KR20070022974A - Process of the production for translucent frost-look sheet of co-polyester - Google Patents

Abstract

The present invention relates to a method for producing a copolyester-based semi-transparent matt sheet, 90 to 99.9% by weight of a transparent polyester copolymerized with 1,4-cyclohexanedimethanol having an intrinsic viscosity of 0.60 to 1.0 dl / g and a melt index ( MI) is characterized by extrusion molding after mixing a sheet raw material containing 0.1 to 10% by weight of polyolefin having 0.005 to 40 g / 10 minutes.

According to the method of the present invention, the transparency of a sheet containing transparent copolyester as a main raw material can be reduced without additives or coating steps, thereby producing a translucent sheet applicable to a high-grade interior. In addition, it is possible to omit a separate additive master batch production process or coating process has the advantage of improving workability and cost reduction.

Copolyester, Translucent, Matte, Sheet, Polyolefin

Description

Process of the production for translucent frost-look sheet of co-polyester}

The present invention relates to a method for producing a copolyester-based translucent matte sheet. More specifically, the present invention relates to a method for producing a semi-transparent matt sheet by extrusion molding using transparent copolyester and polyolefin containing 1,4-cyclohexanedimethanol as a main component.

In general, in the case of a sheet made of a transparent copolyester resin mainly composed of 1,4-cyclohexanedimethanol as a raw material, the sheet is transparent and its inherent luster is expressed on the sheet surface.

On the other hand, the matting effect and / or translucent effect is sometimes used as a high-grade interior sheet or frame cover, but until now, the surface of the sheet is cut by processing the surface of the cooling roll to produce the matting or translucent effect on the plastic sheet. By processing like glass, light has been diffused to make the sheet opaque.

However, in the case of the copolyester resin, even if the processed cooling roll is used, the surface is smooth again because cooling is slow, and this method cannot be used. Therefore, a method of reducing transparency by mixing a certain amount of inorganic materials such as silica or talc is used. When using this method, the surface is not smooth by silica or talc particles, for this reason, when manufacturing a thick sheet, there is a disadvantage in that the adhesion between the sheet and the cooling roll is poor and the sheet falls off the cooling roll.

Therefore, in the present invention, as a result of extensive research in order to solve the above-mentioned problems of the prior art, a polyolefin, which is a material having a large difference in flowability and incompatibility with the transparent copolyester, is blended with the copolyester to form a copolyester. By removing the homogeneity, the glossiness inherent in the copolyester resin is primarily removed, and the opacity is imparted by using the property that the two resins do not have affinity, thereby producing a matte translucent sheet without adding an additive or coating process. It has been found that the present invention has been completed based on this.

Accordingly, an object of the present invention is to provide a method of manufacturing a semi-transparent matt sheet based on a transparent co-polyester resin that can solve all the problems of the prior art described above.

Method for producing a copolyester-based translucent matte sheet according to the present invention for achieving the above object:

90 to 99.9 weight percent of a transparent polyester copolymerized with 1,4-cyclohexanedimethanol having an intrinsic viscosity of 0.60 to 1.0 dl / g and 0.1 to 10 weight percent of a polyolefin having a melt index (MI) of 0.005 to 40 g / 10 minutes. It is characterized by extrusion molding after mixing the sheet raw material.

Here, the copolyester includes 5 to 100 mol% of 1,4-cyclohexanedimethanol with respect to the dicarboxylic acid component.

The polyolefin is polyethylene or polypropylene, preferably polyethylene.

The sheet stock may also further comprise an inorganic matting agent such as silica or talc.

The mixed raw material sheet may be extruded or coextruded into a single layer structure, and during the coextrusion, the raw material sheet is formed at least on the outer surface of the product.

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

As described above, in the present invention, the transparency of the sheet made of transparent co-polyester as a main raw material can be reduced without additives or coating steps, thereby producing a translucent sheet that can be applied to a high-end interior.

According to the method of the present invention, sheet extrusion is performed after mixing a sheet raw material comprising 90 to 99.9% by weight of a transparent polyester resin copolymerized with 1,4-cyclohexanedimethanol and 0.1 to 10% by weight of a polyolefin resin as an initial raw material. Extrusion molding is carried out in a molding machine to prepare a copolyester-based translucent matte sheet.

The transparent copolyester resin used in the present invention has an intrinsic viscosity of 0.60 to 1.0 dl / g, preferably 0.70 to 0.80 dl / g. In this case, when the intrinsic viscosity of the copolyester resin is less than 0.60dl / g, the physical properties of the extruded sheet are too low, and when it exceeds 1.0dl / g, the melt viscosity is too high, making it difficult to extrusion.

The transparent co-polyester resin is prepared by the first step of the esterification reaction and the second step of the polycondensation reaction of the dicarboxylic acid component containing terephthalic acid and the diol component containing 1,4-cyclohexanedimethanol do.

The first step, the esterification reaction may be carried out in a batch or continuous manner, and each raw material may be added separately, but it is most preferable to make a dicarboxylic acid component into a diol component in a slurry form. .

Terephthalic acid may be used as a main component as the dicarboxylic acid component, and in addition, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, Glutaric acid, adipic acid, sebacic acid, 2,6-naphthalenedicarboxylic acid, and the like, but are not particularly limited thereto.

As the diol component, 1,4-cyclohexanedimethanol may be used as a main component, and the amount of the diol component is 5 to 100 mol%, preferably 10 to 80 mol%, more preferably relative to the dicarboxylic acid component. 20 to 40 mol% is most suitable in terms of the desired physical properties.

As the diol component, in addition to ethylene glycol and other glycol compounds, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6 -Hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and the like can be used.

The esterification reaction does not require a catalyst, but may be optionally added to reduce the reaction time.

After the first step of the above-mentioned esterification reaction is completed, the second step of the polycondensation reaction is carried out, which is usually used in the polycondensation reaction to the esterification reactants obtained in the first step before initiating the polycondensation reaction. As a component, a polycondensation catalyst, a stabilizer, a coloring agent, etc. can be selectively used as needed.

On the other hand, the polyolefin resin used in combination with the transparent co-polyester resin prepared in this way is 0.005 ~ 40g / 10 minutes, preferably 0.06 ~ 1.0g / in a Melting Index (MI) of 2.16kg at 190 ℃ 10 minutes is suitable. In this case, when the melt index of the polyolefin resin is out of the above range, since the melt viscosity of the olefin resin is too much different from the melt viscosity of the transparent co-polyester resin, it is difficult to mix well.

Examples of the polyolefin used in the present invention include polyethylene (PE) or polypropylene (PP), and preferably polyethylene.

On the other hand, the amount of the polyolefin resin used when mixing with the transparent co-polyester resin is preferably 0.1 to 10% by weight, preferably 0.5 to 5% by weight. When the amount of the polyolefin resin is less than 0.1% by weight, it is difficult to implement a translucent effect, and when the amount of the polyolefin resin is more than 5% by weight, the permeability is too low to express the effect of the high-quality translucent sheet.

As a method of mixing such a transparent copolyester resin and a polyolefin resin, the copolyester polyester chip and the oligoolefin chip may be directly mixed at a predetermined mixing ratio when the sheet is extruded, but the two kinds of resins may be used in a separate chip state. It is also possible to prepare and use a mixed master batch with two resins without using the present invention, in which case there is an advantage that the copolymerized polyester resin and the polyolefin may be better mixed.

On the other hand, in order to increase the matte effect of the sheet to be molded, an inorganic matting agent such as silica or talc may be additionally used, the amount of which is used is 0.01 to 20% by weight, preferably 1 to 5% by weight. Is typical. The matting agent may be added when producing the mixed master batch of the copolyester resin and the polyolefin resin. Preferably, the co-extrusion may include a matting agent as the outer surface layer of the molded sheet.

