KR20010047581A - Copolyester resin - Google Patents

Abstract

The present invention relates to a copolyester resin, wherein the copolyester resin of the present invention includes an aromatic dicarboxylic acid component as an acid component repeating unit, and ethylene glycol units 55 to 85 relative to all diol components as a diol component repeating unit. Mole% and 15 to 45 mole% of one or more polyethylene glycol units represented by the following Chemical Formula 1 are used, and the intrinsic viscosity measured at 35 ° C. orthochlorophenol is 0.5 to 2.0 dl / g. The copolyester resin according to the present invention has excellent flexibility and is particularly useful not only for plywood lamination or wrapping paper but also for decorative sheet.

In Formula 1, m is an integer of 2 to 4.

Description

Copolyester resin

The present invention relates to co-polyester resins, and more particularly, to co-polyester resins which are excellent in flexibility and are useful not only for plywood lamination and wrapping paper, but especially for cosmetic sheet.

Recently, plastic films used for various purposes are made of various materials such as polyethylene terephthalate, polypropylene, and polyvinyl chloride. Especially, films made of polyvinyl chloride are mainly used for cosmetic plates such as plywood lamination. .

The film used for the decorative plate needs flexibility because it has good adhesion to the decorative plate substrate, that is, plywood, particle board, iron plate, etc. in the bent portion. In this respect, polyvinyl chloride films have been mainly used. However, polyvinyl chloride resins have poor thermal stability, which may cause wrinkles due to heat during the process. Due to various environmental regulations, the market is gradually decreasing.

In order to solve this problem, a film made of polyolefin or polyester has been proposed. However, polyolefin films are poor in scratch resistance and poor in printability, and in particular, are not suitable for bending lamination due to lack of flexibility. In addition, polyester resins, especially polyethylene terephthalate, have not only good mechanical strength, thermal stability and printability, but also excellent durability, chemical resistance, electrical insulation, and environmental friendliness. Not suitable either. Therefore, studies for imparting flexibility to the resin while maintaining the physical properties of the basic polyester are continuing.

For example, US Pat. No. 5,101,009 discloses a copolymerized polyester resin containing terephthalic acid as an acid component and 0.5 to 20 mol% of aliphatic diols having 22 to 34 carbon atoms as a main component of butylene glycol as a diol component. have.

However, this patent does not describe the ductility of the obtained copolyester resin.

Accordingly, the technical problem to be achieved by the present invention is to provide a copolyester resin useful for solving the above problems and excellent flexibility as well as plywood lamination or wrapping paper, in particular for cosmetic sheet.

In order to achieve the above technical problem, the present invention includes an aromatic dicarboxylic acid component as an acid component repeating unit, represented by 55 to 85 mol% of ethylene glycol units and the following general formula (1) relative to the total diol component as a diol component repeating unit 15 to 45 mol% of at least one polyethylene glycol unit is provided, and provides a copolymer polyester resin, characterized in that the intrinsic viscosity measured at 35 ° C. orthochlorophenol is 0.5 to 2.0 dl / g.

<Formula 1>

In Formula 1, m is an integer of 2 to 4.

It is preferable that the copolyester resin of this invention is 20-50 degreeC of glass transition temperature.

The copolyester resin of the present invention preferably has an optical density of 0.3 to 4.0, and more preferably contains 3 to 20% by weight of one or more pigments and / or dyes based on the total weight of the resin. .

Hereinafter will be described in more detail the copolyester resin and the production method according to the present invention.

The present invention includes an aromatic dicarboxylic acid component as an acid component repeating unit, and 55 to 85 mol% of ethylene glycol units and the following at least one polyethylene glycol unit with respect to the total diol components as the diol component repeating unit It provides 15 to 45 mol%, and provides a copolyester resin, characterized in that the intrinsic viscosity measured at 35 ℃, orthochlorophenol is 0.5 to 2.0dl / g.

<Formula 1>

In Formula 1, m is an integer of 2 to 4.

The polyester resin of the present invention polycondenses 15 to 45 mol% of an acid component containing aromatic dicarboxylic acid as a main component and one or more polyethylene glycol units represented by the formula (1) using ethylene glycol as a main component as a diol component repeating unit. You can get it by doing

As aromatic dicarboxylic acid, dimethyl terephthalic acid, terephthalic acid, dimethyl isophthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, 5-sulfoisophthalic acid, 5-sulpop Roxyoxyphthalic acid, diphenyldicarboxylic acid, diphenoxyalkanedicarboxylic acid, adipic acid, sebacic acid may be used.

