JPH0517667A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition composed mainly of polycarbonate and ABS resin, in which the resins are densely mixed with each other and which is excellent in mechanical strength. CONSTITUTION:A resin composition consisting of 10-90 pts.wt. polycarbonate resin, 90-10 pts.wt. ABS resin, and 0.5-10 pts.wt. graft polymer which is formed from a radical-polymerizable macromonomer having a skeleton comprising a polymethyl methacrylate or styrene/acrylonitrile copolymer and other radical- polymerizable monomer and which has epoxy groups in the backbone.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition used for a wide variety of purposes such as general consumption and industrial use, and more particularly, to a polycarbonate / ABS resin composition which has recently received attention. is there.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent heat resistance, impact resistance, transparency, dimensional stability, flame retardancy, etc., but they are superior to general-purpose resins. It is expensive and the moldability is insufficient. There is also a problem that impact strength has a large thickness dependency. ABS resin has impact resistance,
It has characteristics such as excellent water resistance, oil resistance, dimensional stability, moldability, and appearance quality, and its resin properties can be adjusted over a wide range by changing the copolymer composition, so it is used in many applications as a general-purpose resin. On the other hand, ABS resins are basically lacking in heat resistance and weather resistance depending on the application, and thus may be restricted in use. Polycarbonate resin and ABS
In order to make the best use of the advantages of the system resins and to make up for the drawbacks, polymer alloys composed of both have been tried and are already in general use.
Since the polycarbonate resin and the ABS resin have relatively excellent miscibility, the polymer alloy obtained by mixing them has reached a certain level in mechanical strength, but is essentially incompatible. However, the use of the welded portion of the molded product may be insufficient, and the application is limited. The present invention is intended to provide a polycarbonate / ABS resin composition having excellent impact resistance, heat resistance, economical efficiency, moldability, and further improved miscibility.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have investigated means for improving the miscibility of polycarbonate and ABS resins, and as a result, have found that the branch component has excellent compatibility with ABS resins. It was found that a graft copolymer, which is a polymer and has an epoxy group as a backbone component, can improve the miscibility of both resins, and has completed the present invention. That is, the present invention is a resin composition comprising the following three components. (A) Polycarbonate resin 10 to 90 parts by weight (b) ABS resin 90 to 10 parts by weight (c) Radical-polymerizable macromonomer having polymethyl methacrylate or styrene-acrylonitrile copolymer as a skeleton and others Graft polymer containing an epoxy group in the trunk component, which is composed of the radically polymerizable monomer of
~ 10 parts by weight

The present invention will be described in more detail below. Polycarbonate resin The polycarbonate resin used in the present invention is preferably an aromatic polycarbonate generally used for molding, and specifically, the polycarbonate resin represented by the following chemical formula 1 -A resin.

[Chemical 1]In the above chemical formula 1, -X- is, for example, -O-, -S.
-, -SO-, -SO₂-And-C (R)₂-And so on
And F, Cl, Br, CH in the aromatic ring₃ Replacement of etc.
A group may be introduced. Particularly representative polycarbonate
Resin is 4,4-dihydroxydiphenyl-2,2-propan
4,4-dioxia including bisphenol A)
It is a rilalkane-based polycarbonate, but it is 4,4-dihydride.
Roxydiphenyl-2,2-propane (Bisfer A)
Is preferred.

ABS-based resin As the ABS-based resin, a graft copolymer obtained by radical graft-polymerizing a vinyl monomer mainly containing styrene and acrylonitrile in the presence of an elastomer component represented by a diene rubber. Is mentioned. ABS
Examples of the elastomer component that is a constituent component of the system resin include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, diene rubber such as polyisoprene and polychloroprene, ethylene-propylene copolymer, and ethylene. —Propylene-diene Monomer terpolymer, chlorinated polyethylene, olefin rubber such as polyisobutylene, acrylic rubber containing alkyl (meth) acrylate as a main component, and the like, and diene rubber is more preferable. The graft copolymer produced by using the above various elastomer components may be ABS resin, AES resin, ACS resin, A resin, or the like depending on the type of elastomer.
It may be abbreviated as AS resin and the like, but in the present invention, these are collectively referred to as ABS resin.

