KR20190079362A - Thermoplastic resin composition with improved transparency and chemical resistance and molded article comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition having improved transparency and chemical resistance, and a molded article comprising the same. More particularly, the present invention relates to: the thermoplastic resin composition which comprises a polycarbonate resin, a polyester resin, and a polyalcohol compound, thereby remarkably improving transparency and chemical resistance while maintaining excellent processability such as mechanical strength for example, impact resistance inherent in polycarbonate, heat resistance, fluidity and the like; and the molded article comprising the same.

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having improved transparency and chemical resistance and a molded article comprising the same,

The present invention relates to a thermoplastic resin composition having improved transparency and chemical resistance and a molded article comprising the same. More particularly, the present invention relates to a thermoplastic resin composition comprising a polycarbonate resin, a polyester resin and a polyalcohol compound, To a thermoplastic resin composition in which transparency and chemical resistance are remarkably improved while maintaining excellent workability such as strength, heat resistance and fluidity, and a molded article comprising the same.

The polycarbonate resin is a general-purpose thermoplastic engineering plastic produced by polycondensation of bisphenol A and phosgene and having a glass transition temperature of around 150 ° C. It is excellent in mechanical properties such as tensile strength and impact strength, and has excellent properties such as numerical stability, heat resistance and optical transparency Heat-resistant engineering plastics that replace glass, and are used in housing for electric / electronic products, for use in architectural and advertising purposes, and the like.

The physical properties of such a polycarbonate resin originate from the phenyl group and the carboxyl group, and the properties of the molecular structure such as the rigidity of the molecular chain and the binding of the rotation affect the physical properties. However, polycarbonate resins have limited chemical resistance and thus have many limitations for use in applications in contact with organic solvents, certain detergents, strong alkalis, certain fatty acids, oils and greases. Especially, when polycarbonate resin is used for mobile phone housings, TV housings, computer monitor housings, copiers, printers, notebook batteries and lithium battery cases that require contact with various chemical products among electric / electronic fields, heat resistance and mechanical properties In addition, excellent chemical resistance and transparency are required.

Conventionally, efforts have been made to improve the physical properties of polycarbonate by blending polycarbonate with another thermoplastic resin. For example, U.S. Patent No. 3,218,372 discloses a resin composition in which the polycarbonate and the polyalkylene terephthalate are mixed to lower the melt viscosity and to have improved ductility than the polyalkylene terephthalate. However, the two resins used in this patent are poor in compatibility and the composition becomes opaque and the impact strength is lowered. U.S. Patent No. 4,391,954 discloses a resin composition consisting of a copolyester consisting essentially of repeating units derived from a mixture of polycarbonate and isophthalic acid, terephthalic acid and 1,4-cyclohexanedimethanol, Sufficient impact strength can not be obtained. U.S. Patent No. 4,634,737 discloses a resin composed of a copolymerized polycarbonate having an ester bond of 25 to 90 mol% and a copolyester composed of isophthalic acid, terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol, and an olefin acrylate copolymer Although the composition is disclosed, the composition is also opaque and does not provide sufficient impact strength. U.S. Patent No. 4,188,314 discloses a sheet molding comprising polycarbonate and a copolyester derived from isophthalic acid, terephthalic acid and 1,4-cyclohexanedimethanol, and having improved chemical resistance, It does not provide impact strength.

Accordingly, there is still a demand for a resin composition balanced with excellent chemical resistance, transparency, impact resistance, heat resistance and the like as a thermoplastic resin composition utilizing polycarbonate.

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above, and it is an object of the present invention to provide a polycarbonate excellent in transparency and chemical resistance while maintaining excellent workability such as mechanical strength, heat resistance and flowability inherent in polycarbonate And a molded article comprising the thermoplastic resin composition.

In order to solve the above technical problems, the present invention provides a thermoplastic resin composition comprising (A) a polycarbonate resin, (B) a polyester resin, and (C) a polyalcohol compound.

According to a preferred embodiment of the present invention, the thermoplastic resin composition comprises 50 to 90 parts by weight of (A) a polycarbonate resin, (B) 5 to 45 parts by weight of a polyester resin, and (C) ) 0.1 to 10 parts by weight of a polyalcohol compound.

According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition of the present invention.

The thermoplastic resin composition according to the present invention is excellent in transparency and chemical resistance, and has excellent balance of physical properties such as fluidity, impact strength and heat resistance, and can be applied to various applications such as automobiles, electric / electronic parts, office equipment, It can be used for housing and automobile interior and exterior parts which are major parts in various OA and communication devices such as phone.

As used herein, the term "reaction product" means a material in which two or more reactants are formed by reaction.

