JP6266984B2 - Copolymer for improving elongation and impact resistance of PC / ABS resin, this copolymer, PC / ABS resin and resin composition - Google Patents

Description

  The present invention relates to a copolymer for improving elongation and impact resistance of a resin composition (hereinafter referred to as “PC / ABS resin”) comprising a polycarbonate resin and an ABS resin, and the copolymer and the PC / ABS system. The present invention relates to a resin composition containing a resin.

  PC / ABS resins are excellent in impact resistance, heat resistance, and molding processability, and are therefore used in various applications including vehicle parts, home appliances, and office equipment parts.

  Patent Document 1 discloses a technique of blending a styrene-maleic anhydride copolymer oligomer in order to improve the impact resistance of a PC / ABS resin and the appearance of a molded product.

Japanese Patent Laid-Open No. 11-60851

  The PC / ABS resin is required to have excellent elongation in addition to excellent impact resistance and appearance of the molded product. However, Patent Document 1 does not consider the elongation.

  The present invention has been made in view of such circumstances, and includes a copolymer capable of improving the elongation and impact resistance of a PC / ABS resin, and the copolymer and a PC / ABS resin. A resin composition is provided.

  According to the present invention, a styrene-maleic anhydride copolymer essentially comprising a styrene monomer unit and a maleic anhydride monomer unit, the maleic anhydride monomer unit being 5 to 25% by mass, weight A copolymer for improving the elongation and impact resistance of a resin composition comprising a polycarbonate resin and an ABS resin having an average molecular weight (Mw) of 50,000 to 300,000 is provided.

  The present inventors have added a styrene-maleic anhydride copolymer having a maleic anhydride monomer unit content of 5 to 25% by mass and an Mw of 50,000 to 300,000 to a PC / ABS resin. They discovered a phenomenon that the elongation and impact resistance of PC / ABS resin are greatly improved.

  In order to verify when such a phenomenon occurs, the elongation and resistance of a resin composition obtained by adding the above copolymer to a polycarbonate resin, or a resin composition obtained by converting the above copolymer to an ABS resin. When the impact property was measured, in either case, the result that both elongation and impact resistance deteriorated was obtained. From this result, it was found that the phenomenon that both elongation and impact resistance are improved is a phenomenon peculiar to PC / ABS resins.

  Further, elongation when a copolymer having a maleic anhydride monomer unit content of less than 5% or more than 25% or a weight average molecular weight of less than 50,000 or more than 300,000 is added to a PC / ABS resin. As a result of examining changes in impact resistance, at least one of elongation and impact resistance was insufficiently improved.

  From the above, only when a styrene-maleic anhydride copolymer having 5 to 25% by mass of maleic anhydride monomer units and Mw of 50,000 to 300,000 is added to a PC / ABS resin. Thus, it was found that both the elongation and the impact resistance were greatly improved, and the present invention was completed.

Hereinafter, various embodiments of the present invention will be exemplified. The following embodiments can be combined with each other.
In this invention, the copolymer which is 45-85 mass% of styrene monomer units, 10-20 mass% of maleic anhydride monomer units, and 5-45 mass% of (meth) acrylic acid ester monomer units is provided. Is done.
Moreover, according to another viewpoint of this invention, 5-95 mass parts of polycarbonate resin (A), 95-5 mass parts of ABS resin (B), and 1-30 mass parts of said copolymers (C) are included. A resin composition (provided that the total amount of polycarbonate resin and ABS resin is 100 parts by mass) is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the copolymer which can improve the elongation and impact resistance of PC / ABS-type resin, and the resin composition containing this copolymer and PC / ABS-type resin are provided.

<Explanation of terms>
In the specification of the present application, the symbol “to” means “above” and “below”, for example, the description “A to B” means more than A and less than B.

  Hereinafter, embodiments of the present invention will be described in detail.

  The copolymer for improving the elongation and impact resistance of the PC / ABS resin of the present invention is a styrene-maleic anhydride copolymer essentially comprising a styrene monomer unit and a maleic anhydride monomer unit. The maleic anhydride monomer unit is 5 to 25% by mass and the weight average molecular weight (Mw) is 50,000 to 300,000.

  As the styrene monomer unit of this copolymer, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methyl Examples include units derived from styrene monomers such as styrene and α-methyl-p-methylstyrene. These styrene monomer units may be used alone or in combination of two or more. Content of the styrene monomer unit in a copolymer becomes like this. Preferably it is 45-85 mass%, More preferably, it is 52-78 mass%. This is because when the content of the styrene monomer unit in the copolymer is within such a range, the effect of improving the elongation and impact resistance of the PC / ABS resin is particularly large.