The vinyl monomer graft-polymerized to the elastomer is mainly composed of styrene and acrylonitrile, but if necessary, other vinyl monomers such as α-methylstyrene, aromatic substituted styrenes, (meth) are used.
Acrylic ester, methacrylonitrile, (meth)
Acrylic acid, maleic anhydride, N-substituted maleimides represented by phenylmaleimide, and the like may also be used in combination. The preferred proportion of styrene in the total vinyl monomer is 50 to 90% by weight, more preferably 60 to 85%. The preferred ratio of acrylonitrile is 40 to 10% by weight, 35 to 15% by weight
Is more preferable. The proportion of other vinyl monomers is
It is 0 to 20% by weight, preferably 0 to 10% by weight. As the polymerization method, emulsion polymerization, suspension polymerization, bulk polymerization and solution polymerization are adopted, and a polymerization method combining these can also be adopted. The weight ratio of the elastomer component in the ABS resin is preferably 5 to 40% by weight, more preferably 10 to
30% by weight.

Macromonomer In the macromonomer of the present invention, a polymer having a methyl methacrylate polymer unit as a main unit or a styrene-acrylonitrile copolymer has a radical polymerizable group such as a (meth) acryloyl group at one end thereof. Bound, number average molecular weight
It is a macromonomer of 2,000 to 20,000. In the case of a macromonomer having a skeleton of a polymer having a methyl methacrylate polymer unit as a main unit, the proportion of the methyl methacrylate monomer unit is preferably 80% by weight or more. When the content of the methyl methacrylate monomer unit is less than 80% by weight,
AB of a branch component composed of a macromonomer, which is a compatible unit with the ABS resin in the resulting graft polymer.
Poor compatibility with S-based resins. When the skeleton is a styrene-acrylonitrile copolymer, the preferred amount of styrene monomer unit is 60 to 90% by weight, and the preferred amount of acrylonitrile monomer unit is 40 to 10% by weight. When the composition of the styrene-acrylonitrile copolymer deviates from the above range, AB of the branch component in the resulting graft polymer is obtained.
Poor compatibility with S-based resins.

When the number average molecular weight of the macromonomer is less than 2,000, the molecular chain length of the branch component in the obtained graft polymer is too short, and the anchor effect on the ABS resin is insufficient, while it exceeds 20,000. Inferior in copolymerizability,
It is difficult to introduce the desired amount of macromonomer into the graft polymer. Next, a method for synthesizing a macro monomer will be described. In the synthesis of the macromonomer, any of living polymerization methods such as anion living polymerization method, group transfer polymerization method, immortal polymerization method, and radical polymerization method can be adopted, but they are not easily affected by impurities and are industrially used. The radical polymerization method is preferable because it can be easily produced. An example of a method for producing a poly (methyl methacrylate) macromonomer by a radical polymerization method is, for example, a mercaptan compound having a functional group reactive with an epoxy group such as a carboxyl group and a mercapto group as a chain transfer agent, Radical polymerization of methyl acidate to obtain poly (methyl methacrylate) in which functional group reactive with epoxy group is attached to one end of molecule, and then addition reaction of compound having epoxy group and (meth) acryloyl group in the molecule Thus, a macromonomer can be obtained. The number average molecular weight in the present invention is the polystyrene equivalent number average molecular weight measured by gel permeation chromatography.

Graft polymer The graft polymer in the present invention is a graft copolymer obtained by radically polymerizing the above-mentioned macromonomer, epoxy group-containing monomer and, if desired, other vinyl monomers, and the preferred copolymer of the above components. The polymerization rate is 5 to 70% by weight of macromonomer, 1 to 1 of epoxy group-containing monomer.
40% by weight and 0 to 90% by weight of other vinyl monomers.
More preferably, macromonomer 10 to 50% by weight, epoxy group-containing monomer 3 to 30% by weight and other vinyl monomer 4
It is 0 to 80% by weight. In copolymerization, macromonomer
If the amount is less than 5% by weight, the amount of the branch component introduced into the graft copolymer is too small, and the effect of grafting is difficult to be exhibited. On the other hand, if it exceeds 70% by weight, gelation tends to occur at the time of weight. Further, if the epoxy group-containing monomer is less than 1% by weight, the effect of improving the miscibility of the graft polymer does not appear, and if it exceeds 40% by weight, gelation tends to occur at the time of weight. 90 other vinyl monomers
If it exceeds 5% by weight, the effect of improving the miscibility of the graft polymer does not appear.

Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and glycidyl-substituted styrene. Examples of vinyl monomers copolymerized with macromonomers and epoxy group-containing monomers include radically polymerizable vinyl monomers such as (meth) acrylic acid ester, styrene, and (meth) acrylonitrile. Methyl, styrene and acrylonitrile are preferred. The number average molecular weight of the graft polymer is preferably 3,000 to 200,000, and 10,000 to 200,00.
0 is more preferable. When the number average molecular weight is less than 3,000, the effect of compatibilizing the polycarbonate resin and the ABS resin is poor, and the graft polymer having a number average molecular weight of more than 200,000 is apt to cause gelation and thickening during production, which is not preferable. As a method for producing the graft polymer, a general radical polymerization method, for example, a solution polymerization method, a suspension polymerization method, a bulk polymerization method or the like is preferably adopted.