On the other hand, when the co-polyester resin and the polyolefin resin are mixed in a general sheet extruder, the sheet product is molded into a single layer structure. On the other hand, in the case of an extruder capable of forming a multilayer structure by co-extrusion, only the outer surface layer of the molded product may be composed of blending of a copolyester polyester resin and a polyolefin resin, or may be formed through a conventional coextrusion molding method. It may be, but preferably at least on the outer surface of the product to form a raw material sheet comprising the copolyester resin and polyolefin resin.

Hereinafter, the method of manufacturing the copolyester-based semitransparent matte sheet of the present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the scope of the present invention is not limited thereto.

Example 1

A transparent copolyester (hereinafter referred to as PETG) chip having an intrinsic viscosity of 0.78 dl / g and copolymerized with 30 mol% of 1,4-cyclohexanedimethanol relative to an acid component, and a melt index (hereinafter referred to as MI). A high density polyethylene (hereinafter referred to as HDPE) chip having a value of 0.10 g / 10 min was used as a raw material. PETG was dried at 65 ° C. for 6 hours in a dehumidifying dryer before injection, and HDPE was dried at 80 ° C. for 10 hours in a vacuum dryer. Immediately before extrusion, PETG: HDPE was mixed at a ratio of 99.5: 0.5 in a rotary stirrer and introduced into the extruder hopper. The extruder produced a sheet of 0.5 mm using a small HAAKE torque rheometer. The cylinder temperature and die temperature of the extruder were set to 240 ° C., and the chill roll temperature to 40 ° C.

Example 2

To prepare the same thickness sheet using the same extruder as in Example 1, the PETG used was HDPE having an intrinsic viscosity of 0.78 dl / g, MI of 0.10g / 10 minutes. Drying in the same manner as in Example 1, PETG: PE was blended in a ratio of 99: 1 in a rotary stirrer immediately before extrusion, and introduced into an extruder hopper. The cylinder temperature and die temperature of the extruder were set to 240 ° C., and the chill roll temperature to 40 ° C.

Example 3

To prepare the same thickness sheet using the same extruder as in Example 1, the PETG used was HDPE having an intrinsic viscosity of 0.78 dl / g, MI of 0.10g / 10 minutes. Drying was carried out in the same manner as in Example 1, and blended PETG: PE in a ratio of 97: 3 in a rotary stirrer immediately before extrusion to the extruder hopper. The cylinder temperature and die temperature of the extruder were set to 240 ° C., and the chill roll temperature to 40 ° C.

Example 4

To prepare the same thickness sheet using the same extruder as in Example 1, the PETG used was HDPE having an intrinsic viscosity of 0.78 dl / g, MI of 0.10g / 10 minutes. Drying in the same manner as in Example 1 and blended PETG: PE in a ratio of 95: 5 in a rotary stirrer immediately before extrusion was introduced into the extruder hopper. The cylinder temperature and die temperature of the extruder were set to 240 ° C., and the chill roll temperature to 40 ° C.

Example 5

Using the same extruder as in Example 1 to produce a sheet of the same thickness, used PETG polypropylene (hereinafter referred to as PP) having an intrinsic viscosity of 0.78dl / g, MI 0.10g / 10 minutes It was. Drying in the same manner as in Example 1 and blended PETG: PP in a 99.5: 0.5 ratio in a rotary stirrer immediately before extrusion to the extruder hopper. The cylinder temperature and die temperature of the extruder were set to 240 ° C., and the chill roll temperature to 40 ° C.

Example 6

To prepare a sheet of the same thickness using the same extruder as in Example 1, the PETG used was PP having an intrinsic viscosity of 0.78 dl / g, MI of 0.10 g / 10 minutes. Drying in the same manner as in Example 1, PETG: PP was blended in a 99: 1 ratio in a rotary stirrer immediately before extrusion, and introduced into an extruder hopper. The cylinder temperature and die temperature of the extruder were set to 240 ° C., and the chill roll temperature to 40 ° C.

