JPS5898357A - resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polycarbonate resin composition, more specifically a polycarbonate resin composition having improved solvent resistance, impact strength, heat aging resistance, and low temperature impact strength. It is widely used as an engineering plastic because it is impact resistant, self-extinguishing, has higher heat resistance than other resins, and has superior electrical properties and dimensional stability. ing.

However, polycarbonate resins have the following drawbacks, which limit their use. 1) When using polycarbonate resin as a molded product, the impact strength is highly dependent on the thickness of the molded product. For example, λ2■thickness l
The notched impact value of &4 m (174 inch thick) indicates ductile failure, whereas
shows brittle fracture, and the impact strength decreases in the thicker region. 2) The high impact value of the above-mentioned 12m-thick steel notch decreases rapidly at low temperatures. 3) When exposed to high temperature conditions, thermal aging occurs and the above impact strength decreases. 4) Due to low solvent resistance, large-sized molded products with complex shapes and large residual stress may cause stress cracks when exposed to certain solvent atmospheres. Because of these drawbacks, polycarbonate resins, despite having high impact strength, are not suitable for applications requiring resistance to gasoline and paint, impact strength at low temperatures, and heat aging resistance of impact strength, e.g. It was not used much for private vehicle parts.

As a result of intensive research aimed at improving the above-mentioned deficiencies of polycarbonate resins, the present inventors found that Nishimoto resin compositions consisting of polycarbonate resins, aromatic polyesters, butyl rubber, and acrylic elastic polymers have high solvent resistance and low temperature properties. Impact strength and opposition at! It was discovered that it exhibits fearsome heat aging resistance, and the pressure between failures was reached.

That is, the present invention uses polycarbonate resin (Al 2
0-901181i p Aromatic polyester (B) 5
~70 heavy lii part, Zuchino [rubber fcl l-ls
Ill part and acrylic elastic polymer Ill 1-2
0 parts by weight, and ((A) + ■) ) / (C
＋ ＋ (D) ) has a weight ratio of 2 to 20.
This is a resin composition for forming an I image.

The resin composition of the present invention is superior to polycarbonate resins in gasoline resistance, impact resistance for thick-walled molded articles, impact strength at low temperatures, and heat aging resistance of impact strength. ,
Furthermore, it has excellent moldability, tensile strength ring mechanical properties, surface appearance, heat discoloration resistance, etc., and can be widely used in applications that have been limited to polycarbonate resins, such as automobile parts.The present invention Among the components used in the composition, the combination of polycarbonate resin and aromatic polyester is disclosed in Japanese Patent Publications No. 36-14035 and Japanese Patent Publication No. 53-1.
The combination of polycarbonate resin and butyl rubber was reported in Japanese Patent Publication No. 2537 as an improvement in MNl resistance.
Japanese Patent Publication No. 18823 discloses improvements in the impact resistance of thick-walled molded products. However, neither of them describes or suggests the objectives and advantages of the present invention, and in fact, this combination does not provide the characteristics of the resin composition of the present invention.

The polycarbonate resin used in the present invention (
) are prepared by the reaction of a dihydric phenol with a carbonate precursor such as phosgene or the transesterification reaction of a dihydric phenol with a carbonate precursor such as diphenyl carbonate in the presence of an acid acceptor and a molecular weight regulator. be able to. The dihydric phenol that can be used here is preferably bisphenols, particularly λ2-bis(4
-hydroxyphenyl)purpan (hereinafter referred to as bisphenol A) is preferred. Examples of other dihydric phenols include hydroquinone, 4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)alkane, bis(4-hydroxyphenyl)cycloalka/, bis(
4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfite, his(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl)
Examples include ketones, bis(4-hydroxyphenyl) ether, and I-rhodanated bisphenols such as bis(5-dibutyl-4-hydroxyphenyl)purpane. The polycarbonate resin may be a copolymer using one or more homopolymers of these dihydric phenols, or a mixture thereof. It may also be a thermoplastic lantum-branched polycarbonate reacted with a dihydric phenol, which is a polyfunctional aromatic compound, and/or a carbonate precursor.

The aromatic polyester used in this EAVC is composed of an alkylene glycol, such as a glycol having 2 to 10 carbon atoms, and an aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, isophthalic acid, or the like. It is a reaction product (poly7-) with an ester-forming derivative.

Gripoor Toshijin is ethylene glycol, 1,4-butanediol, 1,6-hexanediol.

Examples include 1.4-cyclohexane dimetatool and 1.10-tecamethylene glycol. Preferable aromatic dicarboxylic acids include terephthalic acid and isophthalic acid. Specific examples of aromatic polynysterates include poly(ethylene terephthalate), poly(1°4-butylene terephthalate), and amorphous poly(ethylene terephthalate) copolymer. Main stell, amorphous poly(1,4-butylene terephthalate) copolyester, amorphous poly(1,4
-cyclohexane dimethylene terephthalate) copolyester.

As the butyl rubber (C) used in the present invention, for example, inbutylene and 1 to 7 weight of isoprene,
Synthetic rubbers with a low degree of unsaturation are obtained by copolymerizing them at low temperatures, for example, about -100 DEG C., in the presence of Friedel-Krach type metal chloride such as aluminum chloride.

The acrylic elastic polymer 0 used in the present invention is
Methacrylic esters, sitadiene, and styrene whose main components are acrylic esters.

A copolymer with a copolymerizable monomer such as acrinitrile, for example, an alkyl acrylate whose alkyl group has 2 to 12 carbon atoms (for example, 2-ethylhexyl acrylate).
), n-7' tylacryl 1. - etc.) 40-95% by weight
and butadiene 5 to 40 weights and methyl methacrylate 0
~301 JIIt% and ty 6.01 to 3% by weight of a crosslinking agent (e.g., ethylene dimethacrylate, etc.) is emulsified, and a flocculant is added thereto to obtain an average particle size αl~03μ A latex containing 50 to 80 parts by weight of a cross-linked rubber co-association is first mixed with 20 to 80 parts by weight of styrene, 20 to 50 parts by weight of methyl methacrylate, 0 to 60 parts by weight of acrylic methacrylate, and a crosslinking agent (for domestic dogs, ethylene). After adding 10 to 40 parts by weight of a mixture of dimethacrylate, divinylbenzene #01 to 21, a crosslinking agent (e.g., ethylene dimethacrylate, divinylbenzene) containing 1 to 4 Nm% of a furkyl group is added. Number of carbons is 1
A multicomponent resin obtained by further addition polymerization of 5 to 25 parts by weight of an alkyl methacrylate (for example, methyl methacrylate, etc.) of 4 to 4 is added. A specific example of such an acrylic elastic polymer is the product name HIA-1 from Kenbetsu Kagaku Kogyo 6).
5 and 4c are commercially available.

In the resin composition of the present invention, the blending ratio of each h''-, is 20 to 90 parts by weight, preferably 30 to 80 parts by weight, of polycarbonate resin (A), and aromatic polyester Q.
3) is 5 to 70 layers, preferably j'! -10 to 60 parts, butyl rubber (C1 is 1 to 15% by weight, preferably 2 to 10 parts by weight, acrylic elastic polymer CD) is 1 to 201111 parts, preferably 2 to 15 parts parts by weight, and furthermore, the weight ratio of (pseudo) soil 11/(C1+■)) is 2 to 20. Q31. Even if the amount of the 0.01 component added is less or more than the above-mentioned range, the solvent resistance, impact resistance, impact resistance at low temperature, and heat aging resistance of the resin composition of the present invention will be improved. (C).

■) If the amount of the component added exceeds the above range, layer delamination may occur, damaging the appearance of the molded product or reducing heat resistance.
2J is not preferable.

