WO2019078417A1 - Eco-friendly polycarbonate resin composition having high adhesive property and high stiffness - Google Patents

Abstract

The present invention relates to an eco-friendly polycarbonate (PC) resin composition and, more specifically, to a PC resin composition, which comprises a PC containing plant-derived components so as to be eco-friendly, and comprises specific amount ranges of an ethylene-glycidyl methacrylate copolymer and a thermoplastic polyester-based elastomer resin so as to enable interlayer adhesive strength to increase during 3D printing output and the stiffness of a 3D printed product to improve, thereby being widely applicable in industrial part manufacturing using 3D printing.

Description

Eco-friendly polycarbonate resin composition having high adhesion and high rigidity

The present invention relates to an eco-friendly polycarbonate (PC) resin composition, and more particularly, to an eco-friendly polycarbonate resin composition containing a polycarbonate containing a plant-derived component and having a specific content range of ethylene-glycidyl methacrylate copolymer By incorporating the thermoplastic polyester elastomer resin and the thermoplastic polyester elastomer resin, it is possible to increase the interlaminar bond strength at the time of 3D printing output and to improve the rigidity of the 3D printing output. Thus, the polycarbonate resin composition which can be widely applied to the production of industrial parts using 3D printing .

There are many ways to do 3D printing. Among these resins, polylactic acid, acrylonitrile-butadiene-styrene, polycarbonate, polyimide and the like are used for the lamination method through extrusion of the filament.

A variety of techniques have been introduced for application to 3D printing of material extrusion methods. For example, U.S. Patent Nos. 8920697, 8801990, 8460755 and U.S. Publication No. 2014-0141168 disclose various materials for making support structures . In addition, US Patent Publication No. 2013-0224423 discloses a crystalline resin having a core-shell structure with a laminated material.

However, conventional polylactic acid is an eco-friendly substance, but has a problem in rigidity and heat resistance. Conventional acrylonitrile-butadiene-styrene, polycarbonate, polyimide, and the like have not been environmentally friendly.

It is an object of the present invention to provide a resin composition containing an ethylene-glycidyl methacrylate copolymer and a thermoplastic polyester-based elastomer resin containing a polycarbonate containing a plant-derived component in an environmentally friendly manner and having a specific content Thereby improving the rigidity of the composition and improving the strength of the 3D printing output. Thus, the present invention provides an eco-friendly polycarbonate resin composition that can be applied to various industrial parts using 3D printing.

In order to solve the above technical problems, the present invention provides a thermoplastic resin composition comprising (A) a polycarbonate resin, (B) a plant-derived component-containing polycarbonate resin, (C) an ethylene- glycidyl methacrylate copolymer resin, and (D) (B) 2 to 38 parts by weight of a plant-derived component-containing polycarbonate resin based on 100 parts by weight of the total of the resin components (A) to (D) And 2 to 10 parts by weight of a glycidyl methacrylate copolymer resin, and (D) 1 to 13 parts by weight of a thermoplastic polyester-based elastomer resin.

According to another aspect of the present invention, there is provided a molded article produced by extrusion or injection molding the polycarbonate resin composition.

The polycarbonate resin composition according to the present invention can be used in combination with a polycarbonate containing a plant-derived component in combination with a general polycarbonate, unlike the conventional polycarbonate composition for general 3D printing, which was a material free from environmental friendliness. And further contributes to the prevention of global warming. In addition, since the thermoplastic polyester elastomer resin is included, it exhibits high adhesiveness and high rigidity without deteriorating physical properties and can be particularly suitably used for 3D printing.

Hereinafter, the present invention will be described in more detail.

As the polycarbonate resin (A) contained in the polycarbonate resin composition of the present invention, a commonly used aromatic polycarbonate resin can be used. The (A) polycarbonate resin is a resin different from the (B) plant-derived component-containing polycarbonate resin described below.

The aromatic polycarbonate resin may be one prepared by reacting a dihydric phenol with phosgene or using an ester interchange reaction of a dihydric phenol and a carbonate precursor, and the linear and / or branched polycarbonate homopolymer And polyester copolymers.