The letter "R" used to represent hydrogen, a halogen atom and / or a hydrocarbon group in the formulas described in the present specification has a subscript indicated by a numeral, but the letter "R" But is not limited thereto. The "R" represents, independently of each other, hydrogen, a halogen atom and / or a hydrocarbon group. For example, the "R" s may represent the same hydrocarbon group or may represent other hydrocarbon groups, irrespective of whether two or more "R" have the same or different numbers of subscripts.

Hereinafter, the present invention will be described in detail.

(A) Polycarbonate resin

The resin composition of the present invention comprises a polycarbonate resin as a base resin component.

According to one embodiment of the present invention, the polycarbonate resin included in the resin composition of the present invention may include a polycarbonate block represented by a repeating unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is substituted or unsubstituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom or a nitro group.

Specifically, the alkyl group may be an alkyl group having 1 to 20 carbon atoms, preferably 1 to 13 carbon atoms, and the cycloalkyl group may be a cycloalkyl group having 3 to 6 carbon atoms, and the alkenyl group is an alkenyl group having 2 to 13 carbon atoms And the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms.

In addition, the aromatic hydrocarbon group may be derived from a compound having a structure represented by the following formula (1a).

[Formula 1a]

In formula (1a)

X is a straight, branched or cyclic alkylene group having no functional group; Or a straight, branched or cyclic alkylene group containing at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, naphthyl or isobutylphenyl, A linear alkylene group having 3 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 6 carbon atoms,

Each of R ₆ is independently a halogen atom or an alkyl group (for example, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms) Lt; / RTI >

n and m independently represent an integer of 0 to 4;

The compound of formula (I) may be, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis Ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1, Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2- Bis (3-fluoro-4-hydroxyphenyl) propane, 4-methyl-2,2-bis (4-hydroxyphenyl) Pentane, 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) Methane, resorcinol, hydroquinone, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy- Dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro- Hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p, Dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5- (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1- Bis (4-hydroxyphenyl) propane, 1,4-bis (4-hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) isobutane, 2,2- (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2- 4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, Bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) Hydroxyphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis Bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybenzo It may be a non-4,4'-dihydroxy-diphenyl, methyl hydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxy naphthalene, but is not limited thereto. Representative examples include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Other functional dihydric phenols can be found in US Pat. Nos. US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used singly or in combination of two or more. Can be used.

The polycarbonate resin that can be included in the resin composition of the present invention is preferably an aromatic polycarbonate resin, but the type thereof is not particularly limited, and thermoplastic aromatic polycarbonate resins commonly used in the art can be used.

In one embodiment, the aromatic polycarbonate resin may be prepared from a divalent phenol, a carbonate precursor, and a molecular weight modifier.

The dihydric phenol is one of the monomers constituting the aromatic polycarbonate resin and may be represented by the following formula (2).

(2)

In Formula 2,

X is a straight, branched or cyclic alkylene group having no functional group; Or a straight, branched or cyclic alkylene group containing at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, naphthyl or isobutylphenyl, A linear alkylene group having 3 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 6 carbon atoms,

R ₁ and R ₂ are independently a halogen atom or an alkyl group (for example, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, preferably 3 to 6 carbon atoms ),

n and m independently represent an integer of 0 to 4;

Non-limiting examples of the dihydric phenols include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4- hydroxyphenyl) naphthylmethane, bis Ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1, Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) Preferably, bisphenol A is used.

The carbonate precursor is another monomer constituting the aromatic polycarbonate resin, and examples thereof include carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate, dimethyl carbonate and the like . Preferably, carbonyl chloride (phosgene) is used.

As the molecular weight modifier, a monofunctional compound similar to the monomer used in the production of the thermoplastic aromatic polycarbonate resin may be used. Non-limiting examples of molecular weight regulators include phenol based derivatives such as para-isopropylphenol, para-tert-butylphenol (PTBP), para-cumylphenol, para- -Isononylphenol and the like), aliphatic alcohols and the like. Preferably, para-tert-butylphenol (PTBP) is used.

Examples of the aromatic polycarbonate resin produced from such a dihydric phenol, a carbonate precursor and a molecular weight modifier include linear polycarbonate resin, branched polycarbonate resin, copolycarbonate resin or polyester carbonate resin , And these may be used alone or in combination of two or more.

The preferred aromatic polycarbonate having a viscosity average molecular weight of resin _(v M, as measured in methylene chloride solution) is from 15,000 to 40,000, more preferably 17,000 to 30,000, most preferably 18,000 to 30,000. If the viscosity average molecular weight of the aromatic polycarbonate resin is less than 15,000, the mechanical properties such as impact strength and tensile strength may be largely lowered. If the aromatic polycarbonate resin is more than 40,000, there is a problem in processing the resin due to an increase in melt viscosity.