Present invention +7) The resin composition can be prepared by any method. The method includes, for example, adding aromatic polystyrene), butyl rubber C) and acrylic elastic polymer [)l to polycarbonate resin and mixing them using a V-type blender, super mixer, etc.; "Method of mixing in a molten state using a method, 1c
There is a method in which components () and (D) are mixed in advance in a kneading mill or a Banbury mixer, and this is mixed together with component (B) into the polycarbonate resin (A) directly or by boiling in a molten state.

The composition of the present invention includes additives for the purpose of modifying the resin,
For example, reinforcing materials such as glass fiber, heat stabilizers, antioxidants, blowing agents, light stabilizers, flame retardants, plasticizers, mold release agents, antistatic agents, antistatic agents, dyes, etc. can be added. . Further, other resins such as polypropylene, polystyrene, polymethyl methacrylate, AS resin, ABS resin, and polyphenylene oxide may be mixed.

The present invention will be explained below with reference to Examples. Incidentally, the part in the examples means the xi part. Further, if%'b was determined in the following manner.

! , Solvent resistance evaluation method: Using an injection molding machine, pre-dried pellets were
It was formed into a flat plate measuring 7 m x 127 w x 3 cm, cut into 6 ml pieces with a drill, and then treated at a temperature of 2 s°C and a humidity of 50% for 24 hours. The bolt was tightened to a predetermined torque using a bolt with an M6 processed edge, and the bolt was soaked in gasoline for 5 minutes to observe whether or not cranking occurred. The higher the tightening torque that favors crank generation, the better the solvent resistance.

2 Impact resistance evaluation method: Using an injection molding machine, pre-dried pellets were molded into 64'
mX I L 7mX I 18vm and 64 fog X11
7+wX (L35m+ impact test pieces were each molded,
A 0.25 mR notch was added. The Hj:,w1 piece was treated at a temperature of 23°C and Na5o%Y for 24 hours, and then the impact strength was measured using an Izotsu physical impact tester (manufactured by Toyo Seiki ■). The higher the impact strength, the better the impact resistance.

1 Impact resistance evaluation method at low temperature: The notched impact test piece molded and processed in 2 above was heated to -1θ℃.
After being left in a constant temperature chamber for 1 hour, it was taken out from the constant temperature chamber and its impact strength was immediately measured using the Fizot impact tester described in 2 above.

The higher the impact strength, the better the impact resistance at low temperatures.

Table Heat aging resistance of impact strength: The notched impact test piece molded and processed in 2 above was tested at 125°C.
After being left at Vr for 65 hours in a constant temperature chamber, it was taken out from the constant temperature chamber and treated at a temperature of 23° C. and a humidity of 50% for 24 hours. The impact strength was measured using the Fizot impact tester described in 2 above.The higher the impact strength, the higher the heat aging resistance of the impact strength.

Examples 1 to 6 and Comparative Examples 1 to 5 Pre-dried polycarbonate resin (4) (Kijin Kasei ■
(manufactured by Panrai) L-1250), aromatic polyester and butyl rubber (C) (manufactured by Japan Synthetic Rubber ■: II
R-oss), 7 acrylic elastic polymer 0) (
Chemical industry by prefecture■11! :HIA-15) respectively.
Using the amounts shown in the table, mix in a V-type blender and then
The mixture was extruded into pellets using a wag extruder (manufactured by Chuo Kikai Co., Ltd.: VSK-io). The obtained pellets were injection molded using the evaluation method described above, and were evaluated for solvent resistance, impact resistance, impact resistance at low temperatures,
The heat aging resistance of impact strength was evaluated. The results are shown in Table 1.

It can be seen from Table 1 that the composition of the present invention is excellent in solvent resistance, impact resistance, impact resistance at low temperatures, and heat aging resistance of impact strength.

Percentage applicant: Teijin Kasei Ltd.

Claims (1)

[Claims] Polycarbonate resin (A) 20~901'1FVHI
Consisting of aromatic polyester CB15-70inIBt Butyl Rubber (Incorporated) 1-15 parts by weight and acrylic elastic polymer CD11-20 parts by weight,
Bl)/((Q+<Dl] weight ratio is 2~
20. A resin composition characterized in that: