KR20190063596A - Polycarbonate resin composition for low temperature 3D printing and article comprising the same - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition for 3D printing capable of outputting at low temperatures and an article comprising the same. More particularly, the present invention relates to: the polycarbonate resin composition, which comprises a polycarbonate resin having a specific range of molecular weight and a specific amount of a fluidizing agent, thereby being able to output to a 3D printer at a temperature lower than that of an existing polycarbonate resin composition; and the article comprising the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a polycarbonate resin composition for low-temperature output 3D printing and an article comprising the polycarbonate resin composition for low temperature 3D printing,

The present invention relates to a polycarbonate resin composition for 3D printing capable of outputting at low temperatures and an article comprising the polycarbonate resin composition. More particularly, the present invention relates to a polycarbonate resin composition for 3D printing, which comprises a polycarbonate resin having a specific range of molecular weight, The present invention relates to a polycarbonate resin composition capable of outputting to a 3D printer at a temperature lower than that of a conventional polycarbonate resin composition, and an article containing the polycarbonate resin composition.

The output method of 3D printing varies according to the application. However, considering the equipment price, material supply and output difficulty, the output method most widely used in industry and home is the material extrusion method. The material extrusion method is a method in which a material provided in a filament form is melted and laminates from a nozzle. Examples of the resin for 3D printing filament used in this method include polylactic acid (PLA), acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC) and polyimide (PI).

Of these, polylactic acid resin is the most commonly used resin for 3D printing filament. The polylactic acid resin does not smell at the output and can output at a relatively low temperature, so expensive output equipment is not required. However, since the polylactic acid resin itself has a poor mechanical property, it is necessary to use a resin for 3D printing filament which can output at a relatively low temperature, such as polylactic acid, and exhibits excellent mechanical properties such as high strength.

Polycarbonate resins are engineering plastics with excellent mechanical properties, thermal properties and dimensional stability, and are used in various industrial fields. However, when a polycarbonate resin is used as a resin for a 3D printing filament of a material extrusion type, an expensive output device is required because a high output temperature is required.

Therefore, it is required to develop a resin for 3D printing filament which can output at a relatively low temperature while maintaining excellent mechanical properties.

An object of the present invention is to provide a polycarbonate resin composition for 3D printing capable of outputting to a 3D printer at a relatively low temperature while having excellent mechanical properties, and an article containing the same.

In order to solve the above technical problems, the present invention provides a polycarbonate resin composition comprising (1) a polycarbonate resin and (2) a fluidizing agent, wherein the polycarbonate resin has a viscosity average molecular weight of 16,000 to 20,000, Wherein the content is 3 to 19 parts by weight based on 100 parts by weight of the total of the components (1) and (2).

According to another aspect of the present invention, there is provided an article comprising the polycarbonate resin composition of the present invention.

The polycarbonate resin composition of the present invention can be suitably used for 3D printing because it can output to a 3D printer at a temperature lower than that of a conventional polycarbonate resin composition while maintaining excellent mechanical properties inherent to the polycarbonate resin. Because it does not require equipment, it can improve the economical efficiency of 3D printing and broaden the application range.

Hereinafter, the present invention will be described in detail.

The polycarbonate resin composition of the present invention comprises (1) a polycarbonate resin and (2) a fluidizing agent. The polycarbonate resin composition of the present invention may further optionally contain at least one of (3) other additives.

(1) Polycarbonate resin

The polycarbonate resin that can be included in the resin composition of the present invention is preferably an aromatic polycarbonate resin. However, the polycarbonate resin is not particularly limited as long as the technical idea of the present invention can be realized, and the thermoplastic aromatic A polycarbonate resin can be used.

In one embodiment of the present invention, the aromatic polycarbonate resin may be prepared from a divalent phenol, a carbonate precursor, a molecular weight modifier and the like, and may contain a linear and / or branched polycarbonate homopolymer and a polyester copolymer, .

