KR102041010B1 - Polycarbonate resin composition and article produced therefrom - Google Patents

Abstract

Polycarbonate resin composition of the present invention is a polycarbonate resin; Metaterphenyl compound; And an epoxy ester compound comprising an ester group and an epoxy group. The polycarbonate resin composition is excellent in hydrolysis resistance, transparency, molding processability, surface hardness after molding, and the like.

Description

Polycarbonate resin composition and molded article formed therefrom {POLYCARBONATE RESIN COMPOSITION AND ARTICLE PRODUCED THEREFROM}

The present invention relates to a polycarbonate resin composition and a molded article formed therefrom. More specifically, the present invention relates to a polycarbonate resin composition excellent in hydrolysis resistance, transparency, molding processability, surface hardness after molding and the like and molded articles formed therefrom.

Polycarbonate resins are widely used in automobiles and electronic products because of their excellent mechanical properties such as formability, impact resistance, and rigidity, and excellent electrical properties and transparency. Polycarbonate resins are also used as 3D printing materials (thermoplastic molding compositions).

For 3D printing, the material must first be fluidized and extruded, the molten material should be laminated as the printer nozzle moves, and the material must be cooled to below the solidification temperature to allow the material to solidify. Such materials include polycarbonate resins, ABS (Acrylonitrile-Butadiene-Styrene) resins, polystyrene resins, acrylate resins, amorphous polyamide resins, polyester resins, etc. For shaping, the molecular weight is lowered, or two or more kinds of materials are mixed, so that the surface hardness after molding is lowered and broken, or the hydrolysis resistance is lowered.

Therefore, development of a polycarbonate resin composition excellent in hydrolysis resistance, transparency, molding processability, post-molding surface hardness, etc. suitable for 3D printing materials and the like and molded articles formed therefrom is desired.

Background art of the present invention is disclosed in Japanese Patent Laid-Open No. 2016-097584.

An object of the present invention is to provide a polycarbonate resin composition having excellent hydrolysis resistance, transparency, molding processability, surface hardness after molding, and the like.

Another object of the present invention is to provide a molded article formed from the polycarbonate resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a polycarbonate resin composition. The polycarbonate resin composition is a polycarbonate resin; Metaterphenyl compound; And an epoxy ester compound comprising an ester group and an epoxy group.

In an embodiment, the polycarbonate resin composition may include 100 parts by weight of the polycarbonate resin; 1 to 20 parts by weight of the metaterphenyl compound; And 0.001 to 1 part by weight of the epoxy ester compound.

In embodiments, the polycarbonate resin may have a weight average molecular weight of 12,000 to 30,000 g / mol.

In embodiments, the metaterphenyl compound may be represented by Formula 1:

[Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom, a is an integer of 0 to 4, b and c are each independently an integer of 0 to 5.

In embodiments, the epoxy ester compound may be represented by the following formula (2):

[Formula 2]

In Formula 2, R ₄ and R ₆ are each independently a hydrocarbon group having 1 to 10 carbon atoms, R ₅ and R ₇ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ₄ and R ₅ And R ₆ and R ₇ may be linked to each other to form a ring or not to form, m and n are 0 or 1, and m + n is 1 or 2.

In embodiments, the weight ratio of the metaterphenyl compound and the epoxy ester compound (methterphenyl compound: epoxy ester compound) may be 1: 0.001 to 1: 0.05.

In an embodiment, the polycarbonate resin composition may have a transmittance of 85% or more of a 2.5 mm thick injection molded specimen measured according to ASTM D1003.

In an embodiment, the polycarbonate resin composition may have a glass transition temperature of 110 to 150 ° C.

In an embodiment, the polycarbonate resin composition may have a Vickers hardness of 15 to 20, based on KS B 0811: 2003.

In an embodiment, the polycarbonate resin composition may have a weight average molecular weight change of 2,000 g / mol or less after treating 3.2 mm thick injection molded specimens at 120 ° C. and 1.8 bar steam for 16 hours.

Another aspect of the present invention relates to a molded article formed from the polycarbonate resin composition.

The present invention has the effect of providing a polycarbonate resin composition excellent in hydrolysis resistance, transparency, molding processability, surface hardness after molding and the like and molded articles formed therefrom.

Hereinafter, the present invention will be described in detail.

Polycarbonate resin composition according to the invention (A) polycarbonate resin; (B) metaterphenyl compounds; And (C) an epoxy ester compound.

(A) polycarbonate resin

The polycarbonate resin according to one embodiment of the present invention may be an aromatic polycarbonate resin used in a conventional thermoplastic resin composition. For example, an aromatic polycarbonate resin prepared by reacting diphenols (aromatic diol compounds) with carbonate precursors such as phosgene, halogen formate, and carbonic acid diester can be used as the polycarbonate resin.

In an embodiment, the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1 , 1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) Propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and the like can be exemplified. For example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4- Hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane can be used, specifically, bisphenol- 2, 2-bis (4-hydroxyphenyl) propane called A can be used.

In embodiments, the carbonate precursor is dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate , Carbonyl chloride (phosgene), diphosgene, triphosgene, carbonyl bromide, bishaloformate, and the like. These can be used individually or in mixture of 2 or more types.

The polycarbonate resin may be a branched chain, for example, 0.05 to 2 mol% of a trivalent or more polyfunctional compound, specifically, trivalent or more relative to the total diphenols used for polymerization It can also manufacture by adding the compound which has a phenol group.

The polycarbonate resin may be used in the form of a homo polycarbonate resin, copolycarbonate resin or blends thereof. In addition, the polycarbonate resin may be partially or entirely replaced by an aromatic polyester-carbonate resin obtained by polymerizing in the presence of an ester precursor, for example, a bifunctional carboxylic acid.

In embodiments, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 12,000 to 30,000 g / mol, for example, 16,000 to 23,000 g / mol. In the above range, it is possible to obtain a polycarbonate resin composition having heat resistance, molding processability, mechanical properties, and the like suitable as a 3D printing material.

(B) metaterphenyl compound

The metaterphenyl (m-terphenyl) compound according to an embodiment of the present invention may improve molding processability, surface hardness after molding, etc. of the polycarbonate resin composition, and a compound represented by the following Chemical Formula 1 may be used.

[Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom, a is an integer of 0 to 4, b and c are each independently an integer of 0 to 5.

In an embodiment, the metaterphenyl compound may be included in an amount of 1 to 20 parts by weight, for example, 5 to 15 parts by weight, based on 100 parts by weight of the polycarbonate resin. In the above range, molding processability of the polycarbonate resin composition, surface hardness after molding, and the like can be improved.

(C) epoxy ester compounds

The epoxy ester compound according to one embodiment of the present invention is capable of improving hydrolysis resistance of a polycarbonate resin composition, and includes an ester group and an epoxy group. For example, the compound represented by Formula 2 may be included.

[Formula 2]

In Formula 2, R ₄ and R ₆ are each independently a hydrocarbon group having 1 to 10 carbon atoms, R ₅ and R ₇ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ₄ and R ₅ And R ₆ and R ₇ may be linked to each other to form a ring or not to form, m and n are 0 or 1, and m + n is 1 or 2.

In specific examples, the epoxy ester compound may be exemplified by the compound represented by the following formula (2a) to (2c).

[Formula 2a]

[Formula 2b]

[Formula 2c]

In an embodiment, the epoxy ester compound may be included in an amount of 0.001 to 1 part by weight, for example, 0.01 to 0.5 part by weight, based on 100 parts by weight of the polycarbonate resin. Hydrolysis resistance of a polycarbonate resin composition etc. can be improved in the said range.

In embodiments, the weight ratio ((B) :( C)) of the metaterphenyl compound (B) and the epoxy ester compound (C) is from 1: 0.001 to 1: 0.05, for example, from 1: 0.002 to 1: 0.01 days. Can be. In the above range, the molding processability of the polycarbonate resin composition, surface hardness after molding, hydrolysis resistance, and the like may be more excellent.