The content of the polycarbonate resin in the resin composition of the present invention may be 50 to 90 parts by weight, more preferably 55 to 90 parts by weight, and most preferably 65 to 90 parts by weight, based on 100 parts by weight of the total composition To 90 parts by weight. If the content of the polycarbonate resin in the resin composition of the present invention is less than 50 parts by weight based on 100 parts by weight of the total composition, properties such as transparency, fluidity, heat resistance and impact strength may be deteriorated, and if it exceeds 90 parts by weight, .

(B) a polyester resin

The resin composition of the present invention includes a polyester resin for improving physical properties such as transparency, fluidity and chemical resistance.

According to one embodiment of the present invention, the polyester resin may be prepared by condensation polymerization of at least one aromatic, aliphatic or alicyclic dicarboxylic acid with at least one aliphatic or alicyclic glycol. Preferably, the aromatic dicarboxylic acid is comprised of 6 to 20 carbon atoms, the aliphatic or alicyclic dicarboxylic acid is comprised of 3 to 20 carbon atoms, and the aliphatic or alicyclic glycol is comprised of 2 to 20 carbon atoms .

A polyester resin can be synthesized using the dicarboxylic acid compound and the glycol compound as described above. The production of a polyester resin using a dicarboxylic acid compound and a glycol compound is usually carried out in two stages of an esterification reaction and a polycondensation reaction, and the production process thereof is already well known in the art.

Examples of the dicarboxylic acid compound include terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, 4-, 1,5-, 2,3-, 2,6- or 2,7-) naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-dibenzyldicar And the like may be used, but the present invention is not limited thereto. Preferably, terephthalic acid, isophthalic acid or a mixture thereof is used.

Examples of the glycol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-, 1,3- or 1,4-) cyclohexanedimethanol, neopentyl glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the like, It is not. Preferably, ethylene glycol, cyclohexanedimethanol or a mixture thereof is used.

More specifically, as the polyester resin contained in the resin composition of the present invention, a resin selected from a polyethylene terephthalate resin, a polypropylene terephthalate resin, a polybutylene terephthalate resin or a mixture thereof may be used, It is not. Preferably, a polyethylene terephthalate (PET) resin excellent in heat resistance, chemical resistance, electrical properties, mechanical strength and molding processability and advantageous in terms of economy can be used.

In terms of processability and mechanical properties, the intrinsic viscosity (IV) of the polyester resin at 25 ° C is preferably 0.45 to 1.6 dl / g, more preferably 0.80 to 1.3 dl / g.

The content of the polyester resin in the resin composition of the present invention may be 5 to 45 parts by weight, more preferably 5 to 40 parts by weight, and still more preferably 5 To 35 parts by weight. If the content of the polyester resin in the resin composition of the present invention is less than 5 parts by weight based on 100 parts by weight of the total composition, the processing efficiency at the time of injection and extrusion may be lowered and the chemical resistance and transparency may be deteriorated, If the amount exceeds 45 parts by weight, the solidification rate may be lowered, resulting in a decrease in productivity and a dimensional instability due to posterior deformation may become relatively large.

(C) Polyalcohol  compound

The resin composition of the present invention includes a polyalcohol compound for improving physical properties such as fluidity and transparency.

According to one embodiment of the present invention, examples of the polyalcohol compound include ethylene glycol, propylene glycol, hexaethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexane di (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) propane, and 4,4'-diphenylmethane diisocyanate. -Hydroxyphenyl) sulfone, a polymer polyol (e.g., polycarbonate diol), or a combination thereof.

The content of the polyalcohol compound contained in the resin composition of the present invention may be 0.1 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, and even more preferably 0.1 To 6 parts by weight. If the content of the polyalcohol compound in the resin composition of the present invention is less than 0.1 parts by weight based on 100 parts by weight of the total composition, the flowability may be lowered and the processing efficiency may be lowered. On the other hand, if the content is more than 10 parts by weight, Discoloration of the workpiece may occur.

(D) Any other additional component

In addition to the above-described components, the composition of the present invention may further include additives generally usable in the thermoplastic resin composition to the extent that the composition does not deviate from the intended purpose. The kind and content of the specific additives may be easily selected by those skilled in the art It will be possible.