The dihydric phenol may be selected from the group consisting of 2,2-bis (4-hydroxyphenyl) propane (i.e. bisphenol A), bis (4-hydroxyphenyl) methane, 2,2- -Dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, or a combination thereof, wherein the carbonate precursor is selected from the group consisting of diphenyl carbonate, carbonyl halide, diaryl carbonate, Can be selected.

The viscosity average molecular weight of the polycarbonate resin (A) is preferably 17,000 to 30,000, more preferably 21,000 to 27,000, and even more preferably 21,000 to 25,000. When the viscosity average molecular weight of the polycarbonate resin (A) is within the above range, it is excellent in compatibility when the composition is extruded, and pyrolysis may occur to a small extent.

The content of the polycarbonate resin (A) in the composition of the present invention is, for example, at least 42 parts by weight, at least 45 parts by weight, at least 48 parts by weight, at least 50 parts by weight, and at most 50 parts by weight, based on 100 parts by weight of the total of the resin components (A) And may be 95 parts by weight or less, 90 parts by weight or less, 87 parts by weight or less, 81 parts by weight or less, or 78 parts by weight or less. If the content of the polycarbonate resin (A) in the composition is too small, there may be a problem in the impact strength and the heat resistance. On the contrary, if the amount is too large, the environment-friendly advantage may disappear.

As the polycarbonate resin containing the plant-derived component (B) contained in the polycarbonate resin composition of the present invention, at least a part of the aromatic diol compound used in the melt polymerization of the existing polycarbonate is replaced by a plant- Can be used.

In one embodiment, the plant-derived diol compound may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof, more specifically isosorbide of formula (1).

[Chemical Formula 1]

As the isosorbide, those produced by known techniques can be used.

In one embodiment, the plant-derived component-containing polycarbonate resin (B) is a polycarbonate resin containing the plant-derived diol contained as a polymerization unit in a resin in an amount of 40 wt% based on 100 wt% (For example, 40 to 80% by weight), more specifically 50% by weight or more (for example, 50 to 70% by weight). If the content of the plant-derived diol is too small, the heat resistance is lowered, and pyrolysis may occur during the production of the composition, and the effect of improving the environment-friendliness may be poor.

In one embodiment, the viscosity average molecular weight of the plant-derived component-containing polycarbonate of the present invention (B) may be from 17,000 to 21,000.

The content of the plant-derived component-containing polycarbonate resin in the composition of the present invention is 2 to 38 parts by weight, more specifically 2 to 35 parts by weight, based on 100 parts by weight of the total of the resin components (A) to (D) More specifically from 5 to 35 parts by weight, and even more specifically from 5 to 30 parts by weight. If the content of the plant-derived component-containing polycarbonate resin (B) in the composition is less than the above-mentioned level, the biomass content of the composition is lowered and the environment-friendliness thereof becomes poor. On the other hand, Lt; / RTI >

The (C) ethylene-glycidyl methacrylate copolymer resin contained in the polycarbonate resin composition of the present invention increases the kneading property between the polycarbonate resin (A) and the plant-derived component-containing polycarbonate resin (B) The bonding strength can be improved when bonding.

In the present invention, the term " ethylene-glycidyl methacrylate copolymer " refers to a copolymer comprising ethylene and glycidyl methacrylate, as well as ethylene and glycidyl methacrylate, as well as additional comonomers Is a concept including a copolymer. Such additional comonomers include, for example, vinyl monomers such as vinyl acetate (VA), acrylic monomers (e.g., methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), ethyl methacrylate (EMA), butyl acrylate (BA), butyl methacrylate (BMA), etc.) or a combination thereof.

In the present invention, the content of glycidyl methacrylate (GMA) in the ethylene-glycidyl methacrylate copolymer resin (C) may be 12% by weight or more based on 100% by weight of the copolymer. If the content of glycidyl methacrylate in the copolymer is lower than 12% by weight, the adhesiveness remarkably decreases. In addition, the content of glycidyl methacrylate in the copolymer may be 25% by weight or less, more preferably 22% by weight or less, and even more preferably 20% by weight or less. If the content of glycidyl methacrylate in the copolymer is within the above-mentioned range, the adhesiveness is increased, thereby contributing to the improvement of interlayer adhesion at the time of 3D printing.

