexual polyester composite may be lowered, and when it exceeds 1.5, the polymerization reaction rate is too slow and the productivity of the biodegradable polyester composite may be reduced.

The biodegradable polyester composite according to the present invention, compared to the existing biodegradable polyester resin composite, in particular, directly in the form of a solid crystal or powder without dispersing nano materials (eg, nano cellulose, etc.) in water, etc. Compared to the composite used, it exhibits significantly improved mechanical properties (eg, tensile strength, tensile modulus and elongation, etc.), and the nanomaterial is uniformly dispersed in the composite to have uniform physical properties.

In one embodiment, the biodegradable polyester composite of the present invention may exhibit a tensile strength of greater than 24 MPa.

The tensile strength may be, for example, a value measured using a universal testing machine (UTM) based on ASTM D638.

In addition, in the biodegradable polyester composite according to the present invention, the nanomaterial is uniformly dispersed inside the matrix resin, so that physical properties (particularly, tensile strength) can be uniformly maintained compared to the existing resin composite.

In one embodiment, the polyester composite of the present invention may exhibit a standard deviation of tensile strength of 3 MPa or less.

More specifically, the standard deviation of the tensile strength may be 2.5 Mpa or less, 2.0 MPa or less, 1.5 MPa or less, 1.3 MPa or less, 1.0 MPa or less, 0.95 MPa or less, or 0.89 MPa or less.

The tensile strength standard deviation may be, for example, the standard deviation of values measured for five specimens using a universal testing machine (UTM) according to ASTM D638.

According to another aspect of the present invention, the nanomaterial comprises a step of polymerizing a diol component and a dicarboxyl component comprising a solid dispersion of anhydrosugar alcohol dispersed therein and anhydrosugar alcohol-alkylene glycol, Here, the solid dispersion of the anhydrosugar alcohol is obtained by introducing the nanomaterial into the anhydrosugar alcohol in an aqueous dispersion state, a method for producing a biodegradable polyester composite is provided.

In one embodiment, the solid dispersion of the anhydrosugar alcohol is added to the anhydrosugar alcohol in an aqueous dispersion state of the nanomaterial (eg, a state in which the nanomaterial is dispersed in water at a concentration of 0.1 to 5% by weight) and uniformly After mixing and melting while removing moisture by applying a vacuum at a temperature above the melting point of the anhydrosugar alcohol (for example, at a temperature of 80° C. or higher), it may be a room temperature solid dispersion obtained by cooling the molten mixture to room temperature.

The nanomaterial, anhydrosugar alcohol, anhydrosugar alcohol-alkylene glycol, dicarboxyl component, and diol component that can be additionally used in the manufacturing method are as described above. In addition, the solid dispersion of the anhydrosugar alcohol and its manufacturing method are the same as described above.

In one embodiment, the method for producing the biodegradable polyester composite includes (1) an esterification reaction or transesterification; and (2) subjecting the reaction product obtained in step (1) to a polycondensation reaction.

In one embodiment, in the step (1), the solid dispersion of the anhydrosugar alcohol and the anhydrosugar alcohol-alkylene glycol and a diol component and a dicarboxyl component are mixed with the diol component to the dicarboxyl component. The reaction molar ratio (total number of moles of diol component/total number of moles of dicarboxyl component) is introduced into the reactor so that it becomes 1.0 to 1.5, and then at a temperature of 150 to 250°C (more specifically, 200 to 250°C or 200 to 240°C) and 0.1 to 3.0 kgf/cm 2 (more specifically, 0.2 to 2.0 kgf/cm 2 ) under pressure conditions (reduced pressure conditions) for esterification or transesterification.

The esterification reaction time or transesterification reaction time is usually 1 to 5 hours, more specifically about 3 to 4 hours, and may vary depending on the reaction temperature and pressure, and the reaction molar ratio of the dicarboxyl component to the diol component.

A catalyst is not necessarily required for the esterification reaction or the transesterification reaction (step (1) above), but a catalyst may be used to shorten the reaction time. The esterification reaction or transesterification reaction (step (1) above) may be performed in a batch or continuous manner, and each reaction raw material may be separately input.

In one embodiment, in step (2), a polycondensation reaction of the reaction product obtained in step (1) is performed.

Before the start of the polycondensation reaction, a polycondensation catalyst and a stabilizer may be added to the reaction product of the esterification reaction or the transesterification reaction. As the polycondensation catalyst, a polycondensation catalyst commonly used in this field may be used without limitation, for example, a titanium-based compound, a germanium-based compound, an antimony-based compound, an aluminum-based compound, and a tin-based compound. One type or a mixture of two or more types may be used. As the stabilizer added to the polycondensation reaction, a phosphorus-based compound may be generally used, and for example, phosphoric acid, trimethyl phosphate, triethyl phosphate, or a mixture thereof may be used.

The polycondensation reaction is carried out at a temperature of 200 to 280 °C (more specifically, 210 to 260 °C or 220 to 240 °C) and a reduced pressure of 500 to 0.1 mmHg. The reduced pressure condition is for removing by-products of the polycondensation reaction.