Example 7

To prepare a sheet of the same thickness using the same extruder as in Example 1, the PETG used was PP having an intrinsic viscosity of 0.78 dl / g, MI of 0.10 g / 10 minutes. Drying in the same manner as in Example 1 and blended PETG: PP in a ratio of 97: 3 in a rotary stirrer immediately before extrusion to the extruder hopper. The cylinder temperature and die temperature of the extruder were set to 240 ° C., and the chill roll temperature to 40 ° C.

Example 8

To prepare a sheet of the same thickness using the same extruder as in Example 1, the PETG used was PP having an intrinsic viscosity of 0.78 dl / g, MI of 0.10 g / 10 minutes. Drying in the same manner as in Example 1, PETG: PP was blended in a ratio of 95: 5 in a rotary stirrer immediately before extrusion, and introduced into an extruder hopper. The cylinder temperature and die temperature of the extruder were set to 240 ° C and the chill roll temperature to 40 ° C.

Comparative Example 1

Using the same molding machine used in Example 1, 100% of PETG resin was used as a raw material to form sheets of the same thickness. PETG was dried using a MOTAN dehumidifying dryer and dried for 6 hours using heated air at a drying temperature of 65 ° C. and a dew point of −40 ° C. The cylinder temperature and die temperature of the extruder were set to 240 ° C and the chill roll temperature was maintained at 40 ° C.

Thus, in order to measure the physical properties of the extruded sheet produced according to the method of Examples 1 to 8 and Comparative Example 1, by measuring the haze (Transmittance) and the haze (HAZE) using a haze meter (NIZEON DENSHOKU) The results are shown in Table 1 below.

No. Haze Permeability ° Example 1 14.7 89.1 Example 2 42.4 87.2 Example 3 71.0 84.2 Example 4 75.9 80.8 Example 5 8.3 88.8 Example 6 52.3 82.3 Example 7 90.6 65.4 Example 8 91.3 61.8 Comparative Example 1 1.9 89.8

Sheet products molded according to the method of Examples 1 to 8 had a translucent white tone, the surface was significantly reduced in transparency than the product of Comparative Example 1 molded with 100% copolyester and the haze degree shown in Table 1 above It can be seen that the value comes out significantly higher than Comparative Example 1.

As described above, according to the present invention, it is possible to manufacture a high-quality interior translucent sheet by reducing the transparency, which is a characteristic of the sheet mainly made of transparent copolyester, without any additives or coating process.

In addition, there is an advantage that can be produced by adding a polyolefin immediately without producing a master batch of additives, thereby improving workability and cost reduction.

It is apparent that modifications and improvements are possible by those skilled in the art within the spirit or scope of the present invention. Accordingly, the simple modifications and variations of the present invention are all within the scope of the present invention, and the specific scope of protection of the present invention will be clarified by the appended claims and their equivalents.

Claims (7)

90 to 99.9 wt% of a transparent polyester copolymerized with 1,4-cyclohexanedimethanol having an intrinsic viscosity of 0.60 to 1.0 dl / g and 0.1 to 10 wt% of a polyolefin having a melt index (MI) of 0.005 to 40 g / 10 min. A method for producing a copolyester-based semitransparent matte sheet, which comprises extrusion of a sheet raw material to be extruded. The method of claim 1, wherein the copolymerized polyester comprises 5 to 100 mol% of 1,4-cyclohexanedimethanol based on the dicarboxylic acid component. The method of claim 1, wherein the polyolefin is polyethylene or polypropylene. The method of claim 3, wherein the polyolefin is polyethylene. The method according to claim 1, wherein the sheet material further comprises an inorganic matting agent. The method of claim 5, wherein the inorganic matting agent is silica or talc. The method of claim 1, wherein the mixed raw material sheet is extruded or co-extruded in a single layer structure, the co-extrusion molding, the copolymer sheet, characterized in that the raw material sheet is formed on at least the outer surface of the product Method for producing ester translucent matte sheet.