The content of the (C) ethylene-glycidyl methacrylate copolymer resin in the composition of the present invention is 2 to 10 parts by weight based on 100 parts by weight of the total of the resin components (A) to (D) 3 to 8 parts by weight. If the content of the ethylene-glycidyl methacrylate copolymer resin (C) in the composition is less than the above-mentioned level, the impact strength may be lowered. On the contrary, if the content is higher than the above-mentioned level, the content of the polycarbonate resin is relatively decreased, And the peeling phenomenon may occur.

As the (C) ethylene-glycidyl methacrylate copolymer resin, it is also possible to use a mixture of resins having glycidyl methacrylate (GMA) content of 12% by weight or more.

The thermoplastic polyester elastomer resin (D) contained in the polycarbonate resin composition of the present invention is characterized in that the content of the plant-derived component polycarbonate resin (B) is 100 parts by weight based on the total of the resin components (A) to (D) It is possible to prevent the lowering of the kneading property of the polycarbonate resin (A) and the raw material-containing polycarbonate resin (B) originating from the plant (B) and the lowering of the bonding strength at the time of resin bonding, which may be caused when the content is increased to 20 parts by weight or more.

The thermoplastic polyester elastomer (D) is generally a thermoplastic polymer that is block copolymerized with a hard segment and a soft segment. In general, as the hard segment component, an aromatic dicarboxylic acid, an aromatic dicarboxylate, or a combination thereof may be used. As the soft segment component, a polyalkylene oxide may be used. Can be used.

Examples of the aromatic dicarboxylic acid or aromatic dicarboxylate include terephthalic acid (TPA), isophthalic acid (IPA), 1,5-dinaphthalenedicarboxylic acid, 1,5-dinaphthalenedicarboxylic acid , 5-NDCA), 2,6-dinaphthalenedicarboxylic acid (2,6-NDCA), dimethyl terephthalate (DMT), dimethyl isophthalate or Mixtures of two or more of these may be used, and preferably DMT can be used.

The polyalkylene oxide may be polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol (PTMEG), or a mixture of two or more thereof. , Preferably PTMEG may be used.

The thermoplastic polyester elastomer resin may be a linear or cyclic aliphatic diol having 2 to 8 carbon atoms in addition to the above-mentioned hard segment component and soft segment component. Examples of the aliphatic diol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol or a mixture of two or more thereof And preferably 1,4-butanediol can be used.

In order to improve the stability of the thermoplastic polyester elastomer strand during the production of the thermoplastic polyester elastomer by raising the melt tension of the thermoplastic polyester elastomer and to improve the productivity through the result, the thermoplastic polyester elastomer Additional branching agents may be used. Such branching agents may be glycerol, pentaerythritol, neopentylglycol or a combination thereof, preferably glycerol.

In addition, the preparation of the thermoplastic polyester elastomer can be carried out in the presence of a suitable catalyst (e.g., tetra-n-butoxy titanium (TBT).

Generally, the thermoplastic polyester elastomer which can be used in the present invention can be produced by subjecting the above components to a reactor, followed by melt polymerization comprising two steps of an oligomerization reaction and a polycondensation reaction. The oligomerization reaction is carried out at 140 to 215 ° C. for 3 to 4 hours and the polycondensation reaction is carried out at 210 to 250 ° C. for 4 to 5 hours in a stepwise decreasing step from 760 torr to 0.3 torr to produce a branched elastomer do.

The soft segment content in the total of 100% by weight of the thermoplastic polyester elastomer which can be used in the present invention may be varied, for example, from 5 to 75% by weight, and in particular, considering blow molding processability, mechanical strength, , And 30 to 70% by weight. If the content of the soft segment in the thermoplastic polyester-based elastomer is too small, it is difficult to expect flexibility because the hardness is increased. On the contrary, if it is too much, high heat resistance performance is not expected.

In the present invention, as the component (D), a thermoplastic polyester elastomer resin having a Shore-D hardness of 25D to 80D, preferably 25D to 75D, and more preferably 28D to 72D, can be used.