When the content of the polyethyleneglycol unit of Formula 1 contained as a diol component in the copolyester resin of the present invention is less than 15 mol%, a resin having a level of flexibility suitable for bending lamination cannot be obtained, and when the content exceeds 45 mol%, Glass transition temperature is too low, the thermal stability is poor. The polyethylene glycol content is more preferably 18 to 40 mol%.

The polyethylene glycol of the present invention may be used in any kind of polyethylene glycol within the range defined by the present invention, i.e., in the range of m to 2-4, and two or more kinds of polyethylene glycol may be mixed. The polyethylene glycol unit of the present invention is preferably used by mixing two or more kinds of polyethylene glycol. Although one kind of polyethylene glycol can be used to impart desirable flexibility to the resin, the use of two or more kinds of polyethylene glycols in combination lowers the regularity of the molecular chain. Therefore, when the resin is made into a film, the degree of crystallinity is lowered and the flexibility is also increased.

In the copolyester resin of the present invention, the diol component includes the remaining amount of ethylene glycol units in addition to the polyethylene glycol units of the above content. The ethylene glycol unit maintains the glass transition temperature of the copolyester resin to a certain level or more, and imparts mechanical properties of polyester to the resin.

Copolymerization of such diol components can be carried out according to a conventional polymerization method, and is not particularly limited.

The diol component of the present invention is, for example, alkylene glycols such as 1,3-propanediol, 1,4-butanediol and 2,2-dimethyl-1 in a range that does not impair the flexibility of the copolyester resin of the present invention. , 3-propanediol, 1,4-cyclohexanedimethanol and the like.

It is preferable that the copolyester resin of this invention is melt | dissolved in 25 ml of orthochlorophenol at the density | concentration of 0.05%, 0.1%, and 0.15% at 35 degreeC, and the intrinsic viscosity measured by the 3-point method is 0.5-2.0 dl / g. If the intrinsic viscosity is less than 0.5 dl / g, breakage occurs during stretching in the film with the copolyester resin of the present invention not only decreases the productivity but also the mechanical strength of the final product is poor. In addition, when the intrinsic viscosity exceeds 2.0 dl / g, the melt viscosity of the resin is excessively high, there is a difficulty in the extrusion process of the resin. It is preferable that the glass transition temperature of the final co-polyester resin is 20-50 degreeC, and it is preferable that melting | fusing point is 160-210 degreeC.

In order to impart hiding power or color to the resin, the copolyester resin of the present invention preferably further contains 3 to 20% by weight of one or more pigments and / or dyes based on the total weight of the resin. Pigments and / or dyes to be added to the resin may be any pigment or dye as long as it has thermal stability to withstand the melt extrusion process of 200 to 300 ℃. In order to give a resin the desired color, you may mix and use 2 or more types of pigment and / or dye. As the pigment, for example, titanium dioxide, barium sulfate, carbon black, iron oxide, metal complexes, chromate fragments, azo pigments, quinacridones and dyeing lakes can be used, and titanium dioxide is particularly easy to color the resin. As the dye, for example, monoazo, disazo, anthraquinone, bat dye, modant dye, or the like can be used.

If the content of the pigment and / or dye to be added to the copolyester resin of the present invention is less than 3% by weight based on the total weight of the resin it is difficult to obtain the desired hiding power, if it exceeds 20% by weight of the physical properties of the film made of the resin is poor And breakage of the film frequently occurs during the production process, resulting in poor production.

When the film is prepared from the copolyester resin according to the present invention, the hiding power of the film varies depending on the thickness of the film even when the concentration of the added pigment and / or dye is the same, but in order to be used for a cosmetic plate (optical density, hereinafter referred to as OD) is preferably 0.3 to 4.0. In this range, the surface defects of the cosmetic plate substrate, that is, plywood or particle board, iron plate, etc. can be maintained without the physical properties of the film.

In preparing the film with the copolyester resin of the present invention, in order to improve the running property of the film, the resin may further include inorganic and / or organic fine particles in a range that does not affect the physical properties of the final film. The inorganic fine particles that can be used at this time include silica, alumina, calcium carbonate, and the like, and polycarbonate, polymetal methacrylate, and the like can be used as the organic fine particles. These microparticles | fine-particles can be added individually or in mixture of 2 or more types. The average particle diameter of these fine particles is preferably 0.01 to 0.1 μm, and the amount of the fine particles is preferably 0.1 to 2.0 wt% based on the total amount of the resin.

