KR20080062469A - Polycarbonate resin composition and plastic article - Google Patents

Abstract

A polycarbonate-based resin composition, and a plastic molded product prepared by using the composition are provided to improve impact resistance and chemical resistance. A polycarbonate-based resin composition comprises 60-98 parts by weight of a polycarbonate resin; 1-30 parts by weight of a polyphenylene sulfide resin; and 1-10 parts by weight of a core-shell graft copolymer. Preferably the polycarbonate resin is at least one selected from a linear polycarbonate resin, a branched polycarbonate resin and a polyester carbonate copolymer resin; and the polyphenylene sulfide resin comprises 70 mol% or more of a repeating unit represented by the formula 1.

Description

Polycarbonate-based resin composition and plastic molded article {POLYCARBONATE RESIN COMPOSITION AND PLASTIC ARTICLE}

The present invention relates to a polycarbonate resin composition and a plastic molded article. More specifically, the present invention relates to a polyphenylene carbonate-based resin composition and a plastic molded article which can further improve the chemical resistance of the polycarbonate-based thermoplastic resin.

Polycarbonate-based thermoplastic resins are excellent in impact resistance, self-extinguishing, dimensional stability or heat resistance, and are widely used in various electrical and electronic products or automobile parts.

However, such polycarbonate-based thermoplastic resins exhibit relatively low chemical resistance. For this reason, for example, when coating is performed using the injection molded article of the polycarbonate-based thermoplastic resin as an exterior material, a dilution solution of the paint used for coating may penetrate into the injection molded article, thereby reducing mechanical properties or impact resistance. .

Therefore, many studies have been made to further improve the chemical resistance of the polycarbonate-based thermoplastic resin. For example, attempts have been made to further improve the chemical resistance of polycarbonate-based thermoplastic resins by mixing a polymer having a relatively slow penetration of chemicals into the polycarbonate-based resin composition. However, according to this method, the impact resistance of the polycarbonate-based thermoplastic resin can be lowered.

Accordingly, the present invention is to provide a polycarbonate-based resin composition which can further improve the impact resistance together with the chemical resistance of the polycarbonate-based thermoplastic resin.

Another object of the present invention to provide a plastic molded article prepared using the composition.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

The present invention provides a polycarbonate resin composition comprising 60 to 98 parts by weight of a polycarbonate resin, 1 to 30 parts by weight of a polyphenylene sulfide resin, and 1 to 10 parts by weight of a core-shell graft copolymer. .

The present invention also provides a plastic molded article made of the polycarbonate resin composition.

Other specific details of the embodiments of the present invention are included in the following detailed description.

Hereinafter, specific embodiments of the present invention will be described in detail to enable those skilled in the art to clearly appreciate. However, this is presented as an example of the present invention, whereby the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

According to one embodiment of the invention, a polycarbonate system comprising 60 to 98 parts by weight of the polycarbonate resin, 1 to 30 parts by weight of the polyphenylene sulfide resin, and 1 to 10 parts by weight of the core-shell graft copolymer A resin composition is provided.

Such a polycarbonate-based resin composition includes a polyphenylene sulfide resin having excellent chemical resistance together with a polycarbonate resin which is a basic component. By the addition of such polyphenylene sulfide resin, the chemical resistance of the polycarbonate-based thermoplastic resin can be further improved. In addition, as the core-shell graft copolymer is included together with these two components, impact resistance of the polycarbonate-based thermoplastic resin may be further improved. That is, the polycarbonate resin composition includes a polyphenylene sulfide resin and a core-shell graft copolymer together with the polycarbonate resin in a preferred content ratio, thereby further improving impact resistance together with chemical resistance of the polycarbonate thermoplastic resin. You can.

The structure of such a polycarbonate-based resin composition is specifically described below for each component.

The polycarbonate-based resin composition includes a polycarbonate resin.

The polycarbonate resin may be prepared by reacting a dihydric phenol compound and a phosgene in the presence of a molecular weight modifier and a catalyst according to a conventional production method. In another embodiment, the polycarbonate resin may be prepared using an ester interchange reaction of a dihydric phenol compound and a carbonate precursor such as diphenyl carbonate.

In the production method of such a polycarbonate resin, a bisphenol compound may be used as the dihydric phenol compound, and preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) may be used. . In this case, the bisphenol A may be partially or wholly replaced by another type of dihydric phenol compound. Examples of other types of dihydric phenolic compounds that can be used include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl) cyclo Hexane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Halogenated bisphenols such as sulfoxide, bis (4-hydroxyphenyl) ketone or bis (4-hydroxyphenyl) ether or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane Etc. can be mentioned.

