KR102200870B1 - Polycarbonate resin composition having excellent chemical and light resistance in appearance characteristics with transparency - Google Patents

Abstract

Chemical light-resistant polycarbonate resin composition with excellent metallic color by improving light resistance, which is a disadvantage of conventional polycarbonate (PC) and polycyclohexylenedimethylene terephthalate (PCT) alloys, and maintaining transparency, a characteristic of existing alloy products. Is initiated. The present invention (A) 60 to 89% by weight of a polycarbonate resin; (B) 10 to 39% by weight of polycyclohexylenedimethylene terephthalate resin; And (C) a triazine (Triazine)-based compound, benzotriazole (Benzotriazole)-based compound, and a UV stabilizer including a malonic acid (Maronate)-based compound 0.05-5% by weight; provides a polycarbonate resin composition comprising a.

Description

Polycarbonate resin composition having excellent chemical and light resistance in appearance characteristics with transparency}

The present invention relates to a polycarbonate resin composition, and more particularly, to a resin composition capable of expressing a metallic color, excellent mechanical properties and chemical resistance, and thus can be used as an exterior material.

Polyester-based resins have relatively excellent mechanical strength and elastic strength, and especially, because of their excellent chemical resistance to chemicals, they are widely used in household containers such as various detergents and cosmetics, but have low heat resistance and are not suitable for use as outdoor exterior materials with severe temperature changes. There is an inappropriate problem.

On the other hand, polycarbonate is used in various fields such as construction materials and electronic device housings due to its excellent mechanical properties such as heat resistance and impact resistance. However, it is used in various fields such as hand sanitizers, cosmetics, and air fresheners. There is a problem that the product is deteriorated.

Various attempts have been made to supplement and overcome the problems of these two resins, and among them, a method of alloying a polycarbonate resin and a polyester resin has been actively developed.

Among these alloy resins, polycarbonate and polycyclohexylenedimethylene terephthalate alloy has been developed as a technology that overcomes the shortcomings of both resins by improving chemical resistance and heat resistance to household chemicals, but discoloration and resin aging due to light As it progresses rapidly, it has limitations to be used in outdoor products. Accordingly, the necessity of improving light resistance characteristics is gradually increasing in order to improve long-term durability according to outdoor use.

Korean Patent Publication No. 2018-0031474 discloses a polycarbonate resin composition that exhibits excellent metallic color based on chemical resistance and transparency, but does not mention improving light resistance for use as an outdoor material.

In addition, Korean Patent Application Publication No. 2015-0144114 discloses a polymer resin composition that increases outdoor usability by adding weather-reinforced ASA resin to improve the weather resistance of polyester. There is a problem in that the coloring property decreases.

In addition, Korean Laid-Open Patent No. 2009-0080132 is a technology related to a method of manufacturing a thermoplastic resin that can be used at high temperatures while maintaining transparency through a blend of polycarbonate and polyester, and its use. Polycarbonate and polyester (PCTG, PCT, etc.) ) To achieve transparency and excellent mechanical strength through various composition ratios, but also does not mention light resistance and color (metal) implementation for use as outdoor materials.

The present invention has been devised to solve the above problem, improves light resistance, which is a disadvantage of conventional polycarbonate (PC) and polycyclohexylenedimethylene terephthalate (PCT) alloys, and improves transparency, which is a characteristic of existing alloy products. It is intended to provide a chemical light-resistant polycarbonate resin composition having excellent metallic color by maintaining it.

The present invention in order to solve the above problems, (A) 60 to 89% by weight of a polycarbonate resin; (B) 10 to 39% by weight of polycyclohexylenedimethylene terephthalate resin; And (C) a triazine (Triazine)-based compound, benzotriazole (Benzotriazole)-based compound, and a UV stabilizer including a malonic acid (Maronate)-based compound 0.05-5% by weight; provides a polycarbonate resin composition comprising a.

In addition, the triazine (Triazine)-based compound, benzotriazole (Benzotriazole)-based compound, and malonic acid (Maronate)-based compound provides a polycarbonate resin composition, characterized in that the content is 0.01 to 2% by weight, respectively.

In addition, the triazine (Triazine)-based compound, benzotriazole (Benzotriazole)-based compound and malonic acid (Maronate)-based compound provides a polycarbonate resin composition, characterized in that the compounds represented by the following formulas 1 to 3, respectively. .

[Formula 1]

[Formula 2]

[Formula 3]

In addition, the polycarbonate resin composition is a polycarbonate resin composition, characterized in that the light transmittance (ASTM D1003, 3 mm thick injection specimen, based on the addition of pigment) is 65% or more, and light resistance according to the following measurement method is 70% or more. to provide.

