KR890003011B1 - Anti-heat thermoplastic composition - Google Patents

Abstract

A thermoplastic resin compsn. comprises (a) a copolymer of 10-70 wt. parts and a copolymer 5-50 wt. parts obtd. by the polymerization of at least one monomer of aromatic monoalkenyl, vinyl cyanogen, acrylic acid or alkyl ester in the presence of dienetype rubber component, (b) a copolymer of 5-50 wt. parts comprising olefinic monomer contg. eopoxy gp., (N-substd.) maleimide monomer and monomer of (a), (c) a polycarbonate resin of 20-80 wt. parts, (d) an acid compound of 0.05- 5 wt. parts, and (e) an organic silicon compound of 0.05-5 wt. parts. The compsn. has a good heat resistance.

Description

Thermoplastic resin composition excellent in heat resistance

The present invention relates to a thermoplastic resin composition having excellent thermal properties.

In general, pulley carbonate resin is an engineering plastic with excellent mechanical and thermal properties, and has been widely used as a material for all of you. However, polycarbonate resins have high problems at high temperatures, and thus workability has been greatly a problem, and impact strengths change depending on thickness.

In order to improve such a property, research on the resin composition which alloyed the acrylonitrile- butadiene-styrene graft copolymer (henceforth ABS resin) to polycarbonate resin is actively advanced, and it is already commercialized.

Further, as a result of continuing research for the purpose of improving various properties of these resin compositions, many patents have been proposed. Examples of proposals include United States Patent Nos. 3162695, 3130177, 4128544, 3649712, 4299929, 4145331, 4390657, 4430476, 4393161, 4487881 JP 52-63954, 51-122157, 51-13853, 53-7757, 58-11540 , 57-12047, 59-226054, 59-227942, 60-65055 and EP 0074112, 22979, 0146, 135493 and the like. However, the patents proposed so far have appropriately harmonized the strengths and weaknesses of the respective resins such as mechanical properties, thermal properties, and processability of the alloys of the polycarbonate resin and the ABS resin. That is, the method of improving the mechanical properties, the method of improving the heat resistance, the method of improving the workability, the method of improving the weather resistance, the method of improving the strength of the welldraene, the method of solving the thickness dependence, and the like.

Looking at the method of improving the heat resistance of the various properties in detail, polycarbonate resin is very excellent in heat resistance, while ABS resin is poor in heat resistance there was a limit to increase the heat resistance when alloying these two resins. Suggested contents for the purpose of increasing the heat resistance, the styrene-maleic anhydride copolymer (SMA resin) instead of the ABS resin in the polycarbonate and ABS resin composition or the method of adding SMA and ABS used in the alloy Among the resin components, a method of using a super heat resistant ABS resin in which styrene is replaced with α-methyl styrene for super heat resistance has been proposed, but also has a limit in increasing heat resistance. Of course, a method of maximizing the content of the polycarbonate resin in the polycarbonate and ABS resin composition as a method for improving the heat resistance can be considered, but in this case is excluded from consideration because it violates the purpose of the alloy of the two resins. In addition, polycarbonate and ABS resin alloys are limited in the compatibility of the two resins, the weld line strength is lowered, several proposals to solve this have been published. In other words, U.S. Patent No. 4430476 and European Patent No. 00744112 have attempted to improve compatibility by adding resins and plasticizers such as polyethylene, polypropylene, and olefins such as ethylene propylene terpolymer (EPDM) as the third substance. Japanese Patent Application Laid-Open No. 59-2274942 et al. Proposed the improvement of the weld line strength by the addition of ethylene-ethyl acetate copolymer (EEA). However, the above proposals improved the compatibility of the weld line to improve the weld line strength, while significantly reducing the mechanical strength and thermal properties.

The present inventors have completed the present invention as a result of repeated research for the purpose of significantly increasing the thermal properties and the weld line strength simultaneously while maintaining the above problems, that is, mechanical properties. That is, the polycarbonate and ABS resin composition basically controls the selection and content of acrylonitrile and α-methylstyrene in ABS, which are factors affecting the compatibility between resins, and then simultaneously achieves two purposes of improving heat resistance and compatibility. In order to mix the copolymer of N-phenyl maleimide-styrene-acrylonitrile containing the epoxy group together in the above composition, the compatibility is greatly increased to make the system composed of one phase to increase the weld line strength, Since the N-phenylmaleimide-styrene acrylonitrile copolymer containing an epoxy group has excellent thermal properties, the thermal properties are greatly increased when they are mixed together. That is, the present invention is a thermoplastic resin composition containing each of the following components (A) (B) (C) (D) (E) (F) as main components, which is A) aromatic monoalkenyl monomer, vinyl cyan monomer and acrylic acid. Or 10-70 parts by weight of a copolymer obtained by bulk, suspension or emulsion polymerization of one or more monomers selected from alkyl ester monomers in the presence of a diene rubber component, B) an aromatic mono alkenyl monomer, a vinyl cyan monomer, and 5-50 parts by weight of a copolymer obtained by bulk, suspension or emulsion polymerization of one or more monomers selected from alkyl ester monomers of acrylic acid or methacrylic acid, and C) olefinic monomers containing maleic acid, maleimide, 5-50 parts by weight of a copolymer composed of a monomer such as N-substituted maleimide and the monomer of B), D) 20-80 parts by weight of a polycarbonate resin, and E) an inorganic, organic or organic anhydride F) It is a resin composition comprised from 0.05-5 weight part of organosilicon compounds with respect to 100 weight part of said compositions which consist of 0.05-5 weight part of one or more acid compounds chosen from.

