JPH0692531B2 - Polycarbonate composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polycarbonate composition having excellent chemical resistance.

[Conventional technology]

Polycarbonate resin has excellent heat resistance and impact resistance, and is widely used in fields such as various machine parts such as office equipment and automobile exterior parts such as bumpers, but its chemical resistance is poor, so there are restrictions on the field of use. is there.

For this improvement, it has been attempted to blend a polycarbonate with a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, or a polyolefin such as polyethylene, but the effect of improving chemical resistance and heat resistance is not sufficient. On the other hand, it has been attempted to improve it by blending a nylon resin with a polycarbonate (JP-A-55-14).
2049) and JP-A-59-68368). However, when a nylon resin is blended with a polycarbonate resin, the polycarbonate resin is generally decomposed, the molecular weight of the polycarbonate is remarkably reduced, the strength is reduced, and what is practically not available yet.

[Object of the Invention]

The present inventors have found that even if a nylon resin is blended with a polycarbonate resin, the decrease in the molecular weight of the polycarbonate is small, and therefore, the results of diligent investigations to obtain a polycarbonate having excellent mechanical strength and chemical resistance result in a certain compound. The present invention has been accomplished by finding a composition that meets the purpose by simultaneously blending

That is, with respect to 100 parts by weight of the polycarbonate resin, 1 to 200 parts by weight of a polyamide resin composed of an aliphatic diamine and isophthalic acid and terephthalic acid accounts for 50 to 100% by weight, and an epoxy group or an isocyanate group. The present inventors have found a polycarbonate composition characterized by containing 0.01 to 5 parts by weight of a silane coupling agent.

[Structure of Invention]

The polycarbonate resin used in the present invention is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonic acid ester such as diphenyl carbonate. A typical example of the copolymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the dihydroxydiaryl compound include bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2
-Bis ((4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-)
Hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-promophenyl) propane, 2,2-bis (4- Hydroxy-3,5 digromophenyl) propane, 2,2-bis (4-hydroxy-)
Bis (hydroxyaryl) alkanes such as 3,5 dichlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, such as 1,1-bis (4-hydroxyphenyl) cyclohexane Dihydroxy diaryl ethers such as bis (hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy Diphenyl disulfides, such as diphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxy diphenyl sulfoxide, 4,4'-dihydroxy Dihydroxydiaryl sulfoxides such as -3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfoxide Sulfone, 4,
Examples thereof include dihydroxydiarylsulfones such as 4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.

These may be used alone or in combination of two or more,
In addition to these, piperazine, dipiperidyl, hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like may be mixed and used.

Further, the polyamide resin used in the present invention is a polyamide resin in which a polyamide-forming component composed of an aliphatic diamine and isophthalic acid and terephthalic acid accounts for 50 to 100% by weight. Such a polyamide resin is preferable because it has good compatibility with polycarbonate, good transparency, and good dimensional stability.

Examples of the aliphatic diamine include hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine and the like. Also,
The ratio of isophthalic acid and terephthalic acid is not particularly limited, but is preferably isophthalic acid / terephthalic acid = 1/2 to 2/1
(Weight ratio), particularly preferably isophthalic acid / terephthalic acid = 1/1 to 2/1 (weight ratio).

As another polyamide-forming component that accounts for less than 50% by weight of the polyamide resin of the present invention, use a polyamide obtained by polycondensation of a lactam having 3 or more membered rings, a polymerizable ω-amino acid, a dibasic acid and a diamine You can
Specifically, ε-caprolactam, aminocaproic acid,
Enanthlactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone,
Polymer-forming components obtained from α-piperidone, etc., hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, diamines such as metaxylylenediamine, and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, Examples thereof include a polymer-forming component obtained from a dicarboxylic acid such as dodecane dibasic acid and glutaric acid, or two or more kinds thereof.

The content of the polyamide resin is 1 to 20 parts by weight, preferably 2 to 150 parts by weight, based on 100 parts by weight of the polycarbonate, and if the content is small, the chemical resistance improving effect is small, and if the content is large, the thermal stability is poor. Low strength.

As the silane coupling agent containing an epoxy group or an isocyanate group, various known compounds can be used, but a general formula YnSiX _4-n (wherein Y represents a group having an epoxy group or an isocyanate group, X is the same type or Different hydroxyl groups,
A hydrolyzable group such as an alkoxy group or a halogen atom is shown. A silane coupling agent represented by n is an integer of 1, 2, or 3) is particularly preferable. Specifically, epoxy-based silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and isocyanate-based silane coupling agents such as γ-isocyanatopropyltriethoxysilane. A ring agent can be mentioned. Of course, these silane coupling agents can also be used as a mixture of two or more kinds. The blending amount is 100 parts by weight of the polycarbonate resin.
0.01 to 5 parts by weight, and more preferably 0.02 to 3 parts by weight. If the amount is small, the effect is not obtained, and if the amount is large, the viscosity is remarkably increased and the fluidity is adversely affected. Further, an isocyanate group-containing silane coupling agent is preferable because it reduces the molecular weight of the polycarbonate less than an epoxy group-containing silane coupling agent.

