KR102607279B1 - Polymer Resin Composition and Product Comprising the Same, and Polymer Oriented Film - Google Patents

Abstract

The present invention provides a polymer resin composition containing polycarbonate resin and polyester resin, which has high transparency and greatly improved chemical resistance, scratch resistance, and stretch processability.

Description

Polymer resin composition, molded article containing the same, and polymer oriented film {Polymer Resin Composition and Product Comprising the Same, and Polymer Oriented Film}

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0125451 dated September 27, 2017, and all contents disclosed in the document of the Korean Patent Application are included as part of this specification.

The present invention relates to a polymer resin composition, and more specifically, to a polymer resin composition containing polycarbonate resin and polyester resin, which has high transparency and greatly improved chemical resistance, scratch resistance, and stretching processability.

Polycarbonate resin (PC) not only has excellent flame retardancy and fire resistance due to its self-extinguishing properties, but also exhibits excellent impact resistance and heat resistance, so it is used in various fields such as various construction materials, the exterior of electronic products, packaging materials, cases, boxes, and interior and exterior materials. is being used.

Despite these advantages, polycarbonate resin has a problem of changing its appearance color due to low chemical resistance, for example, by various detergents, feminine cosmetics, or hand sanitizers for children, and is very vulnerable to scratches. It is an amorphous resin. Although it has high transparency, it has the disadvantage of being difficult to manufacture in the form of a thin film due to poor stretching processability.

In other words, despite the inherent excellent physical properties of polycarbonate resin, the expansion of its use is limited due to the above limitations.

The purpose of the present invention is to provide a polymer resin composition in which polycarbonate and polyester resin are physically and/or chemically blended or alloyed.

In order to achieve the above object, the present inventor combined polycarbonate resin and polyester resin, especially polyester resin containing two or more different acids, to maintain the transparency of polycarbonate while maintaining chemical resistance and scratch resistance. and succeeded in producing a polymer resin composition with improved stretch processability, thereby completing the present invention.

Hereinafter, the polymer resin composition according to the present invention will be described in more detail.

Prior to this, the terms or words used in this specification and claims should not be construed as limited to their usual or dictionary meanings, and the inventor should appropriately use the concept of terms to explain his or her invention in the best way. It must be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle of definability.

Therefore, the configuration shown in the embodiments described in this specification is only one of the most preferred embodiments of the present invention and does not entirely represent the technical idea of the present invention, and various equivalents can be substituted for them at the time of filing the present application. It should be understood that there may be variations.

In this specification, singular expressions include plural expressions, unless the context clearly dictates otherwise. In this specification, terms such as “comprise,” “comprise,” or “have” are intended to designate the presence of implemented features, numbers, steps, components, or a combination thereof, and are intended to indicate the presence of one or more other features or It should be understood that this does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.

The polymer resin composition according to the present invention,

polycarbonate resin; and

polyester resin containing at least a heterogeneous acid;

Includes,

The weight ratio of the polyester resin to the polycarbonate resin (=polyester resin/polycarbonate resin) is greater than 0.1 and less than 0.8,

The polyester resin is a polycyclohexylenedimethylene terephthalate resin containing terephthalic acid and isophthalic acid,

The polyester resin is characterized as a polycyclohexylenedimethylene terephthalate resin containing terephthalic acid to isophthalic acid in a molar ratio of 99:1 to 75:25.

The polyester resin as described above can exhibit superior effects in terms of mechanical properties, heat resistance, impact resistance, electrical insulation, etc. by controlling the type and content of its components and polymerization conditions, such as viscosity, weight average molecular weight, or Glass transition temperature, etc. can be controlled. Specifically, in order to improve the above effect, the polyester resin has an intrinsic viscosity of 0.4 to 1.2 dl/g, calculated from the viscosity measured at 35°C after being dissolved in the solvent o-chlorophenol (OCP), and a weight average molecular weight ( Mw) may be 10,000 to 100,000 g/mol, and the glass transition temperature may be 0 to 200°C, more specifically 80 to 120°C. Meanwhile, in the present invention, the weight average molecular weight (Mw) refers to a standard polystyrene conversion value measured by gel permeation chromatography (GPC), and the glass transition temperature (Tg) refers to a value measured by differential scanning calorimetry (DSC). This is the temperature measured using.