 The dihydric phenol is one of the monomers constituting the aromatic polycarbonate resin and may be represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

X is an alkylene group; Linear, branched or cyclic alkylene groups having no functional groups; Or a straight, branched or cyclic alkylene group having at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, naphthyl or isobutylphenyl, Or a branched alkylene group having 3 to 10 carbon atoms, or may be a cyclic alkylene group having 3 to 10 carbon atoms,

R ₁ and R ₂ each independently represent a halogen atom, 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,

n and m each 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, 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- Dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis 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-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1- (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1, , 4-bis (4-hydroxyphenyl) propane, 1,4- Bis (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4- Bis (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, , 4,4'-thiodiphenol [bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl- (4-hydroxyphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis Hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone , 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybenz Dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. However, the present invention 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 carbonate precursor is another monomer constituting the aromatic polycarbonate resin. Non-limiting examples of the carbonate precursor include carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate or dimethyl carbonate . Preferably, carbonyl chloride (phosgene) can be 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 such molecular weight regulators include phenol-based derivatives (e.g., para-isopropylphenol, para-tert-butylphenol (PTBP), para- cumyl phenol, para- Para-isononylphenol and the like), aliphatic alcohols and the like. Preferably, para-tert-butylphenol (PTBP) can be used.

The viscosity average molecular weight of the polycarbonate resin included in the resin composition of the present invention may be 16,000 to 20,000, preferably 17,000 to 20,000, and more preferably 17,000 to 19,000. And even more preferably from 17,000 to 18,500. When the viscosity average molecular weight of the polycarbonate resin is less than 16,000, heat resistance and impact strength are lowered, resulting in loss of excellent mechanical properties inherent to the polycarbonate resin. When the viscosity average molecular weight of the polycarbonate resin exceeds 20,000, Temperature is required, an expensive output device capable of high temperature output is required.

(2)

As the fluidizing agent contained in the polycarbonate resin composition of the present invention, a substance capable of improving the fluidity of the polycarbonate resin composition can be used without any particular limitation, and preferably an aromatic phosphate, an aliphatic phosphate, Can be used.

In the resin composition of the present invention, the content of the fluidizing agent is preferably 3 to 19 parts by weight based on 100 parts by weight of the total amount of the polycarbonate resin (component (1)) and the fluidizing agent (component (2) May be 4 to 19 parts by weight, more preferably 5 to 19 parts by weight, and even more preferably 5 to 15 parts by weight. When the content of the fluidizing agent is less than 3 parts by weight based on the total of 100 parts by weight of the total of the polycarbonate resin (component (1)) and the fluidizing agent (component (2)), the effect of improving the fluidity of the resin composition is insignificant, It is necessary to use an expensive output device capable of high temperature output. When the content of the fluidizing agent is more than 19 parts by weight, extrusion can not be carried out by extrusion using the resin composition, and is obtained in the form of pellets Can not.

(3) Other additives

The polycarbonate resin composition of the present invention may further comprise, in addition to the above-mentioned components (1) and (2), at least one other additive conventionally added to the thermoplastic resin composition for injection molding or extrusion molding. For example, one or more additives selected from the group consisting of antioxidants, lubricants, ultraviolet absorbers, or mixtures thereof.

Specific examples of the antioxidant include tris (nonylphenyl) phosphite, (2,4,6-tri-tert-butylphenyl) (2-butyl- (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Organophosphorus antioxidants such as ritoritol diphosphite or distearyl pentaerythritol diphosphite; (3,5-di-tert-butyl-4-hydroxyphenyl) propionate or octadecyl-3- (3,5- Phenyl) propionate, etc .; a thioester antioxidant such as pentaerythritol tetrakis (3-dodecylthiopropionate), or a mixture of two or more of them may be used, It does not.

Examples of the activator include a polyethylene compound, an ethylene-ester compound, an ethylene glycol-glycerin ester compound, a montane compound, an ethylene glycol-glycerin montanate compound, an ester compound, or a mixture of two or more thereof , But is not limited thereto.

Examples of the ultraviolet absorber include, but are not limited to, a benzotriazole-based compound, a hydroxyphenyltriazine-based compound, a pyrimidine-based compound, a cyanoacrylate-based compound, or a mixture of two or more thereof.

The content of the other additives is not particularly limited and may be used in an amount that can be used to add additional functions within a range not impairing the desired physical properties of the polycarbonate resin composition of the present invention.

According to one embodiment of the present invention, the content of the other additive is selected such that the total amount of 100 parts by weight of the polycarbonate resin (component (1)) and the fluidizing agent (component (2)) in the polycarbonate resin composition of the present invention, 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight. When the content of the other additives is less than 0.1 part by weight based on the total of 100 parts by weight of the total amount of the polycarbonate resin [component (1)] and the fluidizing agent [component (2)], When the content of the other additives is more than 20 parts by weight, the mechanical properties of the resin composition may be poor.

Since the polycarbonate resin composition of the present invention has improved mechanical properties, it can be suitably used for 3D printing and industrial parts production. Particularly, since the polycarbonate resin composition can output to a 3D printer at a temperature lower than that of a conventional polycarbonate resin composition, It does not need equipment for high temperature output, so it is possible to improve the economical efficiency of 3D printing and broaden the application range.

Therefore, according to another aspect of the present invention, there is provided an article comprising the polycarbonate resin composition of the present invention.

The article can be produced by extrusion or injection molding of a polycarbonate resin composition.

According to one embodiment, the article may be, but is not limited to, a filament for 3D printing.

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 ]

The components used in the following examples and comparative examples are as follows:

PC-1: bisphenol A type linear polycarbonate having a viscosity average molecular weight of about 17,000

PC-2: Bisphenol A type linear polycarbonate having a viscosity average molecular weight of about 18,500

PC-3: bisphenol A linear polycarbonate having a viscosity average molecular weight of about 21,000

PC-4: Bisphenol A linear polycarbonate having a viscosity average molecular weight of about 30,000

Fluidizer: aromatic polyphosphate (PX-200, Daihachi)

Other additives: antioxidant (0.5 part by weight), lubricant (1 part by weight) and ultraviolet absorber (0.5 part by weight)

The components shown in the following Table 1 were put into a super mixer and mixed for about 2 minutes to prepare a polycarbonate resin composition. The mixture was extruded by a twin-screw extruder at a temperature of 200 to 240 ° C, .

[Table 1]

The pellets of each of the polycarbonate resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were hot-air dried at a temperature of 90 to 120 ° C. for 4 hours or more, and were then made into filament specimens for a 3D printer having a diameter of 1.75 mm. The properties of each of the prepared filament specimens were measured or evaluated as follows. The results are shown in Table 2 below.

≪ Method for measuring physical properties &

(1) Output temperature: When the filament specimen was output to a nozzle having a diameter of 0.4 mm in a 3D printer of a general material extrusion type, the nozzle temperature at which the product was stably stacked was measured as the output temperature.

(2) Extrudability: When the polycarbonate resin composition was kneaded and extruded by a biaxial melt kneading extruder, it was visually observed whether it could be made into a molding pellet after the insertion of the cutter.

O: manufactured by molding pellets when kneading and extruding a polycarbonate resin composition

X: Not produced as a molding pellet upon kneading extrusion of a polycarbonate resin composition

[Table 2]

As shown in Table 2, the polycarbonate resin compositions of Examples 1 to 6 were produced in the form of pellets for molding during kneading extrusion, and were output to a 3D printer using filament specimens manufactured using molding pellets , The output temperature was 245 DEG C or lower and relatively low temperature output was possible.

However, the filament specimen made of the polycarbonate resin composition of Comparative Example 1 was able to output to a 3D printer only at a high temperature of 270 DEG C, and the filament specimen made of the polycarbonate resin composition of Comparative Example 4 was used only at a high temperature of 260 DEG C Output was possible. In the case of the polycarbonate resin compositions of Comparative Examples 2, 3, 5, and 6, it was impossible to produce the molding pellets by kneading extrusion, and thus it was impossible to produce filament specimens for 3D printers.

Claims (6)

(1) a polycarbonate resin; And
(2) a fluidizer, wherein the polycarbonate resin composition comprises
Wherein the polycarbonate resin has a viscosity average molecular weight of 16,000 to 20,000,
Wherein the content of the fluidizing agent is 3 to 19 parts by weight based on 100 parts by weight of the total of the components (1) and (2)
Polycarbonate resin composition. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin. The polycarbonate resin composition according to claim 1, wherein the fluidizing agent is an aromatic phosphate, an aliphatic phosphate, or a mixture thereof. The polycarbonate resin composition of claim 1, further comprising at least one additive selected from the group consisting of an antioxidant, a lubricant, an ultraviolet absorber, or a mixture thereof. An article comprising the polycarbonate resin composition of any one of claims 1 to 4. 6. The article of claim 5, wherein the article is a filament for 3D printing.