The composition of the present invention may further contain, in addition to the above-mentioned components, additional components ordinarily added to the polycarbonate resin composition such as an ultraviolet absorber, a heat stabilizer, an antioxidant, a fluidizing agent, a lubricant, a flame retardant, More than one additive may be included. In particular, it is possible to make 3D printing possible even at a lower temperature than the conventional one, by further including a fluidizing agent. The content of these additional additive components may be, for example, 1 to 10 parts by weight based on 100 parts by weight of the total of the resin components (A) to (D), but is not limited thereto.

The polycarbonate resin composition of the present invention can be suitably used for 3D printing and industrial parts production because it has an improved bonding strength and a high rigidity.

Therefore, according to another aspect of the present invention, there is provided a molded article produced by extrusion or injection molding the polycarbonate resin composition.

According to one embodiment, the molded article may be 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:

(A): bisphenol A type linear polycarbonate having a viscosity average molecular weight of about 25,000

(B): isosorbide-containing polycarbonate (Mitsubishi Chemical, DURABIO D7340IR)

(C): Ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate content: 19% by weight) (Sumitomo Chemical Co., Ltd.)

(D1): Thermoplastic polyester-based elastomer resin (Shore-D 28) (Samyang Co.)

(D2): Thermoplastic polyester-based elastomer resin (Shore-D 30) (Samyang Co.)

(D3): Thermoplastic polyester-based elastomer resin (Shore-D 40) (Samyang Co.)

(D4): Thermoplastic polyester-based elastomer resin (Shore-D 55) (Samyang Co.)

(D5): Thermoplastic polyester-based elastomer resin (Shore-D 65) (Samyang Co.)

(D6): Thermoplastic polyester-based elastomer resin (Shore-D 72) (Samyang Corp.)

Each component was put into a super mixer with the composition shown in the following Table 1, mixed for about 2 minutes, and then pelletized in an extruder hopper. The extruder was a 12-barrel Japan Steel Works 30 mm extruder. The RPM was set at 200 and the melting temperature was set at 270 ° C as a reference.

[Table 1] (Unit: parts by weight)

The pellets of the prepared examples and comparative compositions were prepared by using an extruder at 270 DEG C for an IZOD impact bond strength specimen, a CHARPY impact bond strength specimen, a tensile strength specimen, and a color specimen. The properties of the prepared specimens were measured or evaluated as follows. The results are shown in Table 2 below.

The IZOD impact bond strength specimens were extruded through two gates opposed to each other in the shape according to ASTM D256, and the specimens were molded and measured using IMPACT test equipment. The higher the impact value, the higher the impact resistance of the printout when outputting to a 3D printer. The results were converted to the standard (100%) results of Example 6.

CHARPY Impact Adhesive Strength Specimens were molded by two gates facing each other in the shape according to ISO 179, and the specimens were molded and measured using IMPACT test equipment. The higher the impact value, the higher the impact resistance of the output during the output to the 3D printer. The results were converted to the standard (100%) results of Example 6.

Tensile Strength Specimens were prepared according to ASTM D638. The tensile strength at break was measured and the higher the tensile strength value, the more suitable for industrial parts. The results were converted to the standard (100%) results of Example 6.

The biomass content was calculated on the basis of the calibration curve based on the content of the plant-derived component-containing polycarbonate measured in accordance with ASTM D6866-11.

The extrudability test was carried out on the basis of a visual inspection, and five persons were rated by rating one step (extrudability poor) to five steps (extrudability is good) per each sample. The final evaluation index was the average value of the total sum. The lower the extrudability grade, the worse the extrudability is, which may cause problems in filament production and 3D printing lamination.

Pearl-like levels of color specimens were evaluated on the basis of visual inspection by grading five persons for each sample in one step (weak Pearl-like) to five (strong Pearl-like). The final evaluation index was the average value of the total sum. The higher the pearl-like grade, the poorer the kneadability of the resin produced, and it may cause a deterioration of the appearance quality due to the dichroism at the time of output by 3D printing.

The surface characteristics of the specimens were observed in the vicinity of GATE and GATE. If a surface peeling phenomenon or an excessive gas marking phenomenon occurs on the surface, uniform output and weak interlaminar adhesive force during 3D printing output may be caused.