Specifically, the polyester resin may be a polycyclohexylenedimethylene terephthalate (PCT) copolymer resin prepared by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, and some isophthalic acid in the terephthalic acid. It may be copolymerized in an amount of 25 mol% or less based on 100 mol% of the dicarboxylic acid-derived repeating unit.

In other words, the polyester resin may be a polycyclohexylenedimethylene terephthalate resin having a molar ratio of terephthalic acid to isophthalic acid of 99:1 to 75:25, and the minimum value of isophthalic acid is 1 mol%. or more, and the maximum value of isophthalic acid may be less than 25 mol%.

If the polycyclohexylenedimethylene terephthalate resin that does not contain isophthalic acid is used, the crystallization rate of the polycyclohexylenedimethylene terephthalate resin increases, which means that the melt of the polymer resin composition containing the resin Since it means that it crystallizes quickly, it may result in a decrease in the stretching processability of the polymer resin composition.

On the other hand, in the case of polycyclohexylenedimethylene terephthalate resin containing isophthalic acid, as in the present invention, the crystallization rate may be relatively delayed, and therefore, the resin composition containing it may be formed into a thin film with desired stretching processability. It can be processed into shapes such as sheets or sheets.

Nevertheless, the content of isophthalic acid relative to terephthalic acid must be 1 mol% or more, and if it is less than that, it is difficult to ensure stretch processability of the polymer resin composition for the reasons described above.

If the content of isophthalic acid relative to terephthalic acid is 25 mol% or more, there is a risk of lowering the melting point of polycyclohexylenedimethylene terephthalate resin.

Specifically, in the above case, the melting point is lowered by about 10 degrees or more from 250 to 260 degrees Celsius, which is the melting point of polycyclohexylenedimethylene terephthalate resin.

The melting point is closely related to the processing temperature as it is about 10 degrees or less compared to the processing temperature of the resin. In the above case, processing of polycyclohexylenedimethylene terephthalate resin for polycarbonate resin with a processing temperature of approximately 290 to 300 degrees Celsius The temperature will drop by more than 40 degrees Celsius.

Therefore, if a polymer resin composition consisting of polycarbonate resin and polycyclohexylenedimethylene terephthalate resin is processed at a processing temperature of 290 degrees Celsius, the polycyclohexylenedimethylene terephthalate resin is completely melted and has a high viscosity. In this case, the polycarbonate resin will have a relatively low viscosity since it is at the melting stage.

Therefore, surface defects such as swells or wrinkles may be formed on the surface of the solidified product due to the difference in viscosity between the two resins. Additionally, the difference in viscosity is a major cause of deterioration in stretching processability.

Therefore, it is important that the content of isophthalic acid relative to terephthalic acid is selected in a way that does not significantly lower the melting point of the polycyclohexylenedimethylene terephthalate resin. Accordingly, in the present invention, the content of isophthalic acid is 25 mol% as described above. It is specific to less than.

Particularly preferably, the polyester resin may be a polycyclohexylenedimethylene terephthalate resin containing terephthalic acid to isophthalic acid in a molar ratio of 95:5 to 80:20. However, in the molar ratio, the minimum value of isophthalic acid may be 5 mol% or more, and the maximum value of isophthalic acid may be 20 mol% or less.

The polycyclohexylenedimethylene terephthalate resin has a crystallization rate slower than that of polybutylene terephthalate (PBT) but much faster than that of polyethylene terephthalate (PET), and has excellent tensile strength and tensile elongation during processing, as well as high heat resistance, It has chemical resistance and is relatively price competitive, so its potential use is very high. In addition, except for liquid crystal polymers, it is a polymer with the highest melting point among existing polyester resins, has a lower moisture absorption rate compared to polyacrylate (PA) polymers, and has excellent discoloration resistance due to heat.

Accordingly, when the polymer resin composition according to the present invention includes a polycyclohexylenedimethylene terephthalate resin as a polyester resin along with a polycarbonate resin, the transparency, which is an advantage of the polycarbonate resin, is maintained while Not only is chemical resistance and scratch resistance improved, but excellent stretching processability is provided, and it can be processed into a thin film or sheet.

However, in the composition ratio of polycarbonate resin and polyester resin, if the ratio of polyester resin is excessively low, the desired stretching processability is not guaranteed. Conversely, if it is excessively high, the transparency and tensile strength of the polymer resin composition Tensile elongation may decrease.

Therefore, in the polymer resin composition according to one embodiment of the present invention, the weight ratio of the polyester resin to the polycarbonate resin is 0.1 or more to less than 0.8, so that the ratio of the polycarbonate resin is relatively high, preferably 0.2 or more. It may be less than 0.7, and more preferably, it may be 0.3 or more to less than 0.6.

It should be noted that the polymer resin composition of the present invention having such a composition can be applied to various industrial uses requiring chemical resistance and scratch resistance, beyond the limited applications to which existing polycarbonate resins and molded products made therefrom have been applied. .

For example, in the case of a multilayer film (or sheet) in which polycarbonate resin and polycyclohexylenedimethylene terephthalate resin are each layered by coextrusion, or a lamination film (or sheet), polycyclohexylenedimethylene The transparency of polycarbonate resin along with the excellent chemical and scratch resistance of terephthalate resin can be applied to ID cards that require special identification, as well as outdoor goods and semiconductors that require resistance to air pollution or acid rain. Applicable to various parts of the process and supplies related to wastewater treatment.

In addition, in the case of a polymer stretched film containing polycarbonate resin and polycyclohexylenedimethylene terephthalate resin obtained by stretching treatment, it can be used for applications such as automobile dashboards, home appliances such as washing machines and refrigerators, and display protection films. You can.

Meanwhile, the polymer resin composition according to the present invention may further include one or more additives selected from the group consisting of antioxidants, pigments, nucleating agents, flame retardants, and anti-dripping agents, depending on the case. .

The antioxidant can suppress yellowing of the polymer resin, improve the appearance of the polymer resin composition and molded products, and inhibit oxidation or thermal decomposition. The antioxidant may include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and a hindered amine-based light stabilizer, and may be a complex containing a monomer having both a phenolic antioxidant group and a phosphorus-based antioxidant group in one molecule. Type antioxidants may also be used.

As the antioxidant, a mixture of a phenol-based primary antioxidant and a phosphorus-based secondary antioxidant, which are excellent in preventing coloring or physical property deterioration of the molded product due to heat or oxidation without reducing heat resistance, may be used. More specifically, a mixture of a phenolic-based primary antioxidant and a phosphorus-based secondary antioxidant may be used. A mixture of the first antioxidant and the phosphorus-based second antioxidant in a weight ratio of 2:1 to 1:2, or 1:1 to 1:2, may be used.

The phenol-based primary antioxidant is 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene)(1,3,5- Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene), 1,6-bis[3-(3,5-di-tert-butyl-4-hydroxy Phenyl)propionamido]hexane (1,6-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]hexane), 1,6-bis[3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionamido]propane (1,6-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]propane), tetrakis[methylene ( 3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane (tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane), etc., among which Any one or a mixture of two or more may be used. Additionally, commercially available phenol-based antioxidants include AO-60 from ADEKA.

In addition, the phosphorus-based secondary antioxidant specifically includes phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphono acetate, and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol. -Di-phosphite (Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di-phosphite), Bis(2,4-di-tert-butylphenyl)pentaerythritol-di-phosphite (Bis(2,4-di-tert-butylphenyl)pentraerythritol-di-phosphite), etc., and any one or a mixture of two or more of these may be used. Additionally, commercially available phosphorus-based antioxidants include S9228 from Doverphos.

If the antioxidant content in the polymer resin composition is too high, the mechanical properties, especially heat resistance, etc. of the polymer resin composition may be reduced. Therefore, when the above-described antioxidant is further included, when the total weight of the resin composition is 100 , Based on this, it may be included in 0.01 to 5 parts by weight, or 0.1 to 1 part by weight, or 0.1 to 0.5 parts by weight.

In addition, the pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, zinc sulfate, barium sulfate, lithopone (BaSO ₄ ·ZnS), white lead (2PbCO3·Pb(OH)2), and carbonic acid. Calcium, alumina, boron nitride, etc. may be used, and any one or a mixture of two or more of these may be used. When the above pigment is further included, it may be included in an amount of 0.01 to 5 parts by weight, or 0.1 to 1 part by weight, or 0.1 to 0.5 parts by weight, based on the total weight of the resin composition being 100. .

The nucleating agent acts as a crystallization nucleus during molding of the resin composition, improves the crystallization rate of the resin composition, and improves the heat resistance and injection moldability of the polyester resin composition.

Specific examples include talc/organic metal salt mixtures, sorbyl-based metal salts, phosphate-based metal salts, quinacridone, calcium carboxylate, montan-based metal salts, amide-based organic compounds, boron nitride or talc, which are inorganic nucleating agents, Any one or a mixture of two or more of these may be used. Among these, considering the significant improvement effect caused by the use of a nucleating agent, boron nitride, an inorganic nucleating agent, can be used, and in the case of a commercially available inorganic nucleating agent, IND-11 from Speer Advanced Materials Co., Ltd. can be used.

When the above-mentioned nucleating agent is further included, it may be included in an amount of 0.01% to 5% by weight, or 0.1% to 1% by weight, or 0.1 to 0.5% by weight, based on the total weight of the resin composition.

The flame retardant may be a phosphorus-based flame retardant, and the phosphorus-based flame retardant has the advantage of being environmentally friendly, replacing halogen-based flame retardants, and having excellent compatibility and fluidity with polycarbonate resin and polyester-based resin.

The phosphorus-based flame retardants include, for example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP), and trixylenyl phosphate. phosphate, TXP), Resorcinolbis(diphenyl phosphate, RDP), Phenyl diresorcinolphosphate, Bisphenol diphenyl phosphate (BDP), Cre Cresyl diphenyl phosphate, Xylenyl diphenyl phosphate, Phenyldi(isopropylphenyl) phosphate, Triisophenylphosphate, diphenyl phosphate ( It may be one or more selected from the group consisting of Diphenyl Phosphate, Resorcinol di Phosphate, and Aromatic Polyphosphate, but is not limited to these alone.

In addition, commercially available phosphorus-based flame retardants include OP-1230 and OP-1240 from Clariant. For compatibility between polycarbonate resin and polyester resin, OP-1230 or OP-1240 is used alone or , or mixtures thereof may be used.

When the above-described flame retardant is further included, it may be included in an amount of 0.01 to 5 parts by weight, or 0.1 to 1 part by weight, or 0.1 to 0.5 parts by weight, based on the total weight of the polymer resin composition as 100. there is.

Examples of the anti-dripping agent include silica (which also functions as a reinforcing filler), asbestos, and fibrillating-type fluoropolymer.

Fluorinated polymers include poly(tetrafluoroethylene), tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, poly(vinylidene fluoride), poly(chlorotrifluoroethylene), etc. Examples include fluorinated polyolefin and a mixture containing at least one of the above anti-dripping agents.

In addition, the commercially available FS-200 from Hannatech can be considered as an anti-dripping agent.

When the above-described anti-dripping agent is further included, based on the total weight of the polymer resin composition as 100, it will be included in an amount of 0.01 to 5 parts by weight, or 0.1 to 1 part by weight, or 0.1 to 0.5 parts by weight. You can.

The present invention also provides a molded article containing the polymer resin composition.

The molded article of the present invention can be applied to a variety of industrial applications requiring chemical resistance and scratch resistance, beyond the limited applications to which existing polycarbonate resins and molded articles made thereof have been applied.

The molded article may be a multilayer film, multilayer sheet, lamination film, or lamination sheet in which one or more layers are made of the polymer resin composition, or polycarbonate resin and polycyclohexylenedimethylene terephthalate resin may be formed by coextrusion molding, respectively. Examples include molded products such as layered multilayer films, multilayer sheets, lamination films, or lamination sheets.

These molded products have the transparency of polycarbonate resin along with the excellent chemical and scratch resistance of polycyclohexylenedimethylene terephthalate resin, such as ID cards that require special identification, and outdoor clothing that requires resistance to air pollution or acid rain. These may be door products, various parts in the semiconductor process, and products related to wastewater treatment.

The present invention also provides a polymer stretched film.

The stretched polymer film according to the present invention,

polycarbonate resin; and

polycyclohexylenedimethylene terephthalate resin containing isophthalic acid;

Includes,

The weight ratio of the polycyclohexylenedimethylene terephthalate to the polycarbonate (=polycyclohexylenedimethylene terephthalate resin/polycarbonate resin) is greater than 0.1 and less than 0.8,

The polycyclohexylenedimethylene terephthalate resin is characterized in that the molar ratio of terephthalic acid to isophthalic acid is 99:1 to 75:25.

In some cases, the weight ratio of the polycyclohexylenedimethylene terephthalate to the polycarbonate may be 0.2 or more to less than 0.7, and specifically, may be 0.3 or more to less than 0.6.