The polycarbonate resin composition according to one embodiment of the present invention may further include an additive included in a conventional polycarbonate resin composition. The additives may include, but are not limited to, flame retardants, fillers, antioxidants, anti drip agents, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, mixtures thereof, and the like. When using the additive, the content may be 0.001 to 40 parts by weight, for example 0.1 to 10 parts by weight, based on 100 parts by weight of the polycarbonate resin.

The polycarbonate resin composition according to an embodiment of the present invention may be in the form of pellets which are mixed with the above components and melt-extruded at 200 to 280 ° C, for example, 220 to 250 ° C, using a conventional twin screw extruder. The polycarbonate resin composition has excellent hydrolysis resistance, transparency, molding processability, surface hardness after molding, and the like, and is particularly useful as a material for 3D printing.

In an embodiment, the polycarbonate resin composition may have a transmittance (light transmittance) of 85% or more, for example, 87 to 99%, of the 2.5 mm thick injection molded specimen measured according to ASTM D1003.

In an embodiment, the polycarbonate resin composition may have a glass transition temperature of 110 to 150 ° C., for example 115 to 130 ° C., measured by differential scanning calorimetry (DSC). In the above range, the molding processability of the polycarbonate resin composition may be excellent.

In an embodiment, the polycarbonate resin composition may have a Vickers hardness of 15 to 20, for example, 16 to 19, measured based on KS B 0811: 2003. In the above range, the surface hardness after molding of the polycarbonate resin composition may be excellent.

In one embodiment, the polycarbonate resin composition has a weight average molecular weight change of 2,000 g / mol or less, for example, 500 to 1,900 g / mol after treating a 3.2 mm thick injection molded specimen with 120 ° C. and 1.8 bar steam for 16 hours. Can be. The hydrolysis resistance of the polycarbonate resin composition may be excellent in the above range.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be prepared in a pellet form, and the prepared pellet may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known by those skilled in the art. Since the molded article is excellent in hydrolysis resistance, transparency, surface hardness, etc., it is useful as a 3D printed molded article, an interior / exterior material of an electric / electronic product, and the like.

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.

Example

Specifications of each component used in the following Examples and Comparative Examples are as follows.

(A) polycarbonate resin

(A1) A bisphenol A polycarbonate resin having a weight average molecular weight of 22,000 g / mol was used.

(A2) A bisphenol A polycarbonate resin having a weight average molecular weight of 16,000 g / mol was used.

(B) metaterphenyl compound

Metaterphenyl (m-terphenyl, a, b and c: 0) of Chemical Formula 1 was used.

[Formula 1]

(C) epoxy ester compounds

The compound represented by the following formula (2a) was used.

[Formula 2a]

Examples 1-8 and Comparative Examples 1-2: Preparation of Polycarbonate Resin Compositions

Each of the components was added in an amount as described in Tables 1 and 2, and then extruded at an extrusion temperature of 300 ° C. to prepare pellets. Extrusion was performed using a twin screw extruder with a diameter of L / D = 36 and 45 mm, and the prepared pellets were dried at 80 ° C. for at least 4 hours, and then in a 6 oz injection molding machine (molding temperature 250 to 260 ° C., mold temperature: 60 ° C.). The specimen was prepared by injection molding. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

Property measurement method

(1) Permeability (Unit%): According to ASTM D1003, the transmittance (total light transmittance) of the 2.5 mm thick injection molded specimen was measured.

(2) Glass transition temperature (Tg, unit: ℃): Using DSC (Q2910, manufactured by TA Instrument), first raise the temperature from 20 ℃ to 160 ℃ at a rate of 20 ℃ / min, then cool slowly and equilibrate at 50 ℃ After the state was maintained, the temperature was further raised to 160 ° C at a rate of 10 ° C / min. The inflection point of the endothermic transition curve was determined by the glass transition temperature.