[Measurement method of light resistance]

For the 3 mm-thick injection specimen of the resin composition, after UV irradiation for 14 days using a lightfastness accelerator (UV-CONE), the ratio of tensile strength after UV irradiation to tensile strength before UV irradiation (tensile strength residual rate) was measured I did.

The polycarbonate resin composition according to the present invention maintains excellent chemical resistance and has excellent transparency by containing a specific UV stabilizer in an alloy of polycarbonate resin and polycyclohexylenedimethylene terephthalate, so that it is easy to express metallic colors and is especially for outdoor use. It is possible to provide a polycarbonate resin composition having dramatically improved light resistance for use as a material.

Hereinafter, a preferred embodiment of the present invention will be described in detail. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted. Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components, unless otherwise stated.

The present inventors have repeatedly researched to develop a polycarbonate resin capable of solving the problem of light resistance, which is a disadvantage of conventional polycarbonate (PC) and polycyclohexylenedimethylene terephthalate (PCT) alloys, and as a result, polycarbonate resin and polycyclo By containing a specific UV stabilizer in the alloy of hexylenedimethylene terephthalate, it has been found that excellent chemical resistance is maintained and its transparency is excellent, so that the expression of metallic color is easy, and light resistance for use as an outdoor material can be remarkably improved. Was reached.

Therefore, the present invention (A) 60 to 89% by weight of a polycarbonate resin; (B) 10 to 39% by weight of polycyclohexylenedimethylene terephthalate resin; And (C) triazine (Triazine)-based, benzotriazole (Benzotriazole)-based and malonic acid (Maronate)-based UV stabilizer including 0.05 to 5% by weight; discloses a polycarbonate resin composition comprising a.

The resin composition has a light transmittance (ASTM D1003, 3 mm thick injection specimen, based on no pigment added) of 65% or more, preferably 70% or more, and light resistance according to the following measurement method: 70% or more, preferably 72% It exhibits the above characteristics, making it easy to realize the metallic color, and as a result of the chemical resistance test according to the method described later, it maintains a level of 75% or more, preferably 80% or more of the tensile strength before the test, and 50% of the elongation before the test. It exhibits a chemical resistance that maintains an abnormal level, preferably 55% or more.

[Measurement method of light resistance]

For the 3 mm-thick injection specimen of the resin composition, after UV irradiation for 14 days using a lightfastness accelerator (UV-CONE), the ratio of tensile strength after UV irradiation to tensile strength before UV irradiation (tensile strength residual rate) was measured I did.

Hereinafter, each component of the polycarbonate resin composition according to the present invention will be described in more detail.

(A) Polycarbonate resin

The polycarbonate (PC) resin used in the present invention has excellent impact resistance, heat resistance, weather resistance, self-extinguishing property, flexibility, processability and transparency, and excellent weather resistance, maintaining high physical properties for a long period of time, and excellent heat resistance and cold resistance. Maintains performance despite changes.

The resin of the polycarbonate is not particularly limited, but may be a polymerized resin including a bisphenol-based monomer and a carbonate precursor.

The bisphenol-based monomer is, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3) ,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2 ,2-bis(4-hydroxy-3chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl )Propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane and α,ω-bis[3-(ο-hydroxyphenyl)propyl] It may be one or more selected from the group consisting of polydimethylsiloxane.

In addition, the carbonate precursor is, for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate , Bis (diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide and bishaloformate may be one or more selected from the group consisting of.

In the present invention, the polycarbonate resin may be, for example, a polymer of bisphenol A having a weight average molecular weight (Mw) of 10,000 to 200,000, preferably 20,000 to 50,000.

In addition, the polycarbonate resin may have a melt index (300°C, 1.2 kg load) of 5 to 15 g/10min, more preferably 7 to 13 g/10min. It has excellent processability and moldability within the above melt index range, and has an excellent balance of properties. If the melt index is lower than the above range, the flowability may be insufficient and unmolding may occur, and if the melt index is high, the impact strength tends to be slightly lowered.

In the present invention, the polycarbonate resin is included in an amount of 60 to 89% by weight in the total resin composition for fluidity, impact resistance, processability, etc. of the final thermoplastic resin composition, preferably 65 to 84% by weight.

(B) Polycyclohexylenedimethylene terephthalate resin

The polycyclohexylenedimethylene terephthalate (PCT) resin used in the present invention includes terephthalic acid (TPA) or dimethylterephthalate (DMT) and 1,4-cyclohexanedimethanol, CHDM) or crystalline polyester produced by transesterification and polycondensation reaction, and has a very high melting point and a very fast crystallization rate.