However, the type of dihydric phenolic compound that can be used for the production of the polycarbonate resin is not limited thereto, and the polycarbonate resin may be manufactured using any dihydric phenolic compound.

In addition, the polycarbonate resin may be a homopolymer using one type of dihydric phenolic compound, a copolymer using two or more types of dihydric phenolic compounds, or a mixture thereof.

In general, the polycarbonate resin may take the form of a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin, and the like, and the polycarbonate resin included in the polycarbonate resin composition may be formed in a specific form. Without limitation, all of these linear polycarbonate resins, branched polycarbonate resins, polyester carbonate copolymer resins, and the like can be used.

Among these, as said linear polycarbonate resin, a bisphenol-A polycarbonate resin can be used, for example, As said branched polycarbonate resin, For example, polyfunctionality, such as trimellitic anhydride or trimellitic acid, Those prepared by reacting an aromatic compound with a dihydric phenolic compound and a carbonate precursor can be used. As the polyester carbonate copolymer resin, for example, one produced by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor can be used. In addition, conventional linear polycarbonate resins, branched polycarbonate resins, or polyester carbonate copolymer resins can be used without limitation.

On the other hand, the polycarbonate resin is included in the content range of 60 to 98 parts by weight. As the polycarbonate resin is included in such a content range, impact resistance and chemical resistance of the polycarbonate-based thermoplastic resin may be further improved.

The polycarbonate-based resin composition further includes a polyphenylene sulfide resin. As the polyphenylene sulfide resin, one containing 70 mol% or more of the repeating unit represented by the following Chemical Formula 1 may be used. The polyphenylene sulfide resin containing 70 mol% or more of such repeating units has high crystallinity, which is a characteristic of the crystalline polymer, and exhibits advantages in heat resistance, chemical resistance, and mechanical strength, and thus may be preferably used in the polycarbonate-based resin composition. have.

[Formula 1]

The polyphenylene sulfide resin may include one or more other repeating units selected from the following Chemical Formulas 2 to 9, in addition to the repeating units of Chemical Formula 1 above. However, the repeating units of Formulas 2 to 9 are preferably contained in less than 50 mol%, preferably less than 30 mol%.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formula 7, R is an alkyl group, nitro group, phenyl group, alkoxy group, carboxyl group or metal carboxylate group.

It is generally known that polyphenylene sulfide resins may have a linear molecular structure that does not include a branched or crosslinked structure, or may have a molecular structure that includes a branched or crosslinked structure, depending on the preparation method thereof. However, as confirmed in the above Chemical Formulas 1 to 9, the polyphenylene sulfide resin included in the polycarbonate-based resin composition may be effectively used having any molecular structure.

Representative methods for producing crosslinked polyphenylene sulfide resins are disclosed in Japanese Patent Application No. 45-3368 and the like, and representative methods for producing linear polyphenylene sulfide resins are disclosed in Japanese Patent Application No. 52-12240 and the like.

In terms of thermal stability and workability of the polyphenylene sulfide resin composition, the polyphenylene sulfide resin has a melt index (MI) of 10 to 300 g / 10 min at a load of 316 ° C and 2.16 kg. It is preferable to have. When the melt index exceeds 300 g / 10 minutes, it may not be preferable in terms of the mechanical strength of the polycarbonate-based thermoplastic resin, and if less than 10 g / 10 minutes, the kneading property or injection process of the polycarbonate-based resin composition In terms of workability of the city may be undesirable.

The polyphenylene sulfide resin is included in the content range of 1 to 30 parts by weight in the polycarbonate-based resin composition. When the content ratio of the polyphenylene sulfide resin exceeds 30 parts by weight, the impact resistance or chemical resistance of the polycarbonate-based thermoplastic resin may be lowered. If it is less than 1 part by weight, the chemical resistance is improved by adding the polyphenylene sulfide resin. The effect may not be enough.

On the other hand, the polycarbonate-based resin composition further comprises a core-shell graft copolymer. The core-shell graft copolymer is prepared by polymerizing a rubber monomer and grafting a predetermined unsaturated compound to a polymerization product of the rubber monomer, and the unsaturated compound is grafted to the core structure of rubber to form a hard shell. It is a core-shell structure.

Such core-shell graft copolymers, for example, polymerize one or more monomers selected from the group consisting of C ₄ to C ₆ diene rubber monomers, acrylate rubber monomers and silicone rubber monomers, and polymerize the monomers. the outcome, one selected from the group consisting of C ₁ ~ C ₈ methacrylic acid alkyl esters, C ₁ ~ C ₈ of methacrylic acid esters, maleic anhydride and C ₁ ~ alkyl or phenyl nuclear-substituted maleimide of C ₄ The above unsaturated compounds may be grafted to form a core-shell structure.

In this case, as the acrylate rubber monomer, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate or 2-ethyl Hexyl methacrylate etc. can be used. And as a hardening | curing agent for superposing | polymerizing such an acrylate rubber monomer, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 3- butylene glycol dimethacrylate, or 1, 4- butylene glycol Dimethacrylate, allyl methacrylate, triallyl cyanurate, etc. can be used.

In addition, the silicone rubber monomer may be prepared from cyclosiloxane. For example, such silicone rubber monomers include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, and tetramethyltetraphenylcyclotetro. Siloxane or octaphenylcyclotetrasiloxane and the like can be used. One or more of the silicone rubber monomers may be polymerized to form a rubber core structure. Examples of the curing agent for the polymerization of the silicone rubber monomers include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, or the like. Tetraethoxysilane and the like can be used.

However, the kind of the rubber monomer usable for forming the core-shell graft copolymer is not limited to the above-described materials, and any other diene rubber monomer, acrylate rubber monomer or silicone rubber monomer may be used. have.

On the other hand, in the unsaturated compound grafted to the core structure of the rubber, the C ₁ to C ₈ methacrylic acid alkyl esters or C ₁ to C ₈ methacrylic acid esters are esters of acrylic acid or methacrylic acid, respectively As a monohydryl alcohol compound having 1 to 8 carbon atoms. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, and the like, and among these, methacrylic acid methyl ester may be preferably used.

The core-shell graft copolymer is included in the content range of 1 to 10 parts by weight of the polycarbonate-based resin composition. If the content ratio of the core-shell graft copolymer is less than 1 part by weight, the effect of improving the impact resistance of the polycarbonate-based thermoplastic resin may not be sufficient. In addition, when the content ratio of the core-shell graft copolymer exceeds 10 parts by weight, mechanical strength such as tensile strength, flexural strength or flexural modulus of the polycarbonate-based thermoplastic resin may be lowered.

Meanwhile, the polycarbonate-based resin composition described above may be flame retardant, lubricant, antibacterial agent, mold release agent, nucleating agent, plasticizer, heat stabilizer, antioxidant, light stabilizer, compatibilizer, pigment, dye, or other inorganic material depending on the use thereof in addition to the above-mentioned components Various additives, such as an additive, can be further included.

A polycarbonate-based thermoplastic resin or a plastic molded article produced therefrom through a conventional method such as mixing each of the above-described components to prepare a polycarbonate-based resin composition, and melt-extruding the polycarbonate-based resin composition in an extruder. Can be prepared.

According to another embodiment of the invention, there is provided a plastic molded article prepared from the polycarbonate-based resin composition described above. Such plastic molded articles include, for example, a resin substrate having a polycarbonate resin bonded thereto to form a resin matrix; Polyphenylene sulfide resin dispersed in the resin matrix of the resin substrate; And a core-shell graft copolymer dispersed in the resin matrix of the resin substrate.

That is, the plastic molded article includes a resin substrate in which a polycarbonate resin is bonded to form a resin matrix, and together with the polyphenylene sulfide resin and the core-shell graft copolymer uniformly dispersed in the resin matrix. As a result, more improved impact resistance and chemical resistance may be exhibited.

Therefore, such a plastic molded article can be suitably used as various exterior electrical and electronic products, automobile parts, etc., especially.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

The specific specification of each structural component of (A) polycarbonate resin, (B) polyphenylene sulfide resin, and (C) core-shell graft copolymer used by the below-mentioned Example and comparative example is as follows.

(A) polycarbonate resin

As the polycarbonate resin, PANLITE L-1250WP of TEIJIN, Japan, which is a bisphenol-A type linear polycarbonate resin having a weight average molecular weight of 25,000 g / mol, was used.

(B) polyphenylene sulfide resin

As the polyphenylene sulfide resin, a linear polyphenylene sulfide resin manufactured by Japan-Japan Ink Corporation (DIC) was used.

(C) core-shell graft copolymer

As a core-shell graft copolymer, METABLEN SX-006 manufactured by Mitsubishi Rayon, Japan, in which styrene and acrylonitrile monomers were grafted to a silicone polymer / acrylic rubber composite, was used.

Examples 1-3 and Comparative Examples 1-3

Each of the components described above were mixed in the content ranges shown in Table 1 to prepare a polycarbonate-based resin composition, and each polycarbonate-based resin composition was introduced into a twin screw extruder having a ￠ = 45 mm to be manufactured in pellet form. It was. Subsequently, after drying for 3 hours or more at 110 ℃, the injection in a 10 oz injection machine under the conditions of the injection temperature of 260 ~ 330 ℃ and mold temperature of 60 ~ 100 ℃ to prepare a flat specimen for evaluation of various properties.

TABLE 1

Example (parts by weight) Comparative example (parts by weight) One 2 3 One 2 3 (A) polycarbonate resin 92 87 85 97 90 57 (B) polyphenylene sulfide resin 5 10 10 - 10 40 (C) core-shell graft copolymer 3 3 5 3 - 3

Various physical properties of the specimen were measured by the following method.

First, the notched Izod impact strength (1/8 "and 1/4") of the specimen was measured according to ASTM D256, a US standard measurement method for measuring the Izod impact strength of plastics using a weight of constant weight. Impact assessment).

In addition, the specimen was immersed in a thinner for 2 minutes of a polycarbonate-based thermoplastic resin containing methyl isobutyl ketone, cyclohexanone and 2-ethoxy ethanol as main components, and then dried at 80 ° C. for 30 minutes. The impact point of the drop was confirmed to confirm the fracture site, and the brittle fracture rate was measured (chemical resistance evaluation).

Various physical properties measured through this method are shown in Table 2 below.

TABLE 2

Referring to Table 2, the specimens of Examples 1 to 3 including the polycarbonate resin, the polyphenylene sulfide resin and the core-shell graft copolymer, the polyphenylene sulfide resin or the core-shell graft copolymer Compared with the specimens of Comparative Examples 1 and 2 that do not include any of the it was confirmed that the improved impact resistance and chemical resistance.

In addition, the specimens of Examples 1 to 3 containing the three constituents in a specific content range are improved impact resistance compared to the specimen of Comparative Example 3 containing a polyphenylene sulfide resin in excess of 30 parts by weight out of the content range And chemical resistance.

According to the present invention, there is provided a polycarbonate-based resin composition which further improves chemical resistance without lowering the impact resistance of the polycarbonate-based thermoplastic resin, thereby enabling the provision of a polycarbonate-based thermoplastic resin having more improved impact resistance and chemical resistance. Can be.

Therefore, the plastic composition which shows the outstanding physical property can be manufactured using the said resin composition, and it can use it suitably for various electrical and electronic components, automobile parts, etc.

Claims (8)

60-98 parts by weight of polycarbonate resin, 1-30 weight part of polyphenylene sulfide resin, Polycarbonate-based resin composition comprising 1 to 10 parts by weight of the core-shell graft copolymer. The polycarbonate-based resin composition of claim 1, wherein the polycarbonate resin comprises one polymer or a mixture of two or more selected from the group consisting of a linear polycarbonate resin, a branched polycarbonate resin, and a polyester carbonate copolymer resin. The polycarbonate-based resin composition of claim 2, wherein the linear polycarbonate resin comprises a bisphenol A-based polycarbonate resin. The polycarbonate-based resin composition of claim 1, wherein the polyphenylene sulfide resin comprises 70 mol% or more of a repeating unit represented by Formula 1 below. [Formula 1]

The polycarbonate-based resin composition according to claim 1, wherein the polyphenylene sulfide resin exhibits a melt index of 10 to 300 g / 10 minutes at a load of 2.16 kg at 316 ° C. The method of claim 1, wherein the core-shell graft copolymer polymerizes at least one monomer selected from the group consisting of C ₄ to C ₆ diene rubber monomers, acrylate rubber monomers and silicone rubber monomers, The polymerization product of the monomer, C ₁ ~ C ₈ methacrylic acid alkyl esters, C ₁ ~ C ₈ of methacrylic acid esters, maleic anhydride and a C ₁ ~ C ₄ alkyl or consisting of phenyl nuclear-substituted maleimide of At least one unsaturated compound selected from the group is grafted to form a core-shell structure. Plastic molded article manufactured from the polycarbonate resin composition according to any one of claims 1 to 6. Resin base material which the polycarbonate resin couple | bonds and forms the resin matrix; Polyphenylene sulfide resin dispersed in the resin matrix of the resin substrate; And A plastic molded article comprising a core-shell graft copolymer dispersed in the resin matrix of the resin substrate.