In one embodiment, the biodegradable polyester composite of the present invention comprises (a) (i) a dicarboxyl component comprising adipic acid and dimethyl terephthalate and an aliphatic dicarboxyl compound other than adipic acid; and (ii) a polymerization reaction product comprising a solid dispersion of anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol and, if necessary, a diol component including another aliphatic diol, at atmospheric pressure or at a pressurization pressure of 0.1 to 3.0 kgf/cm 2 . and an esterification reaction or transesterification reaction at a temperature of 150 to 250° C. for an average residence time of 1 to 5 hours. (b) Next, the esterification or transesterification reaction product is subjected to a polycondensation reaction at a reduced pressure of 500 to 0.1 mmHg and a temperature of 200 to 280° C. for an average residence time of 1 to 10 hours, thereby biodegradation according to the present invention A sexual polyester composite can be prepared. Preferably, the final vacuum degree of the polycondensation reaction is 1.0 mmHg or less, and the esterification or transesterification reaction may be performed under an inert gas atmosphere.

According to another aspect of the present invention, there is provided a molded article comprising the biodegradable polyester composite of the present invention.

The biodegradable polyester composite of the present invention can have uniform physical properties (especially, tensile strength, tensile modulus and elongation, etc.) because the nanomaterial is uniformly dispersed in the composite. Because it is uniform, the defect rate can be very low when applying the product.

The method for producing a molded article by molding the biodegradable polyester composite of the present invention is not particularly limited, and a molded article may be manufactured using a method generally used in the plastic molding field. For example, the molded article of the present invention may be manufactured by extruding or injection molding the biodegradable polyester composite of the present invention.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

[ Example ]

[Solid containing nanocellulose dispersion Produce]

<Nano cellulose fiber ( Nanocellulose fiber( NCF ))Wow no sugar containing alcohol dispersion >

production example A1: Nano Cellulose Fiber 1 by weight % containing dispersion Produce

In a rotary concentrator, 99 g of isosorbide (NOVASORB® Samyang Co., Ltd.) and 100 g of an aqueous solution (KB101, Asia Nano Cellulose Co., Ltd.) in which nanocellulose fibers are dispersed at 1 wt% (KB101, Asia Nano Cellulose Co., Ltd.) were uniformly mixed. Thereafter, the mixture was melted while removing moisture by applying a vacuum under a temperature condition of 80° C. or higher than the melting point of isosorbide. Then, the molten mixture was cooled to room temperature to prepare isosorbide (solid dispersion) in which nano-cellulose fibers were dispersed. The solid dispersion, based on the total weight of the solid dispersion, included 1% by weight of nano-cellulose fibers.

production example A2: 3 nano cellulose fibers by weight % containing dispersion Produce

Except that the content of isosorbide was changed from 99 g to 97 g, and the content of the aqueous solution in which the nano cellulose fibers were dispersed at 1 wt % was changed from 100 g to 300 g, it was carried out in the same manner as in Preparation Example A1. Isosorbide (solid dispersion) in which fibers were dispersed was prepared. The solid dispersion, based on the total weight of the solid dispersion, contained 3% by weight of nano-cellulose fibers.

production example A3: 5 nano cellulose fibers by weight % containing dispersion Produce

Except that the content of isosorbide was changed from 99 g to 95 g, and the content of the aqueous solution in which the nano cellulose fibers were dispersed at 1 wt % was changed from 100 g to 500 g, it was carried out in the same manner as in Preparation Example A1 to nano cellulose Isosorbide (solid dispersion) in which fibers were dispersed was prepared. The solid dispersion, based on the total weight of the solid dispersion, contained 5% by weight of nano-cellulose fibers.

Preparation A4: Preparation of dispersion containing nano-cellulose fibers in an amount of 10% by weight

Except that the content of isosorbide was changed from 99 g to 90 g, and the content of the aqueous solution in which the nano cellulose fibers were dispersed at 1 wt % was changed from 100 g to 1,000 g, it was performed in the same manner as in Preparation Example A1. An isosorbide (solid dispersion) in which cellulose fibers were dispersed was prepared. The solid dispersion, based on the total weight of the solid dispersion, contained 10% by weight of nano cellulose fibers.

<Nano cellulose crystals ( Nanocellulose crystal (NCC)) and no sugar Dispersion containing alcohol>

production example B1: Nanocellulose crystals 1 by weight % containing dispersion Produce

Instead of 100 g of aqueous solution (KB101, Asia Nano Cellulose Co., Ltd.) in which nanocellulose fibers are dispersed at 1 wt% , to prepare isosorbide (solid dispersion) in which nano-cellulose crystals are dispersed in the same manner as in Preparation Example A1. The solid dispersion, based on the total weight of the solid dispersion, contained 1% by weight of nano cellulose crystals.

production example B2: Nanocellulose crystals 3 by weight % containing dispersion Produce

The content of isosorbide was changed from 99 g to 97 g, and 300 g of an aqueous solution in which nano cellulose crystals were dispersed at 1 wt % was used instead of 100 g of the aqueous solution in which nano cellulose fibers were dispersed at 1 wt %, except that 300 g of the aqueous solution was used. It was carried out in the same manner as A1 to prepare isosorbide (solid dispersion) in which nano cellulose crystals were dispersed. The solid dispersion, based on the total weight of the solid dispersion, contained 3% by weight of nano cellulose crystals.

production example B3: nano cellulose crystals 5 by weight % containing dispersion Produce

The content of isosorbide was changed from 99 g to 95 g, and 500 g of an aqueous solution in which nano cellulose crystals were dispersed at 1 wt % was used instead of 100 g of an aqueous solution in which nano cellulose fibers were dispersed at 1 wt %, except that 500 g of the aqueous solution was used. It was carried out in the same manner as A1 to prepare isosorbide (solid dispersion) in which nano cellulose crystals were dispersed. The solid dispersion, based on the total weight of the solid dispersion, contained 5% by weight of nano cellulose crystals.

production example B4: nano cellulose crystals 10 by weight % containing dispersion Produce

The content of isosorbide was changed from 99 g to 90 g, and 1,000 g of an aqueous solution in which nano cellulose crystals were dispersed at 1 wt % was used instead of 100 g of an aqueous solution in which nano cellulose fibers were dispersed at 1 wt %. Isosorbide (solid dispersion) in which nanocellulose crystals were dispersed was prepared in the same manner as in Example A1. The solid dispersion, based on the total weight of the solid dispersion, contained 10% by weight of nano cellulose crystals.

<A mixture of nanocellulose fibers and nanocellulose crystals and no sugar Dispersion containing alcohol>

production example C1: A mixture of nanocellulose fibers and nanocellulose crystals 1 by weight % Preparation of a dispersion comprising

Except for using a mixture of 50 g of an aqueous solution in which nano cellulose fibers are dispersed at 1 wt % and 50 g of an aqueous solution in which nano cellulose crystals are dispersed at 1 wt % instead of 100 g of an aqueous solution in which nano cellulose fibers are dispersed at 1 wt %, Isosorbide (solid dispersion) in which nano-cellulose fibers and nano-cellulose crystals were dispersed was prepared in the same manner as in Preparation Example A1. The solid dispersion contained 1% by weight of a mixture of nano-cellulose fibers and nano-cellulose crystals, based on the total weight of the solid dispersion.

production example C2: a mixture of nanocellulose fibers and nanocellulose crystals 3 middle included in % dispersion Produce

The content of isosorbide was changed from 99 g to 97 g, and instead of 100 g of the aqueous solution in which the nano cellulose fibers were dispersed at 1 wt %, 150 g of the aqueous solution in which the nano cellulose fibers were dispersed at 1 wt % and the nano cellulose crystals were dispersed at 1 wt % Isosorbide (solid dispersion) in which nano-cellulose fibers and nano-cellulose crystals were dispersed was prepared in the same manner as in Preparation Example A1, except that a mixture of 150 g of an aqueous solution was used. The solid dispersion contained 3 wt% of a mixture of nano-cellulose fibers and nano-cellulose crystals, based on the total weight of the solid dispersion.

production example C3: a mixture of nanocellulose fibers and nanocellulose crystals 5 by weight % Preparation of a dispersion comprising

The content of isosorbide was changed from 99 g to 95 g, and instead of 100 g of the aqueous solution in which the nano cellulose fibers were dispersed at 1 wt %, 250 g of the aqueous solution in which the nano cellulose fibers were dispersed at 1 wt % and the nano cellulose crystals were dispersed at 1 wt % Except that a mixture of 250 g of the aqueous solution was used, isosorbide (solid dispersion) in which nano-cellulose fibers and nano-cellulose crystals were dispersed was prepared in the same manner as in Preparation Example A1. The solid dispersion contained 5 wt% of a mixture of nano-cellulose fibers and nano-cellulose crystals, based on the total weight of the solid dispersion.

production example C4: Preparation of dispersion containing a mixture of nano-cellulose fibers and nano-cellulose crystals in an amount of 10 wt%

The content of isosorbide was changed from 99 g to 90 g, and instead of 100 g of the aqueous solution in which the nano cellulose fibers were dispersed at 1 wt %, 500 g of the aqueous solution in which the nano cellulose fibers were dispersed at 1 wt % and the nano cellulose crystals were dispersed at 1 wt % Isosorbide (solid dispersion) in which nano-cellulose fibers and nano-cellulose crystals were dispersed was prepared in the same manner as in Preparation Example A1, except that a mixture of 500 g of an aqueous solution was used. The solid dispersion contained 10% by weight of a mixture of nano-cellulose fibers and nano-cellulose crystals, based on the total weight of the solid dispersion.

[ no sugar alcohol-alkylene glycol ( no sugar alkylene of alcohol oxide preparation of adduct)]

production example D1: isosorbide- ethylene glycol (Ethylene of isosorbide oxide 5 mole adduct)

73.1 g (0.5 mol) of isosorbide, 110 g (2.5 mol) of ethylene oxide, and 0.2 g of sodium hydroxide as a catalyst were placed in a reactor equipped with a nitrogen gas pipe and a cooling device, a stirrer, a thermometer and a heater, and a pressurized reaction device. The temperature was raised gradually. Isosorbide-ethylene glycol (ethylene oxide 5 of isosorbide) in the form in which the hydrogens of the hydroxy groups at both ends of the isosorbide are substituted with hydroxyethyl groups by reacting at a temperature of 120°C to 160°C for 2 to 4 hours molar adducts) were prepared.

[Solid containing nanocellulose dispersion Biodegradable polyester resin composite using]

<Production of biodegradable polyester resin composite using solid dispersion containing nanocellulose fibers and anhydrosugar alcohol and evaluation of physical properties>

Example A1: production example A1 solid dispersion Preparation of biodegradable polyester resin composite using

Put the reactants of the composition shown in Table 1 below in a 5L melt-condensation reactor, add 750 ppm of a titanium-based catalyst based on an acid component (dimethyl terephthalate, DMT), and then increase the temperature to 208° C. for esterification reaction was carried out, and water and alcohol produced as by-products were removed. When alcohol, a by-product, flows out of the system by 80% of the theoretical amount of alcohol generated, 550 ppm of the polycondensation catalyst based on the acid component (DMT) is added to raise the temperature to 238°C, and the pressure of the reaction system is gradually reduced to 1 mmHg. to prepare a biodegradable polyester resin composite.

50 g of the biodegradable polyester resin composite was dissolved in 1 L of chloroform in order to measure the amount of nano cellulose fibers in the obtained biodegradable polyester resin composite, and the remaining crystalline components were filtered, and then this was carried out in a vacuum oven for 24 hours. After drying, the weight was measured to be 0.1 g. Through this, the content of the nano-cellulose fibers of the obtained biodegradable polyester resin composite was calculated to be 0.20% by weight.

Five identical tensile specimens were prepared according to ASTM D638 using the obtained biodegradable polyester resin composite, and the tensile strength of the five tensile specimens was measured using a universal testing machine (UTM). As a result, the average tensile strength The strength was 39.4 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

Example A2: production example A2 solid dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and a biodegradable polyester resin composite was prepared in the same manner as in Example A1. As a result of measuring the content of nano-cellulose fibers in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 0.60 wt%, and in the same manner as in Example A1, the obtained biodegradable polyester resin composite As a result of measuring the average tensile strength of , it was 41.6 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

Example A3: production example A3 solid dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and polymerization was performed under the same conditions as in Example A1 to prepare a biodegradable polyester resin composite. As a result of measuring the content of nano-cellulose fibers in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 0.87 wt %, and the obtained biodegradable polyester resin composite in the same manner as in Example A1. As a result of measuring the average tensile strength of , it was 41.6 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

Example A4: production example A4 solid dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and polymerization was performed under the same conditions as in Example A1 to prepare a biodegradable polyester resin composite. As a result of measuring the content of nano-cellulose fibers in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 1.0 wt %, and the obtained biodegradable polyester resin composite was obtained in the same manner as in Example A1. As a result of measuring the average tensile strength of , it was 44.4 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

<Nanocellulose crystals and no sugar solids containing alcohol dispersion Preparation of biodegradable polyester resin composite using and evaluation of physical properties>

Example B1: production example B1 solid dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and polymerization was performed under the same conditions as in Example A1 to prepare a biodegradable polyester resin composite. As a result of measuring the content of nano cellulose crystals in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 0.20 wt%, and in the same manner as in Example A1, the obtained biodegradable polyester resin composite As a result of measuring the average tensile strength of , it was 39.2 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

Example B2: production example B2 solid dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and polymerization was performed under the same conditions as in Example A1 to prepare a biodegradable polyester resin composite. As a result of measuring the content of nano-cellulose crystals in the obtained biodegradable polyester resin composite in the same manner as in Example A1, it was 0.45 wt%, and the obtained biodegradable polyester resin composite in the same manner as in Example A1. As a result of measuring the average tensile strength of , it was 38.4 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

Example B3: production example B3 solid dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and polymerization was performed under the same conditions as in Example A1 to prepare a biodegradable polyester resin composite. As a result of measuring the content of nano cellulose crystals in the obtained biodegradable polyester resin composite in the same manner as in Example A1, it was 0.75 wt%, and in the same manner as in Example A1, the obtained biodegradable polyester resin composite As a result of measuring the average tensile strength of , it was 39.4 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

Example B4: production example B4 solid dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and polymerization was performed under the same conditions as in Example A1 to prepare a biodegradable polyester resin composite. As a result of measuring the content of nano cellulose crystals in the obtained biodegradable polyester resin composite in the same manner as in Example A1, it was 1.25 wt%, and the obtained biodegradable polyester resin composite in the same manner as in Example A1. As a result of measuring the average tensile strength of , it was 46.2 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

<A mixture of nanocellulose fibers and nanocellulose crystals and no sugar solids containing alcohol dispersion Preparation of biodegradable polyester resin composite using and evaluation of physical properties>

Example C1: production example solid of C1 dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and polymerization was performed under the same conditions as in Example A1 to prepare a biodegradable polyester resin composite. As a result of measuring the content of nano-cellulose fibers and nano-cellulose crystals in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 0.20 wt%, and in the same manner as in Example A1, the obtained biodegradability As a result of measuring the average tensile strength of the polyester resin composite, it was 40.2 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

Example C2: production example C2 solid dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and polymerization was performed under the same conditions as in Example A1 to prepare a biodegradable polyester resin composite. As a result of measuring the content of nano-cellulose fibers and nano-cellulose crystals in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 0.45 wt%, and the biodegradability obtained in the same manner as in Example A1 As a result of measuring the average tensile strength of the polyester resin composite, it was 39.4 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

Example C3: production example C3 solid dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and polymerization was performed under the same conditions as in Example A1 to prepare a biodegradable polyester resin composite. As a result of measuring the content of nano-cellulose fibers and nano-cellulose crystals in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 0.57 wt%, and in the same manner as in Example A1, the obtained biodegradability As a result of measuring the average tensile strength of the polyester resin composite, it was 40.2 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

Example C4: production example C4 solid dispersion Preparation of biodegradable polyester resin composite using

A reactant having the composition shown in Table 1 was put into a 5L melt-condensation reactor, and polymerization was performed under the same conditions as in Example A1 to prepare a biodegradable polyester resin composite. As a result of measuring the content of nano-cellulose fibers and nano-cellulose crystals in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 2.0 wt%, and the obtained biodegradability in the same manner as in Example A1 As a result of measuring the average tensile strength of the polyester resin composite, it was 46.4 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 1 below.

[Table 1]

[Comparative example]

comparative example A1: Nanocellulose particles are not dispersed no sugar Manufacture of biodegradable polyester resin using alcohol and evaluation of physical properties

100 g of pure isosorbide (NOVASORB® Samyang Corporation) was used instead of 100 g of the solid dispersion prepared in Preparation Example A1, and isosorbide-ethylene glycol was not used, and the content of 1,4-butanediol was shown in the table. A biodegradable polyester resin was obtained in the same manner as in Example A1, except that it was changed as described in 2. As a result of measuring the average tensile strength of the obtained biodegradable polyester resin in the same manner as in Example A1, it was 21.0 MPa.

The obtained biodegradable polyester resin was evaluated for physical properties, and the results are shown in Table 2 below.

Compared to the biodegradable polyester resin composite of Examples A1 to A4, B1 to B4, and C1 to C4 according to the present invention, the biodegradable polyester resin of Comparative Example A1 not containing nano-cellulose particles had an average tensile strength It was very low, and it was confirmed that the mechanical properties were poor.

comparative example A2: Nanocellulose particles are not dispersed no sugar alcohol and no sugar Preparation of biodegradable polyester resin using alcohol-alkylene glycol and evaluation of physical properties

A biodegradable polyester resin was obtained in the same manner as in Example A1, except that 100 g of pure isosorbide (NOVASORB® Samyang Corporation) was used instead of 100 g of the solid dispersion prepared in Preparation Example A1. . As a result of measuring the average tensile strength of the obtained biodegradable polyester resin in the same manner as in Example A1, it was 20.0 MPa.

The obtained biodegradable polyester resin was evaluated for physical properties, and the results are shown in Table 2 below.

Compared with the biodegradable polyester resin composite of Examples A1 to A4, B1 to B4, and C1 to C4 according to the present invention, the biodegradable polyester resin of Comparative Example A2 not containing nano-cellulose particles had an average tensile strength It was very low, and it was confirmed that the mechanical properties were poor.

comparative example B1: Nano Cellulose Fiber Powder 1 by weight % melt containing dispersion Preparation of biodegradable polyester resin composite using and evaluation of physical properties

99 g of isosorbide (NOVASORB® Samyang Co., Ltd.) was heated in an oven at 70° C. to obtain 99 g of molten isosorbide. 1 g of nano cellulose fibers in powder form were directly added to 99 g of the molten isosorbide, and the nanocellulose fibers were dispersed in the molten isosorbide by stirring. After that, it was further dispersed for about 1 hour using an ultrasonicator at the same temperature to prepare isosorbide (liquid molten dispersion) in which nanocellulose fibers were dispersed. The molten dispersion, based on the total weight of the molten dispersion, included 1% by weight of nano cellulose fibers.

Then, put the reactant of the composition shown in Table 2 below in a 5L melt-condensation reactor, add 750 ppm of a titanium-based catalyst based on the acid component (dimethyl terephthalate, DMT), and then increase the temperature to 208 ° C. to ester The reaction was carried out, and water and alcohol produced as by-products were removed. When alcohol, a by-product, flows out of the system by 80% of the theoretical amount of alcohol generated, 550 ppm of the polycondensation catalyst is added based on the acid component (DMT), the temperature is raised to 238°C, and the pressure of the reaction system is gradually reduced to 1 mmHg. A biodegradable polyester resin composite was prepared. As a result of measuring the content of nano-cellulose fibers in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 0.20 wt%, and the obtained biodegradable polyester resin composite in the same manner as in Example A1. As a result of measuring the average tensile strength of , it was 22.0 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 2 below.

Compared to the biodegradable polyester resin composites of Examples A1 to A4, B1 to B4, and C1 to C4 according to the present invention, the biodegradable polyester resin composite of Comparative Example B1 has very low average tensile strength, and mechanical properties I could see how bad it was.

comparative example B2: Nano Cellulose Fiber Powder 10 by weight % melt containing dispersion Preparation of biodegradable polyester resin composite using and evaluation of physical properties

Except that the content of isosorbide was changed from 99g to 90g and the content of nanocellulose fibers in powder form was changed from 1g to 10g, it was carried out in the same manner as in Comparative Example B1, so that the nanocellulose fibers were dispersed iso A sorbide (liquid molten dispersion) was obtained. The molten dispersion, based on the total weight of the molten dispersion, contained 10% by weight of nano cellulose fibers.

Thereafter, a reactant having the composition shown in Table 2 was put into a 5L melt-condensation reactor, and a biodegradable polyester resin composite was prepared in the same manner as in Example A1. As a result of measuring the content of nano-cellulose fibers in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 1.0 wt %, and the obtained biodegradable polyester resin composite in the same manner as in Example A1. As a result of measuring the average tensile strength of , it was 20.6 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 2 below.

Compared to the biodegradable polyester resin composites of Examples A1 to A4, B1 to B4, and C1 to C4 according to the present invention, the biodegradable polyester resin composite of Comparative Example B2 has very low average tensile strength, and mechanical properties I could see how bad it was.

comparative example B3: Nanocellulose crystals 1 by weight % melt containing dispersion Preparation of biodegradable polyester resin composite using and evaluation of physical properties

Isosorbide (liquid molten dispersion) in which nanocellulose crystals are dispersed in the same manner as in Comparative Example B1, except that 1g of powdered nanocellulose crystals was used instead of 1g of powdered nanocellulose fibers was obtained. The molten dispersion, based on the total weight of the molten dispersion, contained 1% by weight of nano cellulose crystals.

Thereafter, a reactant having the composition shown in Table 2 was put into a 5L melt-condensation reactor, and a biodegradable polyester resin composite was prepared in the same manner as in Example A1. As a result of measuring the content of nano cellulose crystals in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 0.20 wt%, and in the same manner as in Example A1, the obtained biodegradable polyester resin composite As a result of measuring the average tensile strength of , it was 20.6 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 2 below.

Compared with the biodegradable polyester resin composites of Examples A1 to A4, B1 to B4, and C1 to C4 according to the present invention, the biodegradable polyester resin composite of Comparative Example B3 has very low average tensile strength, and mechanical properties I could see how bad it was.

comparative example B4: nano cellulose crystals 10 by weight % melt containing dispersion Preparation of biodegradable polyester resin composite using and evaluation of physical properties

The content of isosorbide was changed from 99 g to 90 g, and 10 g of nano cellulose crystals in powder form were used instead of 1 g of nano cellulose fibers in powder form. This dispersed isosorbide (liquid molten dispersion) was obtained. The molten dispersion, based on the total weight of the molten dispersion, contained 10% by weight of nano cellulose crystals.

Thereafter, a reactant having the composition shown in Table 2 was put into a 5L melt-condensation reactor, and a biodegradable polyester resin composite was prepared in the same manner as in Example A1. As a result of measuring the content of nano cellulose crystals in the obtained biodegradable polyester resin composite in the same manner as in Example A1, it was 1.25 wt%, and the obtained biodegradable polyester resin composite in the same manner as in Example A1. As a result of measuring the average tensile strength of , it was 21.8 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 2 below.

Compared to the biodegradable polyester resin composites of Examples A1 to A4, B1 to B4, and C1 to C4 according to the present invention, the biodegradable polyester resin composite of Comparative Example B4 has very low average tensile strength, and mechanical properties I could see how bad it was.

comparative example B5: A mixture of nanocellulose fibers and nanocellulose crystals 1 by weight % melt containing dispersion Preparation of biodegradable polyester resin composite using and evaluation of physical properties

Nanocellulose fibers and nanocellulose fibers and An isosorbide (liquid molten dispersion) in which nanocellulose crystals were dispersed was obtained. The molten dispersion, based on the total weight of the molten dispersion, contained 1% by weight of a mixture of nano-cellulose fibers and nano-cellulose crystals.

Thereafter, a reactant having the composition shown in Table 2 was put into a 5L melt-condensation reactor, and a biodegradable polyester resin composite was prepared in the same manner as in Example A1. As a result of measuring the content of the mixture of nano-cellulose fibers and nano-cellulose crystals in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 0.20 wt%, and in the same manner as in Example A1, the obtained biodegradation As a result of measuring the average tensile strength of the sex polyester resin composite, it was 19.8 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 2 below.

Compared with the biodegradable polyester resin composites of Examples A1 to A4, B1 to B4, and C1 to C4 according to the present invention, the biodegradable polyester resin composite of Comparative Example B5 had a very low average tensile strength, and mechanical properties were I could see how bad it was.

comparative example B6: Melt containing a mixture of nanocellulose fibers and nanocellulose crystals in an amount of 10% by weight dispersion Preparation of biodegradable polyester resin composite using and evaluation of physical properties

The content of isosorbide was changed from 99 g to 90 g, and a mixture of 5 g of powdered nano cellulose fibers and 5 g of powdered nano cellulose crystals was used instead of 1 g of powdered nano cellulose fibers. It was carried out in the same manner as B1 to obtain isosorbide (liquid molten dispersion) in which nano-cellulose fibers and nano-cellulose crystals were dispersed. The molten dispersion contained 10% by weight of a mixture of nanocellulose fibers and nanocellulose crystals based on the total weight of the molten dispersion.

Thereafter, a reactant having the composition shown in Table 2 was put into a 5L melt-condensation reactor, and a biodegradable polyester resin composite was prepared in the same manner as in Example A1. As a result of measuring the content of the mixture of nano-cellulose fibers and nano-cellulose crystals in the biodegradable polyester resin composite obtained in the same manner as in Example A1, it was 2.0 wt%, and in the same manner as in Example A1, the obtained biodegradation As a result of measuring the average tensile strength of the sex polyester resin composite, it was 23.4 MPa.

The obtained biodegradable polyester resin composite was evaluated for physical properties, and the results are shown in Table 2 below.

Compared to the biodegradable polyester resin composites of Examples A1 to A4, B1 to B4, and C1 to C4 according to the present invention, the biodegradable polyester resin composite of Comparative Example B6 has very low average tensile strength, and mechanical properties I could see how bad it was.

[Table 2]

<Evaluation of uniformity of dispersion of nano-cellulose particles in biodegradable polyester resin composite>

Tensile strength of each of the five tensile specimens of the biodegradable polyester resin composites obtained in Examples A1 to A4, B1 to B4, and C1 to C4 and Comparative Examples B1 to B6, and their average values and standard deviations was measured and shown in Table 3 below.

[Table 3]

[Evaluation of physical properties]

The evaluation of the physical properties of the biodegradable polyester resin composite prepared in Examples and Comparative Examples was performed as follows.

(1) Intrinsic Viscosity (IV): After dissolving the biodegradable polyester resin composite in a mixture of phenol and tetrachloroethane (weight ratio = 50:50) to prepare a 0.5 wt% solution, using an Uberod viscometer at 35 ° C. Intrinsic viscosity was measured.

(2) Tensile strength: According to ASTM D638, the tensile strength was measured using a universal testing machine (UTM).

As shown in Table 3, the biodegradable polyester resin composites of Examples A1 to A4, B1 to B4, and C1 to C4 in the present invention were prepared by dispersing an aqueous dispersion containing nanocellulose particles in anhydrosugar alcohol. By using the solid dispersion, mechanical properties (tensile strength) were remarkably improved as compared to biodegradable polyester resins (Comparative Examples A1 and A2) not containing nano-cellulose particles.

In particular, as a result of measuring the average and standard deviation of the tensile strength of five tensile specimens of each of the biodegradable polyester resin composites of Examples A1 to A4, B1 to B4, and C1 to C4 according to the present invention, the tensile strength of five tensile specimens With a standard deviation range of 0.89 MPa or less, the tensile strengths of the five tensile specimens were equal to each other, and the tensile strength deviation was low. From this, it can be seen that the nano-cellulose particles are uniformly dispersed in the biodegradable polyester resin composite according to the present invention.

On the other hand, the biodegradable polyester resin of Comparative Example A1 did not contain nano cellulose particles and anhydrosugar alcohol-alkylene glycol, so the molecular weight was lowered, and mechanical properties were also obtained with the biodegradable polyester resin composite of Examples according to the present invention. It was remarkably poor compared to the biodegradable polyester resin of Comparative Example A2 did not contain nano-cellulose particles, and mechanical properties were remarkably poor compared to the biodegradable polyester resin composite of Examples according to the present invention.

In addition, as shown in Table 3, in the case of the biodegradable polyester resin composites of Comparative Examples B1 to B6 according to the present invention, the nanocellulose particles are not uniformly dispersed in the biodegradable polyester resin composite, so the measured tensile strength There was a large variation in tensile strength depending on the specimen.

Specifically, as a result of measuring the average and standard deviation of the tensile strength of five tensile specimens of each of the biodegradable polyester resin composites of Comparative Examples B1 to B6, the standard deviation range of the tensile strength of the five tensile specimens was 3.32 MPa to 6.84 MPa. The variation in tensile strength was very large, indicating that the nano-cellulose particles were non-uniformly dispersed in the biodegradable polyester resin composite.