The PCT resin has excellent heat resistance, chemical resistance, moisture absorption and flow resistance compared to polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), which are general-purpose polyesters, and among them, the heat deflection temperature is 245~260℃ , It is an engineering plastic that can replace metal with a continuous use temperature of 130~150℃. Compared with other polymer resins, such PCT resins have very good color stability and have a significantly lower moisture absorption rate, so they can be used in various ways for housings of electrical and electronic products.

In the present invention, the PCT resin is included in an amount of 10 to 39% by weight in the total resin composition, and preferably may be included in an amount of 15 to 34% by weight. When the content of the PCT resin is less than 10% by weight, the degree of improvement in chemical resistance may be insufficient, and when it exceeds 39% by weight, it may be difficult to implement a metallic color due to decreased transparency.

(C) UV stabilizer

In the present invention, the UV stabilizer is a group of compounds having a characteristic of absorbing UV in the UV-A, UV-B and UV-C regions, and particularly has the characteristic of absorbing UV-B that directly affects the polymer resin, including It imparts light resistance to the polymer resin composition.

As described above, in order to improve the light resistance of the polymer resin composition, benzophenone-based compounds, benzotriazole-based compounds, benzoxazine-based compounds, malonic acid (Maronate)-based compounds, and triazines )-Based compounds may be considered, but in the present invention, in particular, in the present invention, when three kinds of additives consisting of triazine-based compounds, benzotriazole-based compounds, and malonic acid-based compounds are included. It was confirmed that the ideal light resistance characteristics can be exhibited.

At this time, the UV stabilizer may be included in an amount of 0.05 to 5% by weight in the total resin composition, preferably in an amount of 0.1 to 3% by weight, in order to realize ideal light resistance properties, and the three additives, that is, triazine ( Triazine)-based compounds, benzotriazole-based compounds, and malonic acid-based compounds are each contained in an amount of 0.01 to 2% by weight, preferably 0.05 to 0.5% by weight.

In the present invention, as the triazine-based compound, benzotriazole-based compound, and malonic acid-based compound, compounds represented by the following formulas 1 to 3 may be preferably used.

[Formula 1]

[Formula 2]

[Formula 3]

The polycarbonate resin composition according to the present invention may further include an additive suitable for its intended use or effect. For example, by adding a release agent, an anti-drip agent, an antioxidant, a colorant, etc., it can be applied for various purposes.

Hereinafter, a specific example according to the present invention will be described.

First, specifications of components including polycarbonate resins used in Examples and Comparative Examples of the present invention are as follows.

(A) Polycarbonate (PC) resin

A bisphenol A type polycarbonate (PC-1100S, Lotte Chemical) having a weight average molecular weight of 33,000 and a melt index (300°C, 1.2 kgf) of 10 g/10min was used.

(B) Polycyclohexylenedimethylene terephthalate (PCT) resin

PCT resin (SKYPURA 3402, SK Chemicals) having an intrinsic viscosity (IV) of 0.7 dl/g was used.

(C) Polybutylene terephthalate (PBT)

Polybutylene terephthalate (PBT) resin (Kanghui Petrochemical) having an intrinsic viscosity (IV) of 1.1 dl/g was used.

(D) Polyethylene terephthalate (PET)

Polyethylene terephthalate (PET) resin (Lotte Chemical) having an intrinsic viscosity (IV) of 0.8 dl/g was used.

(E-1) Triazaine UV stabilizer

Triazaine UV stabilizer (Tinuvin 1577, Germany BASF) having the structure of Formula 1 was used.

(E-2) Benzotriazole UV stabilizer

Benzotriazole-based UV stabilizer (UV-5411, CYTEC) having the structure of Formula 2 was used.

(E-3) Maronate UV stabilizer

A Maronate UV stabilizer (B-CAP, Swiss Clariant) having the structure of Formula 3 was used.

Example 1

(A) 79.7% by weight of polycarbonate resin, (B) 20% by weight of PCT resin, (E-1) 0.1% by weight of Triazaine UV stabilizer, (E-2) 0.1% by weight of Benzotriazole UV stabilizer and (E-3) Maronate UV stabilizer is quantitatively mixed in 0.1% by weight ratio, and the thermoplastic resin composition is made into chips using a twin-screw extruder heated to 270℃~300℃, dried at 110℃ for 4 hours using a hot air dryer, and then prepared The specimen was injection molded using a mold.

Examples 2 to 4 and Comparative Examples 1 to 6

In Example 1, a specimen was molded in the same manner as in Example 1, except that components (A) to (E) were adjusted to the content of Table 1 below.

Test example

For the specimens according to the Examples and Comparative Examples, the melt index, tensile strength, elongation, heat resistance, chemical resistance, light transmittance and light resistance were measured according to the following method, and the results are shown in Table 2 below.

[How to measure]

(1) Melt Index

According to ASTM D1238, it was measured under the condition of 2.16kg load at 250°C.