The method for producing a film with the copolyester resin of the present invention is not particularly limited, and can be produced according to, for example, a commonly known tee-die method or inflation method.

Taking the tee-di method as an example, a copolyester resin obtained by condensation polymerization of an aromatic dicarboxylic acid component with a diol component of polyethylene glycol and ethylene glycol is melted, and then extruded through a tee die to cool on a rotating casting drum. Solidify to obtain an amorphous sheet. The sheet thus obtained is continuously uniaxially or biaxially stretched to obtain a uniaxial or biaxially stretched polyester film. In some cases, the film may be heat treated at 140 to 200 ° C. to impart dimensional stability.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, it is a matter of course that the scope of the present invention is not limited to the following examples.

<Example>

Example 1

100 parts by weight of dimethyl terephthalate, 30 parts by weight of ethylene glycol and 28 parts by weight of triethylene glycol were added to the reactor, heated to 150 ° C for melting, tetraisopropyl titanate was added as a transesterification catalyst, and the reaction by-products were continued. The reaction was removed for 3 hours. Subsequently, the tetraisopropyl titanate catalyst was further added, and the temperature was raised to 240 ° C. while applying a vacuum to 1 mmTorr or less for 1 hour. Then, the reaction was carried out for 6 hours to obtain a copolyester resin (A) and the content and physical properties of the components are shown in Table 1.

100 parts by weight of the copolymerized polyester resin (A) thus prepared was mixed with an additive consisting of 56 parts by weight of titanium dioxide, 30 parts by weight of zinc-ferrite, and 4 parts by weight of carbon black, using a twin screw compounder to prepare a colored copolymerized polyester masterbatch. Was prepared.

After mixing 75% by weight of the copolymerized polyester resin (A) and 25% by weight of the colored copolymerized polyester master batch, melt extrusion was carried out at 210 ° C. through a T-die to prepare an amorphous sheet, and continuously at 60 ° C. in the longitudinal direction. 2.8 times and 3.2 times in the transverse direction at 120 ℃ to prepare a biaxially stretched copolymer polyester film having a thickness of 50㎛.

The physical properties of the polyester film thus prepared are shown in Table 2.

Examples 2 to 3 and Comparative Examples 1 to 4

Except for using ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol as a diol component of the copolyester, it was prepared in the same manner as in Example 1 to prepare a copolyester resin and its components The content and physical properties of are shown in Table 1.

After preparing the colored copolymer master batch by mixing the additives having the same configuration as in Example 1 to the copolymerized polyester resin thus prepared, and mixed with the copolymerized polyester resin to include a pigment / dye content as shown in Table 2 And the film was manufactured by the method similar to Example 1, and the physical property is shown in Table 2.

Example 4

To 100 parts by weight of the copolymerized polyester resin prepared in the same manner as in Example 1, an additive consisting of 59 parts by weight of titanium dioxide and 10 parts by weight of CI Pigment Yellow 119 as an inorganic pigment, and 2 parts by weight of CI Solvent Yellow 179 as a dye were mixed. To prepare a colored copolymerization master batch. Subsequently, the copolymerized polyester resin and the color copolymerization master batch were mixed to include the pigment / dye content as shown in Table 2, and a film was prepared in the same manner as in Example 1, and the physical properties thereof are shown in Table 2.

Example 5

A copolyester resin was prepared in the same manner as in Example 1. The additives having the same composition as in Example 4 were mixed with the copolyester resin thus prepared to prepare a colored copolymer master batch, and then mixed with the copolyester resin to include pigment / dye content as shown in Table 2. And the film was manufactured by the method similar to Example 1, and the physical property is shown in Table 2.

Various performance evaluations of the copolyester resin and the film prepared according to the Examples and Comparative Examples were carried out as follows, the results are shown in Table 2.

(1) Content of Copolymerization Component

The copolyester resin was dissolved in deuterium-substituted trifluoroacetic acid at a concentration of 20% by weight, and the concentration of each copolymerized component was determined by using 300 MHz ¹ H NMR of JEOL.

(2) extreme viscosity

0.0125 g, 0.025 g and 0.0375 g of copolyester resin were dissolved in orthochlorophenol, respectively, to prepare a solution with a volume of 25 ml, and then the relative viscosity was measured at 35 ° C., and extrapolated when the resin concentration was 0. The ultimate viscosity was obtained.

(3) Glass transition temperature and melting point

The glass transition temperature and melting point were measured using a Perkin Elmer's differential scanning thermal analyzer (DSC-7) at a heating rate of 10 ° C./min.

(4) tensile strength and tensile modulus

Measurement was made using an Instron UTM instrument.

(5) hiding power

Optical Density was measured using a Mcbeth Densitometer (Model: TR927).

(6) color

Visual evaluation under natural light was performed according to Universal Language Level 1.

(7) heat shrinkage

After leaving for 30 minutes in a state where there is no tension in an oven at 120 ℃, the length before and after standing was measured and calculated by the following equation.

Thermal Shrinkage (%) = [(L- ) / L] × 100

Where L is the length of the resin before heat treatment, Is the length of the resin after the heat treatment.

(8) Flexural Lamination Processability

Tensile modulus and breaking strength were measured while the prepared film was heated to 50 ° C., and the bending lamination processability was measured based on the following criteria.

◎: Excellent (when tensile modulus of elasticity is less than 5kg / mm2 and elongation at break is 300% or more)

: Good (tensile modulus of 5kg / mm2 or more, 20kg / mm2, and elongation at break is 300% or more)

(Triangle | delta): Moderate (when tensile modulus is 20 kg / mm <2> or more and elongation at break is 300% or more)

X: Poor (when tensile modulus is 20kg / mm2 or more and elongation at break is 300% or less)

In Table 1, DEG, TEG and Tet-EG refer to diethylene glycol, triethylene glycol and tetraethylene glycol, respectively.

In Table 2, Br, Or and Ye refer to brown, orange and yellow colors, respectively.

Referring to Table 1 and Table 2, when the film is produced with the copolymerized polyester resins of Examples 1 to 5 having the polyethylene glycol component according to the present invention, the tensile modulus is low and the tensile elongation is large, so the bending lamination processability is excellent and the glass is excellent. While the transition temperature is relatively high, the dimensional stability against heat is excellent, whereas the copolymerized polyester resins (Comparative Examples 2 and 3) in which the polyethyleneglycol component exceeds the content of the present invention have low glass transition temperature, indicating poor dimensional stability. have. In addition, the polyester resin (Comparative Example 1) which does not contain a polyethylene glycol component is poor in flexibility in manufacturing into a film, and is poor in lamination workability.

On the other hand, the co-polyester film in which the dye and / or pigment is added according to the present invention is excellent in hiding power, but can be usefully used for the decorative plate substrate, the co-polyester film (Comparative Example 4) is less than 3% by weight pigment It can be seen that the hiding power is poor.

As described above, the copolyester resin according to the present invention has excellent flexibility in manufacturing into a film and good hiding power when dyes and / or pigments are added in the content according to the present invention, so that not only plywood lamination or wrapping paper, but especially a sheet for cosmetic plates Useful for

Claims (8)

An aromatic dicarboxylic acid component as an acid component repeating unit, 15 to 45 mol of ethylene glycol units and at least one polyethylene glycol unit represented by the following general formula (1) relative to the total diol component as a diol component repeating unit Copolyester resin, characterized in that the intrinsic viscosity is 0.5 to 2.0dl / g, including the%, measured in 35 ℃, orthochlorophenol. <Formula 1> In Formula 1, m is an integer of 2 to 4. The method of claim 1, wherein the aromatic dicarboxylic acid component is dimethyl terephthalic acid, terephthalic acid, dimethylisophthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, 5-sulfoy Co-polyester, characterized in that at least one selected from the group consisting of sophthalic acid, 5-sulfopropoxyisophthalic acid, diphenyldicarboxylic acid, diphenoxyalkanedicarboxylic acid, adipic acid, sebacic acid Suzy. The copolyester resin according to claim 1, wherein the glass transition temperature is 20 to 50 ° C. The copolyester resin according to claim 1, further comprising 3 to 20% by weight of at least one pigment and / or dye based on the total weight of the resin. The copolymer according to claim 4, wherein the pigment is at least one selected from the group consisting of titanium dioxide, barium sulfate, carbon black, iron oxide, metal complex, chromate pigment, azo pigment, quinacridone and dyeing lake. Polyester resin. The copolyester resin according to claim 4, wherein the dye is at least one selected from the group consisting of monoazo, disazo, anthraquinone, bat dye, and modant dye. The copolyester resin according to claim 4, wherein the optical density is 0.3 to 4.0. The copolyester resin according to claim 1, further comprising any one or more inorganic and / or organic fine particles selected from the group consisting of silica, alumina, calcium carbonate, polycarbonate, and polymetal methacrylate.