In one embodiment, the composition of the present invention can be used as a lubricant, an antioxidant, a light stabilizer, a hydrolytic stabilizer, a release agent, a pigment, an antistatic agent, a conductivity imparting agent, a magnetic property imparting agent, a crosslinking agent, A coupling agent, or a combination of two or more thereof. The total amount of these additives to be added is usually from 0.2 to 5 parts by weight based on 100 parts by weight of the total composition, but is not limited thereto.

There is no particular limitation on the method for preparing the polycarbonate resin composition of the present invention by using each of the components as described above. The polycarbonate resin composition of the present invention can be produced by a general resin composition manufacturing method known in the art. For example, the compositions of the present invention can be obtained by mixing and uniformly dispersing each component in a mixer.

The thermoplastic resin composition of the present invention is excellent in transparency and chemical resistance, and has excellent balance of physical properties such as fluidity, impact strength and heat resistance, and can be applied to various applications such as automobiles, electric / electronic parts, and office equipment. And can be usefully used in housings and automobile interior and exterior parts, which are major components in various OAs and communication devices such as automobiles.

Therefore, according to another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition of the present invention.

The molded article can be produced by extruding or injection molding a thermoplastic resin composition. The method of processing the thermoplastic resin composition of the present invention to produce a molded article is not particularly limited and may be molded and manufactured by using a general resin composition processing method known in the art.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[ Example ]

Example  1 to 3 and Comparative Example  1 to 3

The components shown in the following Table 1 were mixed by a Henschel mixer, dispersed uniformly, and then extruded at a temperature of 240 to 270 ° C in a biaxial melt mixing extruder having L / D = 40 and? = 25 mm The thermoplastic resin composition was prepared in the form of pellets.

The prepared pellets were dried in a hot air drier at 80 to 100 ° C. for 4 hours or more and then injection molded at 240 to 270 ° C. to prepare specimens. The properties of the prepared specimens were measured and evaluated in the following Table 2, and the results are shown in Table 2.

[Material Used]

(A): Polycarbonate resin: intrinsic viscosity 0.55 dl / g (at 25 占 폚 in methylene chloride)

(B): Polyester resin: polyethylene terephthalate (intrinsic viscosity: 0.80 dl / g (25 DEG C, in phenol / tetrachloroethane 50/50 solution))

(C): polyalcohol compound: polyalcohol compound (MB-PBT, PolyChem) having a water solubility (30 ° C) of 909 g /

[Measurement of physical properties]

(1) flowability was measured at 300 ℃ temperature and 1.2kg _f loading conditions on the basis of ASTM D1238.

(2) Tensile strength: Evaluated according to ASTM D638, and the final test results were calculated as the average of test results of five test pieces.

(3) Transparency: 3 mm thick specimens were evaluated according to ASTM D1003.

(4) Chemical resistance: Test specimens were mounted on a jig bent at a predetermined curvature to give 0.5%, 1.0% and 1.5% strain. The time (unit: hour) in which the crack occurred was measured after uniformly applying the chemical (aromatic) to each specimen mounted on the jig. As the generation of cracks is delayed, the chemical resistance is more excellent.

[Table 1] (content of ingredients: parts by weight)

[Table 2] Measurement results of physical properties

*: The symbol ">" means more than the corresponding value. For example, " 72 " means that cracks were observed after more than 72 hours.

As shown in Table 2, Examples 1 to 3 according to the present invention are superior in chemical resistance to those of Comparative Examples 1 to 3 and have excellent fluidity, mechanical properties, transparency and chemical resistance.

Claims (7)

A) a thermoplastic resin composition comprising a polycarbonate resin, (B) a polyester resin, and (C) a polyalcohol compound. The composition according to claim 1, which comprises 50 to 90 parts by weight of (A) a polycarbonate resin, (B) 5 to 45 parts by weight of a polyester resin, and (C) 0.1 to 10 parts by weight of a polyalcohol compound, based on 100 parts by weight of the total composition To the thermoplastic resin composition. The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin. The thermoplastic resin composition according to claim 1, wherein the polyester resin is selected from a polyethylene terephthalate resin, a polypropylene terephthalate resin, a polybutylene terephthalate resin, or a mixture thereof. The process according to claim 1, wherein the polyalcohol compound is selected from the group consisting of ethylene glycol, propylene glycol, hexaethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, decamethylene glycol, Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-bis (4-hydroxyphenyl) propane, bis A thermoplastic resin composition, and combinations thereof. The positive photosensitive composition as claimed in claim 1, wherein the lubricant, the antioxidant, the light stabilizer, the hydrolytic stabilizer, the releasing agent, the pigment, the antistatic agent, the conductivity imparting agent, the magnetic agent, Wherein the thermoplastic resin composition further comprises at least one additive selected from the group consisting of combinations of two or more thereof. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 6.