(2) Tensile strength and elongation

A specimen for measurement was made according to ASTM D638, and tensile strength and elongation were measured using a universal testing machine.

(3) Heat resistance (heat deflection temperature, HDT)

A specimen for measurement was made according to ASTM D648 and the heat resistance was measured using a heat resistance tester.

(4) Chemical resistance evaluation

After injecting the manufactured pellets at an injection temperature of 260°C using an injection machine, adjust the condition of the injected tensile strength specimen for 24 hours under conditions of 23±2°C and 50±5% relative humidity, and follow the method below. Evaluation was performed.

① The chemical resistance test fixture was manufactured with a critical strain of 1.0%, and the tensile specimen was fixed with the test fixture.

② Sunscreen (SPF 50) and fragrance (general product sold for automobiles) were applied to the tensile specimen for 1 minute, respectively, and then left at 23±2℃ for 168 hours.

③ After 168 hours elapsed at 23±2℃, the tensile specimen was removed from the test fixture and left at 23±2℃ for about 1 to 2 hours.

④ After leaving for 1 to 2 hours as above, the tensile properties of each specimen to which the sunscreen and fragrance were applied were evaluated.

⑤ Chemical resistance When the tensile properties before the test are 75% or more, preferably 80% or more, and 50% of the elongation property, preferably 55% or more, the chemical resistance was evaluated as excellent.

(5) light transmittance

According to ASTM D1003, a measurement specimen (3mm) was prepared and the light transmittance was measured.

(6) light resistance

A specimen was prepared in the same manner as in the chemical resistance evaluation. The tensile strength was measured after irradiation for a certain period of time (1-14 days) using a UV-CONE device, which is a lightfastening device. Compared with before UV irradiation, the tensile strength residual rate was calculated as shown in Equation 1 below.

[Equation 1]

Tensile strength residual rate (%) = tensile strength of the sample after UV irradiation / tensile strength of the sample before UV irradiation × 100

Referring to Table 2, a triazine-based compound, a benzotriazole-based compound, and malonic acid as a UV stabilizer of a specific combination of a polycarbonate resin and a polycyclohexylenedimethylene terephthalate resin alloy according to the present invention. When manufacturing using a polycarbonate resin composition containing a UV stabilizer containing a (Maronate) compound in a specific composition (Examples 1 to 4), it has excellent chemical resistance, and when considering the light transmittance measurement result, it is possible to realize a metallic color. It can be seen that it is very easy, and in particular, it can be seen that the residual rate of tensile strength is high under severe conditions, so that the light resistance for use as an external material is excellent.

On the other hand, when the UV stabilizer is not included (Comparative Example 1), or a specific combination according to the present invention is not achieved (Comparative Examples 2 to 4), even if it is included, it can be seen that the light resistance is significantly lowered.

On the other hand, even if a specific combination of the UV stabilizer presented in the present invention is included, when a general PBT resin or PET resin other than a PCT resin is used as an alloy resin (Comparative Examples 5 and 6), not only the light resistance is lowered, but also heat resistance and chemical resistance. From what is also lowered, it is confirmed that the specific combination of the UV stabilizer compound presented in the present invention is a composition specifically suitable for a specific alloy resin, that is, a PC/PCT alloy resin.

The preferred embodiments of the present invention have been described in detail above. The description of the present invention is for illustration only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention.

Therefore, the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and all changes or modified forms derived from the meaning, scope, and equivalent concepts of the claims are included in the scope of the present invention. It must be interpreted.

Claims (4)

(A) 60 to 89% by weight of a polycarbonate resin;
(B) 10 to 39% by weight of polycyclohexylenedimethylene terephthalate resin; And
(C) 0.05 to 5% by weight of a UV stabilizer including a triazine-based compound, a benzotriazole-based compound, and a malonic acid-based compound;
Including,
The triazine (Triazine)-based compound, benzotriazole (Benzotriazole)-based compound and malonic acid (Maronate)-based compound is a polycarbonate resin composition, characterized in that the compounds represented by the following formulas 1 to 3, respectively.
[Formula 1]

[Formula 2]

[Formula 3]

The method of claim 1,
The content of the triazine-based compound, benzotriazole-based compound, and malonic acid-based compound is 0.01 to 2% by weight, respectively. delete The method of claim 1,
The polycarbonate resin composition has a light transmittance (ASTM D1003, 3 mm thick injection specimen, based on no pigment added) of 65% or more, and a light resistance of 70% or more according to the following measurement method:
[Measurement method of light resistance]
For the 3 mm-thick injection specimen of the resin composition, after UV irradiation for 14 days using a lightfastness accelerator (UV-CONE), the ratio of tensile strength after UV irradiation to tensile strength before UV irradiation (tensile strength residual rate) was measured I did.