Resin Composition The resin composition of the present invention is a resin obtained by mixing the above-mentioned polycarbonate resin, ABS resin and graft polymer in the following proportions as described above. It is a composition. (A) Polycarbonate resin 10 to 90 parts by weight (b) ABS resin 90 to 10 parts by weight (c) Graft polymer 0.5 to 10 parts by weight Resin (a) or resin (b) is less than 10 parts by weight However, the characteristics of the resin are not reflected in the physical properties of the resin composition, which is not preferable. If the amount of the graft polymer is less than 0.5 part by weight, the compatibilizing effect will be insufficient, and if it exceeds 10 parts by weight, the physical properties of the resin composition will be deteriorated and the cost will be disadvantageous.
The above-mentioned respective components can be easily mixed by a usual blending method, that is, by melt-kneading using an extruder, a kneader, an open roll or the like. Preferred is a method of mixing using a Henschel mixer or the like, heating and melting this using an extruder, extruding, and cutting into pellets. The pelletized composition thus obtained is molded into a desired shape by, for example, injection molding, extrusion molding, press molding, blow molding or the like.

In addition to the above-mentioned essential components, other resins may be added to the resin composition of the present invention. That is, in addition to the above three components, a styrene-butadiene block copolymer and hydrogenated product thereof, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyisoprene, polychloroprene, ethylene-propylene copolymer. Polymer, ethylene-propylene-
Elastomers of diene monomer terpolymer, chlorinated polyethylene, polyisobutylene, acrylic rubber containing alkyl (meth) acrylate as a main component, polyurethane, etc.
Can be blended as an impact strength improver within the range of 30% by weight. Acrylonitrile-styrene copolymer, polymethylmethacrylate, polyvinyl chloride, polyallyle-
ABS resin such as polyester, polysulfone or polycarbonate
A hard resin compatible with the resin can be added within the range of 30% by weight. Further, it may contain a small amount of a flame retardant, an ultraviolet absorber, a lubricant, a plasticizer, an additive such as a stabilizer or an antistatic agent, a reinforcing fiber such as glass fiber or carbon fiber, and various inorganic or organic fillers. ..

[0013]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples below. In addition, all% described in each example are% by weight, and parts are parts by weight. Examples 1 to 3 and Comparative Example Polycarbonate (manufactured by Teijin Chemicals Ltd .; trade name Panlite L-1250), ABS resin (manufactured by Nippon Synthetic Rubber Co., Ltd .; trade name ABS-15), and branch Table 1 shows three types of graft polymer (manufactured by Toagosei Kagaku Kogyo Co., Ltd .; trade name Reseda GP-301) having polymethyl methacrylate as a component and an epoxy group-containing acrylic polymer as a stem component.
Dry blending was carried out at the weight ratio shown in 1 above, and the mixture was melt-kneaded at 270 ° C. using a twin-screw extruder to obtain a pellet-shaped resin composition. The resin composition thus obtained was subjected to a tensile test (pulling speed: 10 mm / min) and an Izod impact test. The results are shown in Table 1.

[0014]

[Table 1]

[0015]

According to the present invention, the polycarbonate resin and the ABS resin are finely mixed with excellent miscibility,
A resin composition having excellent mechanical strength can be obtained. The graft polymer of the present invention allows the polycarbonate and A
The mechanism by which the compatibility or microdispersion of the BS resin can be improved is not clear, but the epoxy groups in the graft polymer react with the terminal phenolic hydroxyl groups of the polycarbonate to chemically bond, It is presumed that the produced composite graft polymer stabilized the polycarbonate / ABS interface.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 55/02 LME 7142-4J LMF 7142-4J 63/00 NJX 8416-4J NKH 8416-4J 69 / 00 LPP 8416-4J

Claims (1)

Claims: (A) 10 to 90 parts by weight of a polycarbonate resin, (b) 90 to 10 parts by weight of an ABS resin, and (c) a polymethylmethacrylate or styrene-acrylonitrile copolymer. A resin composition comprising a radical-polymerizable macromonomer having a polymer as a skeleton and another radical-polymerizable monomer, and 0.5 to 10 parts by weight of a graft polymer having an epoxy group in a trunk component.