As a method for blending the polyamide resin and the silane coupling agent into the polycarbonate resin, various methods can be used at any stage until just before the molding of the final molded product. The simplest method is a method of dry blending the polycarbonate and the additive, but this dry blended product may be melt-mixed and extruded to form a pellet. Alternatively, a master pellet prepared by kneading a predetermined amount or more of an addition part may be prepared and blended with a diluent polycarbonate.

In obtaining the final molded product, the blended product or pellet may be supplied to various molding machines such as injection, extrusion, blow, and compression and molded according to a conventional method, but in some cases, additives may be added. Can be added by a molding machine.

Further, the composition of the present invention comprises various well-known additives other than the above-mentioned compound, for example, glass fiber, carbon fiber, reinforcing agent such as metal whiskers, silica, alumina, silica-alumina clay mineral, silica-magnesium. A filler such as a clay mineral, calcium silicate, calcium carbonate, aspest and carbon black, and a lubricant, a nucleating agent, an antioxidant, a flame retardant, an antistatic agent, a weathering agent, etc. may be contained.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The measurement items in the examples were carried out by the following methods.

(1) ηrel of polyamide resin According to JIS K-6810, it was measured using an Ostwald viscosity tube.

(2) Tg (glass transition temperature) It was determined by differential scanning calorimetry.

(3) Polycarbonate molecular weight device: Toyo Soda HLC802UR column: Toyo Soda G5000H6, G4000H6, G3000H6, G20
The solution was measured with tetrahydrofuran using 00H6, (4 columns), and the number average molecular weight was measured.

(4) Tensile strength, elongation According to ASTM D638 (5) Izod impact value 1/8 inch thick test piece ASTM
Followed D-256.

(6) Gasoline resistance test A tensile test piece was subjected to bending strain of 0.5%, immersed in gasoline for 5 minutes, and then air-dried for 24 hours. A tensile test was performed using the test piece to determine the elongation.

[Production Example of Aromatic Polyamide Resin]

Hexamethylenediamine aqueous solution (80wt%) in distilled water 53Kg
13.9 kg, 9.8 kg isophthalic acid, and 4.9 kg terephthalic acid were added and dissolved uniformly with stirring, and 53 g of acetic acid was added, and then charged into an autoclave. Water was distilled until the nylon salt concentration reached 90% by weight while maintaining the internal pressure at 2.5 kg / cm ^{2, then} the pressure was increased to 13 kg / cm ² , and then the water was further distilled to bring the internal temperature to 25
When the temperature reaches 0 ° C, release the internal pressure gently, and finally 700To
After the polymerization was carried out under reduced pressure of rr for 1 hour, the mixture was extruded into chips. The polymer thus obtained is ηtel 2.
2. Tg was 127 ° C.

Examples 1 to 3 and Comparative Examples 1 to 4 100 parts by weight of a bisphenol A type polycarbonate having a molecular weight of 23000 was blended with the above-mentioned aromatic polyamide resin and silane coupling agent after drying as shown in Table-1, It was kneaded into pellets at 280 ° C with a twin-screw vent extruder manufactured by Nakatani Machinery. 3.6oz after drying the pellet with hot air
Using an injection molding machine (TOSHIBA MACHINE IS75S), molding temperature 300 ℃,
A sample for physical property test was prepared at a mold temperature of 80 ° C. Using this, a normal tensile test and Izod impact were measured. It also checked gasoline resistance. In order to reduce the molecular weight of the polycarbonate resin, the molded product was pulverized and then refractory extracted with methylene chloride to extract the polycarbonate. The molecular weight of the extracted polycarbonate was measured by GPC.

For comparison, the same procedure was carried out when an epoxy compound and an isocyanate compound were blended. All of these molded products were transparent.

[Effect of the Invention] As shown in Table 1, the resin composition obtained by the present invention has remarkably excellent chemical resistance, and its commercial utility value is extremely high.

Claims (1)

[Claims] 1. To 100 parts by weight of a polycarbonate resin,
1 to 200 parts by weight of a polyamide resin comprising 50 to 100% by weight of a polyamide-forming component composed of an aliphatic diamine and isophthalic acid and terephthalic acid, and 0.01 to 5 parts by weight of a silane coupling agent having an epoxy group or an isocyanate group. A polycarbonate composition comprising: