KR101859720B1 - Polyester resin composition and preparation method for highly dispersed potyester resin - Google Patents

Abstract

The present invention relates to a polyester resin composition and to a method for producing a highly dispersed polyester resin, and a highly dispersed polyester resin-derived film produced according to the production method has high transmittance of visible light and excellent light blocking rate in the near infrared region. In addition, the film is excellent in the dispersibility of tungsten oxide and has a low haze, thereby being used in various industrial fields such as automobile, building, windows and the like.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition and a method for producing the same,

The examples relate to a polyester resin composition and a method for producing a highly dispersed polyester resin.

Background Art Polyester films are generally used for various industrial materials such as display devices, containers for beverage filling, medical use, packaging materials, sheets, vehicles, architectural use, and windows. Among them, polyester films in industrial fields that require heat shielding are prepared by coating heat shielding materials on polyester films. However, the tungsten-containing oxide, which is a typical heat shielding material, is required to be highly dispersed and has a difficulty in manufacturing (see Korean Patent No. 10-0701735). In addition, the conventional polyester film prepared by coating a heat shielding material has problems such as a decrease in production efficiency at the time of post-processing, an additional process for coating a heat shielding material, and a problem that a coating layer of a heat shielding material is exposed to the external environment There is a problem that the physical properties of the film such as weather resistance are deteriorated.

Korean Patent No. 10-0701735

Thus, the examples are a polyester resin composition capable of producing a polyester resin excellent in dispersibility of a tungsten-containing oxide by introducing a tungsten-containing oxide into a polymerization step of the polyester resin, and a method of producing a highly dispersed polyester resin using the same .

In order to achieve the above object,

A polyester resin composition comprising an ester-based prepolymer, cesium-doped tungsten oxide nanoparticles, a dispersion stabilizer and a surfactant,

Wherein the polyester resin composition contains the cesium-doped tungsten oxide nanoparticles in an amount of 0.1 to 10% by weight based on the total weight of the polyester resin composition.

According to another aspect of the present invention,

Adding a dispersion stabilizer, a surfactant and cesium-doped tungsten oxide nanoparticles to the ester-based prepolymer, and heating and polymerizing,

Wherein the cesium-doped tungsten oxide nanoparticles are used in an amount of 0.1 to 10% by weight based on the total weight of the polymer composition.

According to another aspect of the present invention,

And a highly dispersed polyester resin prepared according to the above production method,

An average transmittance of light having a wavelength of 400 to 780 nm is 50% or more, a light blocking rate of 950 nm is 50% or more,

And a haze measured at 25 占 폚 of a sample of 210 mm 占 297 mm 占 25 占 퐉 (width 占 length 占 thickness) is less than 5%.

The film produced from the highly dispersed polyester resin produced according to one embodiment has high transmittance of visible light and excellent light blocking rate in the near infrared region. In addition, since the film has excellent dispersibility of tungsten oxide and has a low haze of the film, it can be usefully used in various industrial fields such as automobile, building and window.

1 is a photograph of the appearance of the near-infrared ray blocking film produced in Examples 1 to 3 and Comparative Examples 1 to 3.
FIG. 2 is an ultraviolet-visible ray spectrum of the near infrared ray blocking films of Examples 1 to 3.
3 is an ultraviolet-visible light spectrum measured for the near infrared ray blocking films of Comparative Examples 1 to 3.

The polyester resin composition according to one embodiment is a polyester resin composition comprising an ester-based prepolymer, cesium-doped tungsten oxide nanoparticles, a dispersion stabilizer and a surfactant, wherein the polyester resin composition contains the cesium And the doped tungsten oxide nanoparticles in an amount of 0.1 to 10% by weight.

The polyester resin composition comprises 30 to 70% by weight of an ester-based prepolymer, 0.1 to 10% by weight of cesium-doped tungsten oxide nanoparticles, 0.1 to 30% by weight of a dispersion stabilizer and 0.1 to 30% Of surfactant . Specifically, the polyester resin composition comprises 45 to 70% by weight of an ester-based prepolymer, 0.5 to 5% by weight of cesium-doped tungsten oxide nanoparticles, 0.5 to 30% by weight of a dispersion stabilizer, 20 wt% surfactant < RTI ID = 0.0 > . More specifically, the polyester resin composition comprises 50 to 70 wt% of an ester-based prepolymer, 0.5 to 3 wt% of cesium-doped tungsten oxide nanoparticles, 1 to 30 wt% of a dispersion stabilizer, and 1 To 20% by weight of a surfactant . When the cesium-doped tungsten oxide nanoparticles are contained within the above-mentioned content range, it is economical because of the excellent effect of blocking the near-infrared ray compared to the addition amount of the nanoparticles, and the haze of the film can be controlled to less than 10%.

Ester system Prepolymer

The term "prepolymer" generally means a polymer having a relatively low molecular weight in which a degree of polymerization is interrupted at an intermediate stage in order to easily form a final molded product. The prepolymer may be formed by itself or after reacting with another polymerizable compound, and may be prepared, for example, by esterifying a diol compound and a dicarboxylic acid compound.

Examples of the diol compound used in the preparation of the ester-based prepolymer include ethylene glycol, 1,4-cyclohexanedimethanol, 1,3-propanediol, 1,2-octanediol, Butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol) 1,3-propanediol, 2,2-diethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl- -Dimethyl-1,5-pentanediol, spiroglycol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane ) And diethylene glycol (2- (2-hydroxyethoxy) ethan-1-ol).

Examples of the dicarboxylic acid compound used in the preparation of the ester-based prepolymer include aromatic dicarboxylic acids such as terephthalic acid, dimethylterephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and orthophthalic acid; Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid; Alicyclic dicarboxylic acid; Esters thereof; And mixtures thereof.

Cesium Doped  Tungsten oxide nanoparticles

The cesium-doped tungsten oxide nanoparticles may be represented by CsWO _x, where X may be from 1 to 10. Specifically, the cesium-doped tungsten oxide nanoparticles may be represented by CsWO _x, where X may be from 3 to 5.

The cesium-doped tungsten oxide nanoparticles may have an average diameter of 1 to 800 nm. Specifically, the cesium-doped tungsten oxide nanoparticles may have an average diameter of 50 to 600 nm, 50 to 500 nm, or 70 to 300 nm.

Dispersion stabilizer

The dispersion stabilizer may include at least one selected from the group consisting of 1,1-dichloroethane, potassium hydroxide, sodium hydroxide, adipic acid salt and amide. Specifically, the dispersion stabilizer is selected from the group consisting of 1,1-dichloroethane, potassium hydroxide, sodium hydroxide, poly (1,6-hexamethylene adipate) and N, N'- (N, N'-dibenzyl-1,6-diaminohexane) may be included. More specifically, the dispersion stabilizer includes 1,1-dichloroethane, potassium hydroxide, sodium hydroxide, poly (1,6-hexamethylene adipate) and N, N'-dibenzyl-1,6-diaminohexane can do. More specifically, the dispersion stabilizer may comprise 1 to 20% by weight of 1,1-dichloroethane, 1 to 20% by weight of potassium hydroxide, 1 to 20% by weight of sodium hydroxide, 10 to 50% by weight of Poly (1,6-hexamethylene adipate) and 20 to 60% by weight of N, N'-dibenzyl-1,6-diaminohexane.

The poly (1,6-hexamethylene adipate) may have a number average molecular weight of 100 to 10,000. Specifically, the poly (1,6-hexamethylene adipate) may have a number average molecular weight of 1,000 to 10,000, 1,000 to 7,000, or 1,000 to 5,000.

Surfactants

The surfactant may include at least one member selected from the group consisting of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfate, sodium hexylbenzenesulfonate, and citric acid. Specifically, the surfactant may include sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfate, sodium hexylbenzenesulfonate, and citric acid. More specifically, the surfactant comprises 10 to 50 wt.% Sodium dodecylsulfate, 10 to 40 wt.% Sodium dodecylbenzenesulfonate, 1 to 20 wt.% Sodium dodecylnaphthalenesulfate, 1 to 20% by weight of sodium hexylbenzenesulfonate and 10 to 50% by weight of citric acid .

According to one embodiment of the present invention, there is provided a method for producing a highly dispersed polyester resin comprising the steps of adding a dispersion stabilizer, a surfactant and cesium-doped tungsten oxide nanoparticles to an ester-based prepolymer and heating and polymerizing the cesium-doped tungsten The oxide nanoparticles are used in an amount of 0.1 to 10% by weight based on the total weight of the polymer composition.

In the above method, cesium-doped tungsten oxide nanoparticles are added during the polymerization of the polyester resin to increase the degree of dispersion of the nanoparticles to increase the transmittance of the visible light and the light blocking rate of the near infrared region. Can be manufactured.

The ester-based prepolymer, dispersion stabilizer, surfactant and cesium-doped tungsten oxide nanoparticles are as described for the polyester resin composition.

Wherein the polymeric composition comprises from 30 to 70% by weight of ester based prepolymer, from 0.1 to 10% by weight of cesium-doped tungsten oxide nanoparticles, from 0.1 to 30% by weight of a dispersion stabilizer and from 0.1 to 30% Active agent . Specifically, the polymer composition comprises 45 to 70% by weight of ester based prepolymer, 0.5 to 5% by weight of cesium-doped tungsten oxide nanoparticles, 0.5 to 30% by weight of a dispersion stabilizer and 0.5 to 20% by weight % Of surfactant . More specifically, the polymer composition comprises 50 to 70% by weight of an ester based prepolymer, 0.5 to 3% by weight of cesium doped tungsten oxide nanoparticles, 1 to 30% by weight of a dispersion stabilizer, and 1 to 20 By weight of surfactant . When the cesium-doped tungsten oxide nanoparticles are contained within the above-mentioned content range, it is economical because of the excellent effect of blocking the near-infrared ray compared to the addition amount of the nanoparticles, and the haze of the film can be controlled to less than 10%.

 In the highly disperse polyester resin, the cesium-doped tungsten oxide nanoparticles are added to the ester-based prepolymer, and the mixture is heated to 80 to 180 ° C for primary polymerization. Then, a dispersion stabilizer and a surfactant are added and heated to 100 to 200 ° C Followed by secondary polymerization.

The highly disperse polyester resin prepared according to the above-described preparation method may have an intrinsic viscosity (IV) of 0.35 to 1.50 dl / g.

Near infrared  Barrier film

In addition, one embodiment includes a highly dispersed polyester resin produced according to the above-described production method, and has an average transmittance of 50% or more of light having a wavelength of 400 to 780 nm and a light blocking rate of 950 nm %, And a haze measured at 25 占 폚 of a sample of 210 mm 占 297 mm 占 25 占 퐉 (width 占 length 占 thickness) is less than 5%. Specifically, the near-infrared ray blocking film has an average transmittance of light having a wavelength of 400 to 780 nm of 50 to 85%, a blocking rate of light having a wavelength of 950 nm of 50 to 80%, a size of 210 mm x 297 mm x 25 m (width x Length x thickness) of 0.1 to 4% or 0.1 to 2% as measured on a sample at 25 캜.

The near infrared ray shielding film may have a thickness of 15 to 50 mu m. Specifically, the near-IR blocking film may have a thickness of 20 to 35 탆. The near-IR blocking film may be in the form of unstretched, uniaxially stretched, biaxially stretched, or the like.

The near infrared ray blocking film has a high average transmittance of visible light having a wavelength of 400 to 780 nm of at least 50% and an average transmittance of light of a near infrared region having a wavelength of 900 to 2000 nm as low as less than 50%.

The near infrared ray blocking film may have a b * value of -1.5 to 1.7 in an L * a * b * color system.

The above-mentioned near infrared ray shielding film is excellent in dispersibility of tungsten oxide and has a low haze of the film, and thus can be usefully used in various industrial fields such as automobiles, architectural use and window.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example  One. High dispersion  Production of polyester resin

1,000 g of terephthalic acid (TPA) and 550 g of ethylene glycol (EG) were mixed and esterified at a temperature of about 170 캜 for about 20 hours to prepare an ester type prepolymer. Thereafter, 430.6 g of a dispersion stabilizer, 215.3 g of cesium-doped tungsten oxide nanoparticles (manufactured by KANPI NANO, product name: ANP-TF, chemical formula: CsWO _x , where x is 3.2 and average particle diameter is 272.2 nm) 21.7 g were added and mixed by stirring.

Examples of the dispersion stabilizer include 1,1-dichloroethane, potassium hydroxide, sodium hydroxide, poly (1,6-hexamethylene adipate) (number average molecular weight: about 3,800) and N, N'- Diaminohexane in a weight ratio of 1: 1: 1: 3: 4 was used. Also, a mixture containing sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfate, sodium hexylbenzenesulfonate and citric acid in a weight ratio of 3: 2: 1: 1: 3 was used as the surfactant Respectively.

The mixed composition was subjected to polymerization reaction at 275 캜 for 3 hours to prepare a highly dispersed polyester resin (weight average molecular weight: 35,000, intrinsic viscosity (IV): 0.68 dl / g).

Example  2 and 3, and Comparative Example  1 to 3

As shown in the following Table 1, a polyester resin was prepared in the same manner as in Example 1, except that the content of cesium-doped tungsten oxide nanoparticles, the surfactant, and the dispersion stabilizer was changed.

Content of CsWO _x Content of Surfactant Content of dispersion stabilizer Example 1 0.5 wt% (21.7 g) 10.0 wt% About 20% Example 2 1.0 wt% (43.5 g) 10.0 wt% About 20% Example 3 1.5 wt% (65.2 g) 10.0 wt% About 20% Comparative Example 1 0.5 wt% (21.7 g) - - Comparative Example 2 1.0 wt% (43.5 g) - - Comparative Example 3 1.5 wt% (65.2 g) - -

Experimental Example  One.

Each of the polyester resins of Examples 1 to 3 and Comparative Examples 1 to 3 was cast at 280 占 폚 to prepare an unstretched sheet, stretched 3.3 times in the MD direction at 78 占 폚, stretched 4.0 times in the TD direction at 135 占 폚 And the film was opened and fixed at 210 캜 for 30 seconds to prepare a near infrared ray blocking film having a thickness of 25 탆. An external view of the near-IR blocking film is shown in Fig.

The properties of the near infrared ray blocking film were evaluated by the following methods, and the results are shown in Table 2 and Figs. 2 and 3 below.

(1) the blocking rate (%) of light having a wavelength of 950 nm

For the near infrared ray shielding film, the blocking rate of light having a wavelength of 950 nm was measured with SD2400 manufactured by EDTM.

(2) Haze (%)

The near infrared ray blocking film was cut into a size of 210 mm × 297 mm × 25 μm (width × length × thickness) and haze of the film was measured by the ASTM D 1003 method using an NDH-5000W haze meter at 25 ° C.

(3) L * a * b * colorimetric system

The color of the near infrared ray blocking film was measured using a spectrophotometer (manufacturer: HunterLab, model: UltraScan Pro).

(4) Ultraviolet-visible light spectrum

The ultraviolet-visible spectrum (UV-VIS spectrum) of the near infrared ray blocking film was measured using SHIMADZU UV-2450. The results are shown in FIGS. 2 and 3.