Specifically, the polycyclohexylenedimethylene terephthalate resin may be a resin prepared by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, and some isophthalic acid in the terephthalic acid is derived from dicarboxylic acid repeating. It may be copolymerized at a content of 25 mol% or less per unit of 100 mol%.

That is, in the molar ratio, the minimum value of isophthalic acid may be 1 mol% or more, and the maximum value of isophthalic acid may be less than 25 mol%.

If the polycyclohexylenedimethylene terephthalate resin that does not contain isophthalic acid is included, since the crystallization rate of the polycyclohexylenedimethylene terephthalate resin is relatively fast, stretching processability cannot be expected, and for this reason, , it is difficult for polymer stretched films to have a substantially thin thickness.

On the other hand, as in the present invention, in the case of polycyclohexylenedimethylene terephthalate resin containing isophthalic acid, the crystallization rate is relatively delayed, so that the resin composition can be processed under desired stretching processability, The stretched polymer film may have a relatively thin thickness, specifically 50 micrometers or less, more specifically 30 micrometers or less, and more specifically 20 micrometers or less.

Nevertheless, the content of isophthalic acid relative to terephthalic acid must be 1 mol% or more, and if it is less than that, the stretched polymer film cannot achieve the desired thin form for the reasons described above.

If the content of isophthalic acid relative to terephthalic acid is 25 mol% or more, there is a risk of lowering the melting point of polycyclohexylenedimethylene terephthalate resin.

Specifically, in the above case, the melting point is lowered by about 10 degrees or more from 250 to 260 degrees Celsius, which is the melting point of polycyclohexylenedimethylene terephthalate resin.

The melting point is closely related to the processing temperature as it is about 10 degrees or less compared to the processing temperature of the resin. In the above case, the processing temperature of polycyclohexylenedimethylene terephthalate resin is for polycarbonate resin with a processing temperature of approximately 290 to 300 degrees Celsius. It will drop by more than 40 degrees Celsius.

Therefore, if the stretched polymer film was manufactured by processing at a processing temperature of 290 degrees Celsius, the polycyclohexylenedimethylene terephthalate resin is completely melted and has a high viscosity, whereas the polycarbonate resin is at the melting stage and has a relatively low viscosity. Because of this, the stretched polymer film may have swells or wrinkles formed on its surface due to differences in viscosity.

Therefore, it is very important that the content of isophthalic acid relative to terephthalic acid is contained in a range that does not significantly lower the melting point of the polycyclohexylenedimethylene terephthalate resin. Accordingly, in the present invention, the content of isophthalic acid is 25 moles as described above. It is specific to less than %.

Particularly preferably, the polycyclohexylenedimethylene terephthalate resin may be a resin containing terephthalic acid to isophthalic acid in a molar ratio of 95:5 to 80:20. However, in the molar ratio, the minimum value of isophthalic acid may be 5 mol% or more, and the maximum value of isophthalic acid may be 20 mol% or less.

The polymer stretched film according to the present invention can be used as a display protection film and home appliances such as automobile dashboards, washing machines, and refrigerators.

The polymer resin composition according to the present invention contains polycarbonate resin and polyester resin, specifically, polyester resin containing terephthalic acid and isophthalic acid, and maintains the transparency, which is an advantage of the polycarbonate resin, while maintaining the internal resistance, which is a vulnerability. Not only is chemical resistance and scratch resistance improved, but excellent stretching processability is provided, and there is an advantage in that it can be processed into a thin film or sheet.

In addition, the polymer stretched film according to the present invention can have improved transparency, chemical resistance, and scratch resistance for the same reasons as above, and has a thickness of 50 micrometers or less, specifically 30 micrometers or less, and more specifically 20 micrometers. It may be in the form of the following relatively thin film or sheet.

Hereinafter, the operation and effects of the invention will be described in more detail through specific examples of the invention. However, these examples are merely presented as examples of the invention, and the scope of the invention is not determined by them.

Example 1

A polymer film with a thickness of 50 micrometers was made using a polymer resin composition blended with 30% by weight of polycyclohexylenedimethylene terephthalate resin and 70% by weight of polycarbonate, which has a molar ratio of 85:15 of terephthalic acid to isophthalic acid. Produced.

Example 2

A polymer film with a thickness of 15 micrometers was made using a polymer resin composition blended with 30% by weight of polycyclohexylenedimethylene terephthalate resin and 70% by weight of polycarbonate, which has a molar ratio of 85:15 of terephthalic acid to isophthalic acid. Produced.