  Examples of the maleic anhydride monomer unit of this copolymer include units derived from maleic anhydride. Content of the maleic anhydride monomer unit in a copolymer is 5-25 mass%, Preferably it is 10-20 mass%, More preferably, it is 12-18 mass%. This is because when the content of the maleic anhydride monomer unit in the copolymer is within such a range, the effect of improving the elongation and impact resistance of the PC / ABS resin is particularly large.

  This copolymer preferably further contains a (meth) acrylic acid ester monomer unit. As the (meth) acrylic acid ester monomer units, methyl methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate, and Examples include units derived from each acrylate monomer such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate and the like. Among these, a methyl methacrylate unit is preferable. These (meth) acrylic acid ester monomer units may be one kind or a combination of two or more kinds. Content of the (meth) acrylic acid ester monomer unit in a copolymer becomes like this. Preferably it is 5-45 mass%, More preferably, it is 10-35 mass%. This is because when the content of the meth) acrylate monomer unit in the copolymer is within such a range, the effect of improving the elongation and impact resistance of the PC / ABS resin is particularly large.

  Particularly preferred structural units of the copolymer of the present invention are 45 to 85% by mass of styrene monomer units, 10 to 20% by mass of maleic anhydride monomer units, and 5 to (meth) acrylic acid ester monomer units. They are 45 mass%, Preferably they are 52-78 mass% of styrene monomer units, 12-18 mass% of maleic anhydride monomer units, and 10-35 mass% of (meth) acrylic acid ester monomer units.

  The copolymer of the present invention comprises a copolymerizable vinyl monomer unit other than a styrene monomer unit, a maleic anhydride monomer unit, and a (meth) acrylic acid ester monomer unit. It may be contained within a range not impairing the effects of the invention, and is preferably 5% by mass or less. Examples of the copolymerizable vinyl monomer unit include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, N-methylmaleimide, and N-ethylmaleimide. N-alkylmaleimide monomers such as N-butylmaleimide and N-cyclohexylmaleimide, N-arylmaleimide monomers such as N-phenylmaleimide, N-methylphenylmaleimide and N-chlorophenylmaleimide Examples are units derived from the body. Two or more types of copolymerizable vinyl monomer units may be used.

The copolymer of the present invention has a weight average molecular weight (Mw) of 5 to 300,000, preferably 100,000 to 200,000, more preferably 120,000 to 180,000. This is because when Mw is in the above range, the effect of improving the elongation and impact resistance of the PC / ABS resin is particularly large. The weight average molecular weight (Mw) is a value in terms of polystyrene measured by gel permeation chromatography (GPC), and is a value measured under the measurement conditions described below.
Device name: SYSTEM-21 Shodex (manufactured by Showa Denko)
Column: 3 series PL gel MIXED-B Temperature: 40 ° C
Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).

Next, the manufacturing method of the copolymer of this invention is demonstrated.
The polymerization mode is not particularly limited and can be produced by a known method such as solution polymerization or bulk polymerization, but solution polymerization is more preferable. The solvent used in the solution polymerization is preferably non-polymerizable from the viewpoint that a by-product is difficult to produce and that there are few adverse effects. The type of solvent is not particularly limited. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone, ethers such as tetrahydrofuran and 1,4-dioxane, toluene, ethylbenzene, xylene, and chlorobenzene Aromatic hydrocarbons, etc. are mentioned, but methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of the solubility of the monomer and copolymer and the ease of solvent recovery. The addition amount of the solvent is preferably 10 to 100 parts by mass, more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the copolymer to be obtained. If it is 10 parts by mass or more, it is suitable for controlling the reaction rate and the polymerization solution viscosity, and if it is 100 parts by mass or less, it is suitable for obtaining a desired weight average molecular weight (Mw).

  The polymerization process may be any of a batch polymerization method, a semi-batch polymerization method, and a continuous polymerization method, but the batch polymerization method is suitable for obtaining a desired molecular weight range and transparency.

  The polymerization method is not particularly limited, but is preferably a radical polymerization method from the viewpoint that it can be produced with high productivity by a simple process. The polymerization initiator is not particularly limited. For example, dibenzoyl peroxide, t-butyl peroxybenzoate, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl peroxy Known organic compounds such as isopropyl monocarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyacetate, dicumyl peroxide, ethyl-3,3-di- (t-butylperoxy) butyrate Known azo compounds such as peroxides, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, azobismethylbutyronitrile, and the like can be used. Two or more of these polymerization initiators can be used in combination. Among these, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 70 to 110 ° C.

  The copolymer having a preferable weight average molecular weight (Mw) in the range of 100,000 to 200,000 includes a solvent addition amount and a chain transfer agent addition amount in addition to the adjustment of the polymerization temperature, the polymerization time, and the polymerization initiator addition amount. It can be obtained by adjusting. Although it does not specifically limit as a chain transfer agent, For example, using well-known chain transfer agents, such as n-dodecyl mercaptan, t-dodecyl mercaptan, and 2, 4- diphenyl-4-methyl- 1-pentene. Can do.

  After the polymerization is completed, the polymerization solution is optionally provided with a heat resistant stabilizer such as a hindered phenol compound, a lactone compound, a phosphorus compound, or a sulfur compound, a light stabilizer such as a hindered amine compound or a benzotriazole compound, Additives such as lubricants, plasticizers, colorants, antistatic agents and mineral oils may be added. The addition amount is preferably less than 0.2 parts by mass with respect to 100 parts by mass of all monomer units. These additives may be used alone or in combination of two or more.

  There is no limitation in particular about the method of collect | recovering the copolymer of this invention from a polymerization liquid, A well-known devolatilization technique can be used. For example, a method of continuously feeding the polymerization liquid to a twin-screw devolatilizing extruder using a gear pump and devolatilizing a polymerization solvent, an unreacted monomer and the like can be mentioned. The devolatilizing component including the polymerization solvent, unreacted monomer, etc. is condensed and recovered using a condenser, etc., and the polymerization solvent can be reused by purifying the condensate in a distillation tower. .

  The copolymer of the present invention thus obtained can be used as an agent for improving the elongation and impact resistance of PC / ABS resins. The method for kneading and mixing the copolymer of the present invention and the PC / ABS resin to obtain a resin composition is not particularly limited, and a known melt-kneading technique can be used. Examples of the melt-kneading apparatus that can be suitably used include a single screw extruder, a meshing type co-rotating or meshing type counter-rotating twin screw extruder, a screw extruder such as a non- or incomplete meshing type twin screw extruder, a Banbury mixer, There are kneaders and mixing rolls.

The resin composition containing the copolymer of the present invention and a PC / ABS resin comprises 5 to 95 parts by mass of a polycarbonate resin (A), 95 to 5 parts by mass of an ABS resin (B), and the copolymer (C) of the present invention. It is preferable that 1-30 mass parts is included. However, the total of the polycarbonate resin (A) and the ABS resin (B) is 100 parts by mass. By blending the polycarbonate resin (A), the ABS resin (B), and the copolymer (C) at such a ratio, the elongation and impact resistance improving effect by the copolymer (C) is suitably exhibited. .
In this resin composition, the polycarbonate resin (A) is preferably 10 to 90 parts by mass, and more preferably 20 to 80 parts by mass. Moreover, preferably ABS resin (B) is 90-10 mass parts, More preferably, it is 80-20 mass parts. Furthermore, a copolymer (C) becomes like this. Preferably it is 5-27 mass parts, More preferably, it is 7-25 mass parts. This is because, in such a blending amount, the effect of improving elongation and impact resistance by the copolymer (C) is particularly high.

  A stabilizer, a plasticizer, a lubricant, an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant, and the like may be blended in the resin composition as long as the effects of the present invention are not impaired.

In Examples , Comparative Examples , and Reference Examples of the present invention, ABS resin (B) and copolymer (C) produced by the method shown in the following production examples were used. Further, Iupilon E-2000 manufactured by Mitsubishi Engineering Plastics was used as the polycarbonate resin (A).

<Example of production of ABS resin (B)>
In a 200 L reactor equipped with a stirrer, 143 parts of polybutadiene latex (solid content 35%, average particle size 350 nm), 1 part of sodium stearate, 0.2 part of sodium formaldehyde sulfoxylate, tetrasodium ethylenediaminetetraacetic acid 0.01 part, 0.005 part of ferrous sulfate and 150 parts of pure water were charged, and the temperature was heated to 50 ° C., to which 45 parts of a monomer mixture consisting of 75% styrene and 25% acrylonitrile, t- 1.0 part of dodecyl mercaptan and 0.15 part of cumene hydroperoxide were continuously added in 6 hours. After addition, the temperature was raised to 65 ° C. and polymerization was conducted for 2 hours. After adding 0.3 part of an antioxidant (Irganox 1076 manufactured by Ciba Specialty Chemicals) to the obtained latex, 300 parts of 5% calcium chloride aqueous solution and hydrochloric acid were added so as to have a pH of 4, and coagulated. A white powder was obtained after washing with water and drying. 27 parts of this powder and 73 parts of AS resin (AS-XGS manufactured by Denki Kagaku Kogyo Co., Ltd.) were melt-kneaded and pelletized at a cylinder temperature of 230 ° C. with a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.). Got.

<Example of production of styrene-maleic anhydride copolymer (C)>
20% maleic anhydride solution dissolved in methyl isobutyl ketone so that maleic anhydride has a concentration of 20% by mass and methyl so that t-butylperoxy-2-ethylhexanoate is 2% by mass. A 2% t-butyl peroxy-2-ethylhexanoate solution diluted in isobutyl ketone was prepared in advance and used for the polymerization.
A 120-liter autoclave equipped with a stirrer was charged with 2.6 kg of a 20% maleic anhydride solution, 25 kg of styrene, 10 kg of methyl methacrylate, and 30 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. The temperature was raised to 88 ° C. over 40 minutes with stirring. While maintaining 87 ° C. after the temperature rise, a 20% maleic anhydride solution was added at a rate of 1.9 kg / hour, and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 375 g / hour, respectively. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated up to 120 ° C. over 4 hours at a heating rate of 8 ° C./hour while maintaining the addition rate of 1.9 kg / hour. The addition of the 20% maleic anhydride solution was stopped when the addition amount reached 22.8 kg. After the temperature increase, the polymerization was terminated by maintaining 120 ° C. for 1 hour. The polymerization solution is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and methyl isobutyl ketone and a small amount of unreacted monomer are devolatilized, and extruded into a strand to cut it. A polymer (C-1) was obtained. The composition of the obtained copolymer (C-1) was analyzed by C-13 NMR method. Furthermore, molecular weight measurement was performed with a GPC apparatus.
Similarly, the composition can be changed by changing the addition amount of maleic anhydride, styrene and methyl methacrylate, and the molecular weight can be changed by changing the addition amount of t-dodecyl mercaptan. Polymers (C-2) to (C-9) and comparative copolymers (CC-1) to (CC-4) were obtained. Table 1 shows the analysis results of the compositions and weight average molecular weights of these copolymers.

<Examples / Reference Examples / Comparative Examples / Reference Examples>
After mixing said polycarbonate resin (A), ABS resin (B), and copolymer (C) with the mixing | blending shown in Table 2-Table 3 using a Henschel mixer, a twin-screw extruder (Toshiba machine company make TEM) -35B), the mixture was melt-kneaded at a cylinder temperature of 260 ° C. and pelletized to obtain a resin composition.
The following evaluation was performed on this resin composition. The evaluation results are shown in Tables 2 to 3.

(Elongation)
In accordance with JIS K7161-1994 and JIS K7162-1994, using an injection molded dumbbell shaped piece, using Shimadzu Autograph AG-Xplus, the nominal strain at the time of tensile fracture was measured at a tensile speed of 50 mm / min, The elongation characteristic value was used.

Next, the elongation values in Examples , Reference Examples, and Comparative Examples containing the copolymer (C) are the same as those in the polycarbonate resin (A) and the ABS resin (B) without the copolymer (C). The percent change in elongation (%) was calculated by dividing by the value of elongation in the same reference example. Specifically, for Examples 1 to 11 , Reference Examples 6 to 9 and Comparative Examples 1 to 5, the elongation values in each Example , Reference Example, and Comparative Example are the elongation values in Reference Example 3. The elongation change rate (%) was calculated by dividing. For Example 12, Comparative Example 6, and Comparative Example 7, the elongation change rate (%) was calculated by dividing the respective elongation values by the elongation values in Reference Example 2, Reference Example 1, and Reference Example 4. did.

Furthermore, based on the elongation change rate, the degree of elongation improvement was evaluated according to the following criteria.
A: Elongation change rate is 150% or more B: Elongation change rate is 130% or more and less than 150% C: Elongation change rate is 115% or more and less than 130% D: Elongation change rate is 100% or more and less than 115% E: Elongation change rate Is less than 100%

(Charpy impact strength)
The Charpy impact strength was measured based on JIS K7111-1: 2012 using a test piece without a notch and adopting an edgewise impact direction. The measuring machine used was a digital impact tester manufactured by Toyo Seiki Seisakusho.

Next, the Charpy impact strength values in Examples , Reference Examples, and Comparative Examples containing the copolymer (C) are the same as those of the polycarbonate resin (A) and the ABS resin (B). The rate of change in Charpy impact strength (%) was calculated by dividing by the value of Charpy impact strength in a reference example with the same amount. Specifically, for Examples 1 to 11 , Reference Examples 6 to 9 and Comparative Examples 1 to 5, the Charpy impact strength values in each Example , Reference Example, and Comparative Example were used, and the Charpy Impact in Reference Example 3 was used. The rate of change in Charpy impact strength (%) was calculated by dividing by the strength value. For Example 12, Comparative Example 6, and Comparative Example 7, the Charpy impact strength changes by dividing the respective Charpy impact strength values by the Charpy impact strength values in Reference Example 2, Reference Example 1, and Reference Example 4. The rate (%) was calculated.

Furthermore, based on the Charpy impact strength change rate, the degree of improvement in Charpy impact strength was evaluated according to the following criteria.
A: Charpy impact strength change rate is 270% or more B: Charpy impact strength change rate is 200% or more and less than 270% C: Charpy impact strength change rate is 130% or more and less than 200% D: Charpy impact strength change rate is 100% or more Less than 130% E: Charpy impact strength change rate is less than 100%

(Appearance of molded product)
Using an injection molding machine (IS-50EPN manufactured by Toshiba Machine Co., Ltd.), 50 samples of a cylindrical molded product having a diameter of 30 mm and a height of 50 mm were produced under molding conditions of a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C. Appearance evaluation was performed by counting the number of samples in which appearance defects such as silver, flow mark, gas burn, coloring, and bubbles were visually observed. The evaluation criteria are as follows.
A: The number of appearance defect samples is 0 B: The number of appearance defect samples is 1 to 2 C: The number of appearance defect samples is 3 to 4 D: The number of appearance defect samples is 5 to 6 E: The appearance defect More than 7 samples

(Discussion)
In Comparative Example 1, since the content of the maleic anhydride monomer unit in the copolymer (C) was too small, both the improvement in elongation and the improvement in impact resistance were insufficient.
In Comparative Example 2, since the content of the maleic anhydride monomer unit in the copolymer (C) was too much, both the improvement in elongation and the improvement in impact resistance were insufficient. Also, the appearance of the molded product was not good.
In Comparative Example 3, since the Mw of the copolymer (C) was too small, both the improvement in elongation and the improvement in impact resistance were insufficient.
In Comparative Example 4, since the Mw of the copolymer (C) was too large, the improvement in elongation was insufficient.
In Comparative Example 5, since the amount of the copolymer (C) added was too large, both the improvement in elongation and the improvement in impact resistance were insufficient.
In Comparative Example 6, since the resin composition did not contain the ABS resin (B), both the improvement in elongation and the improvement in impact resistance were insufficient.
In Comparative Example 7, since the resin composition did not contain the polycarbonate resin (A), both the improvement in elongation and the improvement in impact resistance were insufficient.
In Examples 1 to 12 and Reference Examples 6 to 9 , the copolymer (C) having a maleic anhydride monomer unit content of 5 to 25% by mass and Mw of 50,000 to 300,000 is 1 to Since 30 parts by mass was added, both the improvement in elongation and the improvement in impact resistance were great, and the appearance of the molded product was also good.
Furthermore, in Examples 1-4, a composition is styrene monomer unit 45-85 mass%, maleic anhydride monomer unit 10-20 mass%, (meth) acrylic acid ester monomer unit 5-45 mass%. And 1 to 30 parts by mass of the copolymer (C) having an Mw of 100,000 to 200,000, both of the improvement in elongation and the improvement in impact resistance are very large, and the appearance of the molded product is very It was good.

Claims (1)

Polycarbonate resin (A) 5 to 95 parts by weight, ABS resin (B) 95 to 5 parts by mass, seen including a co polymer (C) 1 to 30 parts by weight,
The copolymer (C) is a styrene-maleic anhydride copolymer having a styrene monomer unit, a maleic anhydride monomer unit, and a (meth) acrylic acid ester monomer unit as essential components. Styrene monomer unit 45-85 mass%, maleic anhydride monomer unit 10-18 mass%, (meth) acrylic acid ester monomer unit 5-45 mass%, weight average molecular weight (Mw) 50,000- 300,000 resin composition (however, the total of polycarbonate resin and ABS resin is 100 parts by mass).