(%) Of light having a wavelength of 950 nm Haze (%) color L * a * b * Example 1 55 0.8 95 ± 5 -0.3 ± 1.0 0.4 ± 1.0 Example 2 65 1.0 94 ± 5 -0.6 ± 1.0 0.5 ± 1.0 Example 3 75 1.5 93 ± 5 -0.9 ± 1.0 0.6 ± 1.0 Comparative Example 1 10 15.1 94 ± 5 -0.2 ± 1.0 1.0 ± 1.0 Comparative Example 2 55 58.1 84 ± 5 -1.2 ± 1.0 5.4 ± 1.0 Comparative Example 3 75 75.3 72 ± 5 -1.8 ± 1.0 9.3 ± 1.0

As shown in Table 2, the near infrared ray shielding films prepared from the highly disperse polyester resins of Examples 1 to 3 exhibited a significantly lower than 50% blocking ratio of light with a wavelength of 950 nm and a significantly lower haze of less than 3% 3 > near-infrared ray blocking film. The significantly lower haze of the near-IR blocking film according to the embodiment is a result of showing that the dispersion degree of cesium-doped tungsten oxide nanoparticles is high.

As shown in FIGS. 2 and 3, the near infrared ray blocking films of Examples 1 to 3 have a transmittance of visible light having a wavelength of 400 to 780 nm of 50% or more, a transmittance of light having a wavelength of 900 to 2,000 nm in the near- Respectively.

Claims (10)

A polyester resin composition comprising an ester-based prepolymer, cesium-doped tungsten oxide nanoparticles, a dispersion stabilizer and a surfactant,
Wherein the polyester resin composition comprises 30 to 70% by weight of the ester-based prepolymer, 0.1 to 10% by weight of the cesium-doped tungsten oxide nanoparticles, 0.1 to 30% by weight of the dispersion stabilizer, 30% by weight of said surfactant,
Wherein the dispersion stabilizer comprises 1,1-dichloroethane, potassium hydroxide, sodium hydroxide, poly (1,6-hexamethylene adipate) and N, N'-dibenzyl-1,6-diaminohexane,
Wherein the surfactant comprises sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfate, sodium hexylbenzenesulfonate and citric acid,
The film having a thickness of 25 占 퐉 produced from the polyester resin composition had a haze of 0.1 to 4% at 25 占 폚 based on 210 mm 占 297 mm (width x length) and a b * value in the L * a * 1.5 to 1.7, and an average transmittance of light having a wavelength of 900 to 2,000 nm is less than 50%.
delete The method according to claim 1,
Wherein the cesium-doped tungsten oxide nanoparticles have an average diameter of 1 to 800 nm.
delete delete Adding a dispersion stabilizer, a surfactant and cesium-doped tungsten oxide nanoparticles to the ester-based prepolymer, and heating and polymerizing,
Wherein the polymeric composition comprises from 30 to 70% by weight of the ester-based prepolymer, from 0.1 to 10% by weight of the cesium-doped tungsten oxide nanoparticles, from 0.1 to 30% by weight of the dispersion stabilizer and from 0.1 to 30% Of said surfactant,
Wherein the dispersion stabilizer comprises 1,1-dichloroethane, potassium hydroxide, sodium hydroxide, poly (1,6-hexamethylene adipate) and N, N'-dibenzyl-1,6-diaminohexane,
Wherein the surfactant comprises sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfate, sodium hexylbenzenesulfonate and citric acid,
The film having a thickness of 25 占 퐉 produced from the polymer composition had a haze of 0.1 to 4% at 25 占 폚 based on 210 mm 占 297 mm (width x length), a b * value in the L * a * 1.7, and an average transmittance of light having a wavelength of 900 to 2,000 nm is less than 50%.
The method according to claim 6,
Wherein the cesium-doped tungsten oxide nanoparticles have an average diameter of 1 to 800 nm.
delete The method according to claim 6,
The cesium-doped tungsten oxide nanoparticles are added to the ester-based prepolymer, and the mixture is heated to 80 to 180 DEG C to carry out a primary polymerization, then a dispersion stabilizer and a surfactant are added, and the mixture is heated to 100 to 200 DEG C for secondary polymerization, A method for producing a highly dispersed polyester resin.
And a highly dispersed polyester resin prepared according to the production method of any one of claims 6, 7 and 9,
Wherein the average transmittance of light having a wavelength of 400 to 780 nm is 50% or more, and the light blocking rate of a light having a wavelength of 950 nm is 50% or more.

Images