The thermoplastic resin composition prepared as the main component is not only excellent in mechanical properties and low temperature properties, but also particularly excellent in thermal properties and weld line strength. The thermoplastic resin composition achieved in the present invention cannot be obtained if any of the component blending ratios of the components in the above-mentioned components (A) (B) (C) (D) (E) (F) is different.

으로 여기서 A 성분은 디하이드릭 페놀 양단에 방향족 라디칼을 갖는 성분으로서 구체적인 식은 다음과 같다.The graft copolymer of component A) used in the present invention is prepared by bulk, suspension, emulsification, or a mixture thereof. For example, in the emulsion polymerization method of ABS resin, butadiene is first polymerized to make polybutadiene latex, and then vinyl cyanide monomer and styrene or α-methyl styrene monomer are added to polybutadiene and these monomers to graft the multicomponent and polyphase. ABS resin). The composition ratio of each component can be arbitrarily adjusted by putting the remaining monomer into polybutadiene. Graft copolymer The rubber component used may include butadiene type rubber and isoprene type rubber. The amount of the graft copolymer is 10-70 parts by weight, preferably 25-50 parts by weight based on the weight ratio of the component graft copolymer. The diameter is 0.1-1.5μ, preferably 0.1-0.5μ. Examples of the aromatic vinyl monomers include 30-70 parts by weight of styrene, α-methyl styrene vinyl toluene, t-butylstyrene, halogen-substituted styrene, or mixtures thereof, specifically styrene, α-methylstyrene, or mixtures thereof. As the vinyl monomer, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like are used, and preferably 15 to 35 parts by weight of acrylonitrile is used. In addition, a vinyl monomer copolymerizable with the two kinds of monomers may be used in the same amount. Examples thereof include vinyl monomers such as maleimide, N-substituted maleimide, alkyl ester methacrylic ester, alkyl acid and methacrylic acid. The graft copolymer of component A) thus prepared is preferably 10-60 parts by weight, more preferably 20-50 parts by weight. The copolymer of component B) is prepared in the same way as component A) by bulk, suspension, emulsion polymerization or a mixture thereof. The aromatic vinyl monomer and vinyl cyanide monomer and the copolymerizable vinyl monomer used in component B) are the same as those described in component A), and the amount of the aromatic vinyl monomer is 60-80 parts by weight of the vinyl cyanide monomer is 20-40 parts by weight. do. The copolymer of the (B) component thus prepared is preferably 5-40 parts by weight, more preferably 7-30 parts by weight. The copolymer of component C) is prepared by bulk, suspension, emulsion polymerization, or a mixture thereof as with component A). The aromatic vinyl monomers and vinyl cyanide monomers used in component C) are the same as those described in component A), and examples of olefin monomers containing epoxy groups include unsaturated glycidyl esters, unsaturated glycidyl ethers, and epoxy alkenes P-glycinyl styrene Examples of the monomer of the N-substituted maleimide include N-phenylmaleimide, and the amount of these monomers used is 20-60 parts by weight of aromatic vinyl monomer and 10-35 parts by weight of vinyl cyanide monomer. 1-10 weight part of olefin monomers containing, and 10-40 weight part of monomers of maleimide are used. The C) component copolymer thus copolymerized is preferably used 5-40 parts by weight, more preferably 7-40 parts by weight. The general formula of the polycarbonate of the D) component

Here, component A is a component having aromatic radicals at both ends of the dihydric phenol, and the specific formula is as follows.

Wherein R ₁ and R ₂ are hydrogen alkyl or petyl group, the alkyl has 1-6 carbon atoms and n value is between 40-300. Polycarbonates are aromatic polycarbonates, aliphatic carbonates, aromatic aliphatics, polycarbonates, which are specifically 2,2'-bis (4-hydroxyphenyl) alkanes, bis (4-hydroxyphenyl) ethers, bis (4-hydroxyphenyls) The polymer or copolymer by bisphenol or halogenated phenols, such as a sulfoxide. In addition, the manufacturing method of the polycarbonate resin is 1,546,311, 962,274, U.S. Patent Nos. 3,248,414, 3,251,668, 3,187,065, 3,028,365, 2,999,846, 2,964,974, 2,970,137, 2,991,273, 2,999,835, 3,334,154, 4,131,843, 4,131,843, 4,132,843, 154, 4,001, etc. And examples of representative polycarbonate resins are detailed in Encyclopedia of Polymer Science and Technology Vo1.10, page 710-764 (1969). 20-80 parts by weight of such D) component polycarbonate resin is more preferably 30-70 parts by weight. If the polycarbonate resin is used in an amount of 20 parts by weight or less or 80 parts by weight or more, the above-described composition cannot be exhibited. E) The component is added to the resin composition of the present invention as a small amount of an organic acid or an organic anhydride, as disclosed in Japanese Patent Application Laid-Open No. 58-11550, US Pat. This increases the thermal stability of the stay. Representative examples include maleic acid, butyric acid, maleic anhydride, and butyric anhydride. The addition amount thereof is used at 0.05-5 parts by weight. When it is used at 0.05 parts by weight or less, the thermal stability of the resin composition cannot be increased. It is greatly reduced. F) As the organo-silicon compound, polysiloxane of the following general formula, silane of R ₁ R ₂ R ₃ R ₄ Si, etc. may be used.

Wherein R ₁ R ₂ R ₃ R ₄ is lower alkyl or aryl and m is 1-2,000. Specific examples are polymethyl siloxane, tetraethylsilane and the like, and the amount thereof is preferably 0.05-0.3 parts by weight and more preferably 0.05-0.25 parts by weight. The resin composition of the present invention can be diversified by appropriately adding additives such as lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, processing aids, mold release agents, foaming agents, antistatic agents, pigments, and dyes according to the purpose of the resin composition as described above. have. In addition, a flame retardant may be used in the resin composition of the present invention for flame retardation, and various reinforcement-glass fibers, talc mica, calcium carbonate, and the like may be used to improve rigidity. Hereinafter, the present invention will be described in detail in the Examples. Parts used in the present invention are based on weight.

Production Example 1

Preparation of Graft Copolymer (A)

100 parts of butadiene, 120 parts of ion-exchanged water, 0.2 parts of sodium lauryl sulfite and 0.2 parts of t-dodecyl mercaptan were added, and 0.1 parts of potassium persulfate was added at a reactor temperature of 40 ° C for polymerization for 15 hours to obtain a polybutadiene latex. . 40 parts of this polybutadiene latex, 100 parts of ion-exchanged water, 45 parts of styrene, 15 parts of acrylonitrile, 0.3 parts of sodium lauryl sulfate, and 0.3 parts of t-dodecyl mercaptan were added and polymerized at a reactor temperature of 100 ° C. for 2 hours. The copolymer is referred to as ABS-1. 30 parts of polybutadiene latex obtained in Preparation Example 1), 0.3 parts of sodium lauryl sulfate, 100 parts of ion-exchanged water, 25 parts of α-methylstyrene, 15 parts of styrene, 10 parts of acrylonitrile, t-dodecyl mercaptan 0.1 The part obtained in the reactor was polymerized at a reaction temperature of 90 ° C. for 2 hours and referred to as ABS-2.

Production Example 2)

Preparation of Copolymer (B)

100 parts of ion-exchanged water, 35 parts of α-methyl styrene, 40 parts of styrene, 25 parts of acrylonitrile, 0.3 parts of sodium lauryl sulfate, and 0.3 parts of t-dodecyl mercaptan were added to the closed reactor. The copolymer obtained by polymerization over time is called SAN.

Production Example 3

Preparation of Copolymer (C)

200 parts of ion-exchanged water, 0.7 parts of sodium lauryl sulfate, 52 parts of styrene, 15 parts of acrylonitrile, 30 parts of N-phenyl maleim, 3 parts of 3,4-epoxy butene, t-dodecyl mer 0.1 part of captan is placed in a reactor, and the copolymer obtained by polymerization at a reaction temperature of 90 ° C. for 4 hours is referred to as P-SAN-1.

Production Example 4)

Preparation of Copolymer (C)

50 parts of ion-exchanged water, 0.7 parts of sodium lauryl sulfate, 50 parts of styrene, 8 parts of α-methyl styrene, 15 parts of atilo, 22 parts of N-phenyl maleimide, 5 parts of glycidyl methacrylate The copolymer obtained by adding 0.1 part of t-dodecyl mercaptan to the reactor and polymerizing at a reaction temperature of 90 ° C. for 4 hours is referred to as P-SAN-2.

Example 1

20 parts by weight of the copolymer ABS-1 prepared in the preparation example, 30 parts by weight of SAN, 10 parts by weight of P-SAN-1, and polykanate resin (Japan Teijin Chemical Products: Pannite L-125OY) 40 In addition, a resin mixture consisting of 0.3 parts of maleic acid as a thermal retention stabilizer, 0.5 parts of polydimethylsiloxane (molecular weight: 20,000), 0.2 parts of ethylene bis steamide as a lubricant, and 0.5 parts of other heat stabilizers was used as a Henschel mixer. ) And uniformly mixed for 5 minutes, extruded by using an extruder at a temperature of about 230-260 ° C., and then made into pellets. In order to measure heat resistance and other physical properties, the pellets were pre-dried at 110 ° C. for about 3 hours using a re-drying dryer or a hot air dryer, and the results were measured by the following method.

a) flow characteristics; Melt viscosity was determined by an Instron capillary rheometer under a shear rate of 250 ° C. and 352.2 sec.

b) Physical property test: Pellets obtained above were tested by using a 2.5-ounce injection machine to prepare tensile strength, impact strength, thermal deformation temperature test specimens, and weld-line test specimens according to ASTM specification.

Example 2

Extrusion was carried out in the same manner as in Example 1, except that 30 parts by weight of SAN in 20 parts by weight and 10 parts by weight of P-SAN-1 were 20 parts by weight in the composition of Example 1 to observe the effect of component (C) of the present invention. And the results of the experiment through injection molding are shown in Table 1.

Example 3

Among the components of Example 2, 20 parts by weight of P-SAN-2 was used instead of 20 parts by weight of P-SAN-1, and the remainder of the composition was tested in the same manner as in Example 1 and shown in Table 1.

Example 4

18 parts by weight of the graft copolymer ABS-2 prepared in the preparation example, 10 parts by weight of SAN, 12 parts by weight of P-SAN-1, 60 parts by weight of polycarbonate resin, maleic anhydride as a thermal retention stabilizer In order to improve 0.3 part low temperature properties, 0.5 parts of polymethyl ethyl siloxane, 0.2 parts of ethylene bis steamide as a lubricant, and 0.5 parts of other heat stabilizers were tested in the same manner as in Example 1, and the results are shown in Table 1.

Example 5

P-SAN-2 used in Example 4 was added and the remainder was tested in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1

In order to investigate the effect of P-SAN-1 on the mechanical and thermal properties of the composition, in the composition of Example 2, 40 parts by weight of SAN was used instead of 20 parts by weight of P-SAN-1, and the rest was made with the same composition. In the same manner as in Example 1, the mechanical, thermal and flow characteristics are shown in Table 1.

Comparative Example 2

In order to investigate the effect of P-SAN-2 on the mechanical and thermal properties of the composition, in the composition of Example 3, 40 parts by weight of SAN was used instead of 20 parts by weight of P-SAN-2, and the rest was made with the same composition. Tested in the same manner as in Example 1, the mechanical, thermal and flow characteristics are shown in Table 1.

Comparative Example 3

In order to observe the effect of component E) of the present invention, pellets of the resin composition were prepared in the same manner as in Example 1 except for the maleic acid as the retention heat stabilizer in Example 2. The resultant was placed in a cylinder at 260 ° C. for 5 minutes, and then injected in the same manner as in Example 1 to prepare a specimen and to measure and compare the physical properties thereof.

Comparative Example 4

In order to observe the effect of component F) of the present invention, except for polydimethylsiloxane in Example 2, the rest of the composition was the same composition and the effect on low temperature properties was measured. Pellets were made in the same manner as in Example 1, and injection molding was carried out to measure the low temperature properties at -30 ° C.

Claims (3)

A) 10-70 parts by weight of a copolymer obtained by bulk, suspension or emulsion polymerization of one or more monomers selected from aromatic mono alkenyl monomers, vinyl cyan monomers and acrylic acid or alkyl ester monomers in the presence of a diene rubber component; , B) 5-50 parts by weight of a copolymer obtained by bulk, suspension or emulsion polymerization of at least one monomer selected from aromatic mono alkenyl monomers, vinyl cyan monomers and alkyl ester monomers of acrylic acid or methacrylic acid, and C 5-50 parts by weight of a copolymer comprising an olefinic monomer containing an epoxy group, a maleimide N-substituted maleimide monomer and a monomer of B), D) 20-80 parts by weight of a polycarbonate resin, E) an inorganic acid, F) organosilicon to 100 parts by weight of the composition, consisting of 0.05-5 parts by weight of at least one acid compound selected from organic acids or organic acid anhydrides The resin composition consisting of from 0.05 to 5 parts by weight of compound. The resin composition according to claim 1, wherein the epoxy group-containing olefinic monomer is unsaturated glycidyl ester, unsaturated, glycidyl ether, epoxy alkene-P-glycidyl styrene. The resin composition according to claim 1, wherein the N-substituted maleimide is N-phenyl maleimide.