(3) Vickers hardness: Based on KS B 0811: 2003, Vickers hardness was measured using a diamond pyramidal indenter with a facing angle of 136 DEG under 196.1 N load conditions.

(4) Hydrolysis resistance evaluation (wet heat evaluation, unit: g / mol): After measuring the weight average molecular weight (Mw) of the polycarbonate resin composition injection molded specimen having a thickness of 3.2 mm using GPC (gel permeation chromatography) After the specimen was placed in an autoclave and treated (maintained) for 16 hours at 1.8 bar and steam at 120 ° C., the weight average molecular weight was measured in the same manner, and the weight average molecular weight difference before and after the wet heat evaluation ( ΔMw) was calculated.

Example One 2 3 4 5 6 7 8 (A) (parts by weight) (A1) 100 100 100 100 100 100 - - (A2) - - - - - - 100 100 (B) (parts by weight) 5 5 5 10 10 10 5 10 (C) (parts by weight) 0.02 0.04 0.1 0.02 0.04 0.1 0.04 0.1 Permeability (%) 89 89 89 87 87 87 89 87 Glass transition temperature (℃) 117 117 116 116 116 116 117 116 Vickers hardness 17.5 17.5 17.5 17.5 17.5 17.5 17.5 17.5 Hydrolysis resistance (ΔMw, g / mol) 1,500 1,000 1,000 1,500 1,000 1,000 1,200 1,200

Comparative example One 2 (A) (parts by weight) (A1) 100 100 (A2) - - (B) (parts by weight) - 10 (C) (parts by weight) 0.04 - Permeability (%) 87 87 Glass transition temperature (℃) 140 110 Vickers hardness 14 20 Hydrolysis resistance (ΔMw, g / mol) 1,000 2,300

From the above results, it can be seen that the polycarbonate resin composition according to the present invention has all excellent hydrolysis resistance, transparency (transmittance), molding processability (glass transition temperature), surface hardness after molding (Vickers hardness) and the like.

On the other hand, in the case of Comparative Example 1 without using the metaterphenyl compound, it can be seen that the molding processability, surface hardness, etc. are reduced, and in Comparative Example 2 without the epoxy ester compound, the hydrolysis resistance is significantly reduced. Can be.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (11)

100 parts by weight of polycarbonate resin;
1 to 20 parts by weight of the metaterphenyl compound represented by Formula 1; And
Contains 0.001 to 1 part by weight of an epoxy ester compound including an ester group and an epoxy group represented by Formula 2;
The glass transition temperature is 110 to 130 ° C, Vickers hardness is 15 to 20 measured according to KS B 0811: 2003, and the weight average after treating 3.2 mm thick injection molded specimens with 120 ° C and 1.8 bar steam for 16 hours. Polycarbonate resin composition for 3D printer, characterized in that the molecular weight change is 2,000 g / mol or less:
[Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ are each independently an alkyl group or halogen atom having 1 to 5 carbon atoms, a is an integer of 0 to 4, b and c are each independently an integer of 0 to 5;
[Formula 2]

In Formula 2, R ₄ and R ₆ are each independently a hydrocarbon group having 1 to 10 carbon atoms, R ₅ and R ₇ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ₄ and R ₅ and R ₆ and R ₇ may be linked to each other to form a ring or not to form, m and n are 0 or 1, and m + n is 1 or 2.
delete The polycarbonate resin composition for a 3D printer according to claim 1, wherein the polycarbonate resin has a weight average molecular weight of 12,000 to 30,000 g / mol.
delete delete The polycarbonate resin composition for a 3D printer according to claim 1, wherein the weight ratio (metaterphenyl compound: epoxy ester compound) of the metaterphenyl compound and the epoxy ester compound is 1: 0.001 to 1: 0.05.
The polycarbonate resin composition for a 3D printer according to claim 1, wherein the polycarbonate resin composition has a transmittance of 85% or more of a 2.5 mm thick injection molded specimen measured according to ASTM D1003.
delete delete delete The molded article formed from the polycarbonate resin composition for 3D printers of any one of Claims 1, 3, 6, and 7.