 [Table 2]

As can be seen from the results in Table 2 above, the compositions of Examples 1 to 12 exhibit a tensile strength of more than 50% of the results of Example 6, which are both based on IZOD impact bond strength and CHARPY impact bond strength, More than 95% of the results, at the same time satisfying the biomass content of 2% or more, satisfying the extrudability grade of 3.2 or more and the Pearl-like grade of 1.6 or less at the same time. When these properties are satisfied at the same time, they can be suitably used for eco-friendly 3D printing and have high rigidity and can be applied to industrial parts.

On the other hand, in Comparative Example 1, the eco-friendliness was poor due to a low Biomass content, and Comparative Example 2 was inferior in extrudability grade and Pearl-like grade due to deficiency of thermoplastic polyester elastomer resin, and IZOD impact adhesion strength and CHARPY impact adhesion All of the strength is very poor and it is not suitable as a material for 3D printing output. In Comparative Example 3, the content of the thermoplastic polyester elastomer resin was so high that the tensile strength was below the standard and the surface condition of the color sample was also poor, which was unsuitable for 3D printing materials. In Comparative Example 4, the plant-derived component-containing polycarbonate resin , The Pearl-like grade did not meet the criteria, the surface condition of the color sample was poor, and the CHARPY impact adhesive strength was also inadequate for use as a material for 3D printing.

Claims (11)

1. (A) a polycarbonate resin, (B) a plant-derived component-containing polycarbonate resin, (C) an ethylene-glycidyl methacrylate copolymer resin, and (D) a thermoplastic polyester-

   (B) a plant-derived component-containing polycarbonate resin in an amount of 2 to 38 parts by weight based on 100 parts by weight of the total of the resin components (A) to (D), (C) an ethylene-glycidyl methacrylate copolymer And 2 to 10 parts by weight of a resin, and (D) 1 to 13 parts by weight of a thermoplastic polyester-based elastomer resin.

   Polycarbonate resin composition.
2. The polycarbonate resin composition according to claim 1, wherein (A) the polycarbonate resin has a viscosity average molecular weight of 17,000 to 30,000.
3. The polycarbonate resin composition according to claim 1, wherein the plant-derived component (B) in the plant-derived component-containing polycarbonate resin is a plant-derived diol compound.
4. 4. The polycarbonate resin composition according to claim 3, wherein the plant-derived diol compound is isosorbide, isomannide, isoidide or a mixture of two or more thereof.
5. The polyol composition according to claim 3, wherein the content of the plant-derived diol contained as the polymerization unit in the polycarbonate resin (B) containing the plant-derived component is 40% by weight or more based on 100% Carbonate resin composition.
6. The ethylene-glycidyl methacrylate copolymer resin according to claim 1, wherein the glycidyl methacrylate content of the ethylene-glycidyl methacrylate copolymer resin is 12% by weight or more based on 100% by weight of the ethylene-glycidyl methacrylate copolymer , A polycarbonate resin composition.
7. The polycarbonate resin composition according to claim 1, wherein (D) the thermoplastic polyester-based elastomer resin has a Shore-D hardness of 25D to 80D.
8. The resin composition according to claim 1, which comprises 45 to 81 parts by weight of a polycarbonate resin (A), 5 to 35 parts by weight of a plant-derived component-containing polycarbonate resin (B), based on 100 parts by weight of the total of the resin components (A) , (C) 3 to 10 parts by weight of an ethylene-glycidyl methacrylate copolymer resin, and (D) 1 to 10 parts by weight of a thermoplastic polyester-based elastomer resin.
9. The positive resist composition according to claim 1, wherein at least one additive selected from an ultraviolet absorber, a heat stabilizer, an antioxidant, a fluidizing agent, a lubricant, a flame retardant or a flame retardant aid is added in an amount of 1 to 100 parts by weight, 10 parts by weight of a polycarbonate resin composition.
10. A molded article produced by extrusion or injection molding the polycarbonate resin composition according to any one of claims 1 to 9.
11. 11. A molded article according to claim 10, wherein the filament is a 3D printing filament.