Example 3

A polymer film with a thickness of 15 micrometers was made using a polymer resin composition blended with 30% by weight of polycyclohexylenedimethylene terephthalate resin and 70% by weight of polycarbonate, which has a molar ratio of terephthalic acid to isophthalic acid of 95:5. Produced.

Example 4

A polymer film with a thickness of 15 micrometers was made using a polymer resin composition blended with 30% by weight of polycyclohexylenedimethylene terephthalate resin and 70% by weight of polycarbonate, which has a molar ratio of 80:20 of terephthalic acid to isophthalic acid. Produced.

Example 5

A polymer film with a thickness of 15 micrometers was made using a polymer resin composition blended with 20% by weight of polycyclohexylenedimethylene terephthalate resin and 80% by weight of polycarbonate, which has a molar ratio of 85:15 of terephthalic acid to isophthalic acid. Produced.

Example 6

A polymer film with a thickness of 15 micrometers was made using a polymer resin composition blended with 40% by weight of polycyclohexylenedimethylene terephthalate resin and 60% by weight of polycarbonate, which has a molar ratio of 85:15 of terephthalic acid to isophthalic acid. Produced.

Comparative Example 1

A polymer film with a thickness of 50 micrometers was produced using a resin made of 100% by weight polycarbonate.

Comparative Example 2

A polymer film with a thickness of 50 micrometers was made using a polymer resin composition blended with 50% by weight of polycyclohexylenedimethylene terephthalate resin and 50% by weight of polycarbonate, which has a molar ratio of 85:15 of terephthalic acid to isophthalic acid. Produced.

Comparative Example 3

A polymer film with a thickness of 50 micrometers was made using a polymer resin composition blended with 30% by weight of polycyclohexylenedimethylene terephthalate resin and 70% by weight of polycarbonate, which has a molar ratio of terephthalic acid to isophthalic acid of 100:0. Produced.

Comparative Example 4

A polymer film with a thickness of 50 micrometers was made using a polymer resin composition blended with 30% by weight of polycyclohexylenedimethylene terephthalate resin and 70% by weight of polycarbonate, which has a 70:30 molar ratio of terephthalic acid to isophthalic acid. Produced.

Experimental Example 1

The physical properties of the polymer films produced in Examples 1 to 4 and Comparative Examples 1 to 4 were compared, and the results are shown in Table 1 below.

Here, Tg / Tm / Tmc (°C) is the physical property value of the polycyclohexylenedimethylene terephthalate resin used in the present invention. (Not polymer film physical properties)

For reference, chemical resistance was evaluated by immersion and ESCR tests in acetone, toluene, ammonia, etc., and qualitative comparisons were made according to the degree of crack / haze.

Scratch resistance was evaluated through a pencil hardness test. The pencil hardness of existing polycarbonate molded products is 2B, and the pencil hardness grades are as follows.

- Pencil hardness grades: (soft) ~ 3B - 2B - B - HB - H - 2H - 3H ~ (hard)

division unit Example Comparative example One 2 3 4 5 6 One 2 3 4 PC wt% 70 70 70 70 80 60 100 50 70 70 PCT wt% 30 30 30 30 20 40 x 50 30 30 IPA mol% 15 15 5 20 15 15 x 15 x 30 film thickness μm 50 15 15 15 15 15 50 50 50 50 transparency % >90 >90 >90 >90 >90 >90 >90 >80 >85 >85 Tg ℃ 87 87 89 86 108 88 87 91 83 Tm ℃ 265 265 281 255 265 265 265 288 234 Tmc ℃ 190 190 220 155 190 190 190 250 145 Tensile Strength (MD) kg/ ^cm2 990 1518 1486 1584 1365 1415 660 726 858 792 Tensile elongation (MD) % 255 465 480 455 430 440 150 135 120 270 chemical resistance Qualitative ◎ ◎ ◎ ◎ ○ ◎ Ⅹ ◎ ○ ◎ Scratch resistant pencil hardness B HB~B HB~B HB~B HB-B HB-B 2B 2B B~2B B~2B Compared to Example 1
Features (Pros and Cons) stretched film
(up to 3 times) chemical resistance
Lowering transparency/
Tensile properties
Lowering elongation
Lowering surface
error

The results in Table 1 above are summarized as follows.