As described above, in the case of the biodegradable polyester resin composites of Examples A1 to A4, B1 to B4, and C1 to C4 according to the present invention, the nanocellulose particles are uniformly dispersed in the composite, and thus the tensile strength is high. In the case of the biodegradable polyester resin composites of Comparative Examples B1 to B6, which did not follow the present invention, although exhibited uniform physical properties, the nano-cellulose particles were not uniformly dispersed in the composite, so the biodegradation of Examples according to the present invention Compared with the sex polyester resin composite, relatively poor tensile strength was realized and non-uniform physical properties were exhibited.

Claims (15)

A biodegradable polyester composite comprising:
It includes a matrix resin and a nanomaterial dispersed in the matrix resin,
Here, the matrix resin is a polyester resin that is a polymerization reaction product of a diol component and a dicarboxyl component comprising a solid dispersion of anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol in which the nanomaterial is dispersed,
The solid dispersion of the anhydrosugar alcohol is obtained by introducing the nanomaterial into the anhydrosugar alcohol in an aqueous dispersion state,
wherein the composite exhibits a standard deviation of tensile strength of 3 MPa or less;
Biodegradable polyester composite. According to claim 1, wherein the nanomaterial is nanocellulose, carbon nanofibers, carbon nanotubes, iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold , platinum, kaolin, clay, talc, mica, silica, bentonite, dolomite, calcium silicate, magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, aluminum silicate , zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, silicon carbide, silicon nitride, boron nitride, barium titanate, diatomaceous earth, carbon black, rock wool, graphene, graphite , graphene oxide, azo-based compound, diazo-based compound, condensed azo-based compound, thioindigo-based compound, indanthrone-based compound, quinacrindone-based compound, anthraquinone-based compound, benzimidazolone-based compound, perylene-based compound, phthalocyanine compound, anthrapyridine compound, dioxazine compound, polyethylene resin, polypropylene resin, polyester resin, nylon resin, polyamide resin, aramid resin, urethane resin, polystyrene resin, polylactic acid, cellulose acetate fiber, hemicellulose, lignin, A biodegradable polyester composite, which is selected from chitin, chitosan, starch, or mixtures thereof. The biodegradable polyester composite according to claim 1, wherein the nanomaterial is selected from nanocellulose, carbon nanofibers, carbon nanotubes, or mixtures thereof. 4. The biodegradable biodegradation of claim 3, wherein the nanocellulose is selected from nanocellulose fibers, nanocellulose crystals or mixtures thereof, and the carbon nanotubes are selected from single-walled carbon nanotubes, multi-walled carbon nanotubes or mixtures thereof. Sex polyester composite. According to claim 1, wherein the content of the nanomaterial, based on the total weight of the composite, 0.1% to 10% by weight, biodegradable polyester composite. According to claim 1, wherein the anhydrosugar alcohol is mono-anhydrosugar alcohol, dianhydrosugar alcohol, or a mixture thereof, biodegradable polyester composite. The method according to claim 1, wherein the solid dispersion of the anhydrosugar alcohol is mixed with the nanomaterial in an aqueous dispersion state, and melted while removing moisture at a temperature above the melting point of the anhydrosugar alcohol, and then melted Which is obtained by cooling the mixture to room temperature, a biodegradable polyester composite. The biodegradable polyester composite according to claim 1, wherein the anhydrosugar alcohol-alkylene glycol is an adduct obtained by reacting an alkylene oxide with hydroxyl groups at both ends or one terminal of the anhydrosugar alcohol. The biodegradable polyester composite of claim 1, wherein the dicarboxyl component is selected from an aliphatic dicarboxyl compound, an aromatic dicarboxyl compound, or a combination thereof. The biodegradable polyester composite of claim 1, wherein the diol component further comprises an additional diol component in addition to the solid dispersion of the anhydrosugar alcohol and the anhydrosugar alcohol-alkylene glycol. The biodegradable polyester composite of claim 1 , exhibiting a tensile strength greater than 24 MPa. A method for producing a biodegradable polyester composite, comprising:
A solid dispersion of anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol in which the nanomaterial is dispersed therein, comprising the step of polymerizing a diol component and a dicarboxyl component,
Here, the solid dispersion of the anhydrosugar alcohol is obtained by introducing the nanomaterial into the anhydrosugar alcohol in an aqueous dispersion state,
wherein the composite exhibits a standard deviation of tensile strength of 3 MPa or less;
A method for producing a biodegradable polyester composite. The method according to claim 12, wherein the solid dispersion of the anhydrosugar alcohol is mixed with the nanomaterial in an aqueous dispersion state, and melted while removing moisture at a temperature equal to or higher than the melting point of the anhydrosugar alcohol, and then melted A method for producing a biodegradable polyester composite, which is obtained by cooling the mixture to room temperature. A molded article comprising the biodegradable polyester composite of any one of claims 1 to 11. delete