First, the polymer films of Examples 2 to 6 were processed to a thin thickness of 15 micrometers while the resin composition was stretched during film molding. This means that films based on polycarbonate resin can also be used in a variety of industrial components.

On the other hand, the polymer films of Comparative Examples 1 to 4 were processed to a relatively thick thickness of 50 micrometers without stretching the resin composition during film molding. This is largely related to tensile strength and tensile elongation, which will be described later.

Second, the polymer film of Example 1 had improved tensile properties, chemical resistance, and scratch resistance, and maintained transparency compared to the polymer film of Comparative Example 1, which can be directly compared thereto.

Accordingly, it can be seen that the physical properties of the polymer composition containing polycarbonate and polycyclohexylenedimethylene terephthalate resin and the polymer film produced therefrom have improved physical properties compared to the use of polycarbonate alone.

Third, as in Examples 2 to 6, the polymer film made of a polymer resin composition containing isophthalic acid in an appropriate mole % was obtained from Comparative Examples 3 and 4 without isophthalic acid or with an excessive mole % addition. Compared to polymer films, it can be seen that the tensile strength and tensile elongation are significantly superior.

In particular, in the case of Comparative Example 3 without isophthalic acid, film production was difficult as the polycyclohexylenedimethylene terephthalate resin contained in the polymer resin composition rapidly crystallized.

In other words, when producing the polymer films of the examples, the stretch processability is excellent, making it possible to implement a thinner film. On the other hand, when producing the polymer films of the comparative examples, the stretch processability is relatively poor, making it possible to implement a thin film. It's difficult.

Fourth, in the case of Comparative Example 4, in which isophthalic acid is relatively excessive, it can be seen that the melting point is very low, which causes a large difference in processing temperature between polycarbonate and polycyclohexylenedimethylene terephthalate resin, so that during the processing process, both resins Surface defects were formed due to differences in viscosity.

That is, it is undesirable for isophthalic acid to be excessively included, more than 25 mol%.

Fifth, it can be seen that all of the polymer films according to Examples 1 to 6 have excellent chemical resistance and scratch resistance compared to Comparative Example 1 produced with polycarbonate alone, and in addition, polycarbonate and polycyclo It can be seen that this is significant when compared with Comparative Example 2, where the proportion of hexylenedimethylene terephthalate resin was excessive, and Comparative Examples 3 and 4, where the mole percentage of isophthalic acid was insufficient or excessive.

Claims (11)

polycarbonate resin; and
polyester resin containing at least a heterogeneous acid;
Includes,
The weight ratio of the polyester resin to the polycarbonate resin (=polyester resin/polycarbonate resin) is greater than 0.1 and less than 0.8,
The polyester resin is a polycyclohexylenedimethylene terephthalate resin containing terephthalic acid and isophthalic acid,
The polyester resin is a polymer resin composition that is a polycyclohexylenedimethylene terephthalate resin containing terephthalic acid to isophthalic acid in a molar ratio of 95:5 to 80:20.
delete The polymer resin composition according to claim 1, wherein the weight ratio of the polyester resin to the polycarbonate resin is 0.2 or more to less than 0.7.
The polymer resin composition according to claim 1, wherein the weight ratio of the polyester resin to the polycarbonate resin is 0.3 or more to less than 0.6.
The polymer resin composition according to claim 1, wherein the polyester resin has a viscosity of 0.4 dl/g to 1.2 dl/g.
A molded article comprising the polymer resin composition according to any one of claims 1, 3 to 5.
The molded article according to claim 6, wherein the molded article is a multilayer film, multilayer sheet, lamination film, or lamination sheet in which one or more layers are made of the polymer resin composition.
The molded article according to claim 6, wherein the molded article is a multilayer film, multilayer sheet, lamination film, or lamination sheet in which polycarbonate resin and polycyclohexylenedimethylene terephthalate resin are each layered.
polycarbonate resin; and
polycyclohexylenedimethylene terephthalate resin containing isophthalic acid;
Includes,
The weight ratio of the polycyclohexylenedimethylene terephthalate to the polycarbonate resin (=polycyclohexylenedimethylene terephthalate resin/polycarbonate resin) is greater than 0.1 and less than 0.8,
The polycyclohexylenedimethylene terephthalate resin is a stretched polymer film in which the molar ratio of terephthalic acid to isophthalic acid is 95:5 to 80:20.
delete The stretched polymer film according to claim 9, wherein the thickness is from 1 micrometer to 50 micrometers.