JPH01182363A - Resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition outstanding in impact, heat an chemical resistances and moldability, especially suitable for automobile out plies, comprising a specified proportion of a polyphenylene ether resin, aromatic polyamide, and aromatic polycarbonate. CONSTITUTION:The objective composition comprising (A) 20-90wt.% of a polyphenylene ether resin produced by oxidative polymerization of a phenolic compound of the formula [R<1>-R<5> are each H, halogen or (substituted) hydrocarbon, at least one of them being H] (e.g., phenol, cresol), (B) 5-60wt.% of an aromatic polyamide (e.g., nylon salt produced from an aromatic dicarboxylic acid such as isophthalic acid or terephthalic acid and an aliphatic diamine), and (C) 5-70wt.% of an aromatic polycarbonate. Preferably, 100 pts.wt. of this composition be additionally incorporated with 0.5-80 pts.wt. of a styrene- based polymer.

Description

Detailed Description of the Invention [Field of Industrial Application] The resin composition of the present invention has excellent impact resistance, heat resistance, and chemical resistance, and is a composition with good moldability. parts, auto parts, household items, equipment housings,
It is applied to a wide range of fields such as mechanical parts, extrusion molded sheets, films, and blow molded products, and is particularly suitable for use in automobile outer panels.

[Conventional technology]

Although polyphenylene ether resin has excellent thermal, mechanical, and electrical properties, it has poor moldability, so it is sold as a blend containing polystyrene resin under the trademark Noryl by General Electric Company. ing. However, the use of this modified product is limited due to its poor resistance to solvents.

Furthermore, Japanese Patent Publication No. 11.2-13712 describes that polyphenylene ether may be added to aromatic polycarbonate in order to make it resistant to cracking due to concentrated stress and to have a higher heat distortion temperature. Although the composition described above is known, the molding processability is significantly poor, and polyphenylene ether and aromatic polycarbonate have poor resistance to solvents, so blended resin compositions of these two also have poor solvent resistance. The disadvantages were that it was inferior in performance and lacked practicality.

Furthermore, Tokkosho! also offers resin compositions containing polyphenylene ether, polystyrene, and polycarbonate, and resin compositions containing polyphenylene ether, rubber-modified polystyrene, high styrene rubber, and polycarbonate. ;/-37191 Publication, Tokko Akira! ;/
However, since all of the constituent resins have poor solvent resistance, the blended resin composition in this case also has poor solvent resistance. The reality is that it cannot be applied to applications where solvent resistance is strictly required.

[Purpose of the invention]

The present invention relates to a resin composition that is made by blending polyphenylene ether resin, aromatic polyamide, and aromatic polycarbonate resin using an industrially easy method, and has excellent moldability and excellent mechanical and thermal properties. It is.

[Structure of the invention]

Hereinafter, the configuration of the present invention will be specifically explained.

In the present invention, (A) polyphenylene ether resin has the general formula (wherein R'', R'', R3, R' and R6 are selected from hydrogen atoms, halogen atoms, hydrocarbon groups or substituted hydrocarbon groups) (of which one is always a hydrogen atom) This is a polymer obtained by oxidatively polymerizing a phenol compound represented by the following formula with oxygen or an oxygen-containing gas using an oxidative coupling catalyst.

R', R2, R3, R4 and R in the above general formula
Specific examples of 5 include hydrogen, chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, and chlorophenyl. , methylphenyl, dimethylphenyl, ethylphenyl, etc.

Specific examples of the phenol compound of the above general formula include phenol, 01m or p-cresol, 46-, co,! −
, co, lI- or J, 3-dimethylphenol, coatathyl-6-phenyl-phenol, J, 6-siphenylphenol, co, t, -diethylphenol, coatathyl-6-ethylphenol, co, J, ! ;-1λ,
Examples include 3,6- and co-, II, 6-drimethylphenol. Two or more of these phenolic compounds may be used (・.

It is also possible to copolymerize a phenol compound having the above general formula with a dihydric phenol such as bisphenol A, tetrabromobisphenol A, resorcinol, and )1-hydroquinone nato.

The aromatic polyamide (B) used in the present invention is formed from an aromatic dicarboxylic acid such as isophthalic acid or terephthalic acid and an aliphatic diamine, and contains 90 to 100% by weight of aromatic polyamide forming components, and lactam. Alternatively, it means a polyamide resin in which the aliphatic polyamide forming component consisting of an aliphatic diamine and an aliphatic dicarboxylic acid is 60 to 0% by weight.

Polymerization of aromatic polyamides is usually produced by the so-called melt polymerization method by adding lactam to a nylon salt consisting of diamine and dicarboxylic acid or an aqueous solution thereof, if necessary, but depending on the composition of isophthalic acid and terephthalic acid, It can also be produced by a solution method or an interfacial polymerization method.

Here, the composition of isophthalic acid and terephthalic acid can be in any ratio, but if the ratio of terephthalic acid is large, the melting point of the polyamide will be 300° C. or higher, so it is preferable that the terephthalic acid content is 30% by weight or less. Usually, the weight ratio of isophthalic acid to terephthalic acid is 0:0 to 0:0.

Other copolymerizable components include lactams with three or more membered rings, polymerizable ω-amino acids, dibasic acids and diamines,
Specifically, ε-caprolactam, aminocaproic acid,
Polymers such as enantholactam, tuaminohbutanoic acid, //-aminoundecanoic acid, deaminononanoic acid, α-pyrrolidone, α-piperidone, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, Kotsu 2-bis( Diamines such as 41-amino-3-methylcyclohexyl) pronokone and metaxylylene diamine, adipic acid, cepatic acid, dodecanibasic acid,
Dicarboxylic acids such as geltaric acid can be mentioned.

The aromatic polycarbonate resin (C) used in the present invention is a polycarbonate resin 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 carbonate ester such as diphenyl carbonate. It is a combination or copolymer, and a typical example is Tip 2-
Polycanibonate resins made from bis(terhydroxyphenyl)furopane (bisphenol A) are mentioned.

In addition to bisphenol A, the dihydroxydiaryl compounds include bis(4!-hydroxyphenyl)methane, l,/-bis(terhydroxyphenyl)ethane,
Tips - monobis(<=-hydroxyphenyl)butane, -
, Nibis(terhydroxyphenyl)octane, Bis(lI-hydroxyphenyl)phenylmethane, Tip 2
-bis(lI-hydroxy-3-methylphenyl)propane, /, /-bis(cuhydroxy-3-tert-butylphenyl)furopane, -92-bis(ll-hydroxy-3-bromophenyl)furono(n), 2. Nevis (
lI-Hydroxy-3,A-dibromophenyl)propane, co-bis(4!-hydroxy-3,3-dichlorophenyl)propane, bis(hydroxyaryl)alkanes, /,/-bis(terhydroxyphenyl) ) cyclopentane, bis(hydroxyaryl)cycloalkanes such as /, l-bis(lI-hydroxyphenyl)cyclohexane, da, da'-dihydroxydiphenyl ether, "e"-dihydroxy-3,3'-
Dimethyl diphenyl ether, dihydroxydiarylethers such as 5, lI'-dihydroxydiphenyl sulfide, +, +'-dihydroxy-3,3'-
Dihydroxydiaryl sulfides such as dimethyl diphenyl sulfide, da, da'-dihydroxydiphenyl sulfoxide, +, lI'-dihydroxy-3,3
Dihydroxydiaryl sulfoxides such as '-dimethyldiphenyl sulfoxide, da, di'-dihydroxydiphenyl sulfone,! , 4”-dihydroxy-3,
Examples include dihydroxydiarylsulfones such as 3'-dimethyldiphenylsulfone.

These can be used alone or in a mixture of two or more,
In addition to these, piperazine, diviveridyl, hydroquinone, resorcinol, 4! , 4! '-Dihydroxycyphele and the like may be used in combination.

It is preferable that the composition of the present invention further contains a styrene polymer from the viewpoint of impact resistance.

Specific examples of rubber-modified styrenic resins include, for example:
Butadiene rubber modified polystyrene, butadiene rubber modified styrene-acrylonitrile copolymer, acrylic rubber modified polystyrene, acrylic rubber modified styrene-acrylonitrile copolymer, ethylene-propylene copolymer modified polystyrene, ethylene-methyl methacrylate copolymer modified polystyrene Examples include.

Among them, styrene/butadiene copolymer, styrene/
Butadiene block copolymer, hydrogenated styrene/butadiene block copolymer, stisine/isoprene block copolymer, styrene/ethylene/butylene block copolymer, styrene/ethylene/propylene block copolymer, Noyo5 A copolymer having a styrenic hydrocarbon polymer block-conjugated diene elastomer block copolymer or a styrenic hydrocarbon polymer block-olefin elastomer block copolymer as a constituent component can be preferably used.

These styrenic hydrocarbon, polymer block-conjugated diene elastomer block copolymers are normal elastomer block copolymers of styrene hydrocarbon blocks and conjugated diene blocks, such as linear block copolymers,
Alternatively, a radial block copolymer may be mentioned. (Refer to JP-A-4/-20'12/s2) Typical styrenic hydrocarbons used here include styrene, α-methylstyrene, vinylxylene, ethylvinylxylene, vinylnaphthalene, and and conjugated dienes include butadiene, isoprene, 1,3-pentadiene or 3-dimethylbutadiene, and mixtures thereof.

The terminal blocks of these block copolymers may be the same or different.

The number average molecular weight of these block copolymers is 10.00
0~goo, ooo, preferably 20.000~SOθ
,000.

Further, the content of styrene hydrocarbon in the block copolymer is preferably 70 to 70% by weight, more preferably 15% by weight.
- SS weight %.

The styrenic hydrocarbon polymer block-olefin elastomer block copolymer used in the present invention can be obtained by selectively hydrogenating the conjugated diene moiety of the styrenic hydrocarbon polymer block-conjugated diene diistomer block copolymer. This is obtained by The unsaturated bond content in the hydrogenated copolymer is 20% of the original value.
The amount reduced to below is used. The preferable unsaturated bond content for differential use is 70% or less of the original content,
More preferably, it is 5% or less.

Regarding the blending ratio of polyphenylene ether, aromatic polyamide, and polycarbonate, if polyphenylene ether exceeds 90% by weight, moldability and solvent resistance will deteriorate, and if it is less than 20% by weight, thermal properties will deteriorate.

If the amount of aromatic polyamide exceeds 60% by weight, the compatibility between the resins will be poor, resulting in a decrease in mechanical properties and thermal properties, and if it is less than 3% by weight, the solvent resistance will be poor.
If it exceeds 0% by weight, solvent resistance will deteriorate, and if it is less than 5% by weight, the compatibility between the resins will deteriorate and the mechanical properties will deteriorate significantly.

Therefore, polyphenylene ether is 20~? O wt%, preferably 30 to go wt%, aromatic polyamide 5 to 60 wt%, preferably 10 to 50 wt%, aromatic polycarbonate S to 0 wt%, preferably 70 to go
The blending ratio is 60% by weight.

When blending a styrene polymer, if it exceeds 0 parts by weight, the thermal properties will deteriorate, and if it is less than 0.3 parts by weight, based on the weight of the blend of polyphenylene ether, aromatic polyamide, and aromatic polycarbonate. , the effect of improving impact resistance is low.

Therefore, the styrenic polymer is 0.3 to go parts by weight,
It is desirable to blend 2 to 50 parts by weight.

In this way, by selecting the above blending ratio, a resin composition surprisingly excellent in mechanical properties, thermal properties, solvent resistance, and moldability can be obtained, and moreover, it shows good compatibility. In addition, a molded product with excellent appearance can be obtained without any layer separation.

The blending of polyphenylene ether, aromatic polyamide, and polycarbonate is carried out by the melt mixing method well known to those skilled in the art, and there are no particular restrictions on the mixing temperature or time, but a temperature of 130 to 350°C is generally recommended, and specific Examples include extruders, Banbury mixers, rolls, and nitanas.

Furthermore, although the compounding order of polyphenylene ether, aromatic polyamide, and polycarbonate is arbitrary, commercially it is desirable to compound the three resins simultaneously and melt-knead them.

In addition to the above-mentioned formulations, the composition of the present invention may contain various well-known additives, such as glass fibers, carbon fibers, reinforcing agents such as metal whiskers, silica, alumina, silica-alumina clay minerals, and silica-magnesium clay minerals. It may contain fillers such as minerals, calcium silicate, calcium carbonate, asbestos, and carbon black, as well as other lubricants, nucleating agents, antioxidants, flame retardants, antistatic agents, weathering agents, and the like.

It is also possible to blend other resins within a range that does not impair the properties of the composition of the present invention.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Core 6-dimethyl/1I-phenylene ether (B) obtained by dissolving it in ethanol, adding manganese chloride-ethylenediamine, and oxidizing it in an oxygen atmosphere Hexamethylenediamine aqueous solution (0 wt%)/ , 7.9kliF, isophthalic acid q, gkg, and terephthalic acid I 1.9 tcg were added, stirred and dissolved uniformly, and then acetic acid 33! After adding i, place it in an autoclave. While maintaining the internal pressure at λj kg/cm'', water was distilled out until the concentration of nylon salt reached ?0% by weight, and then the pressure was increased to /Jkg/crr?, water was further distilled out, and the internal temperature was raised to 230°C. Once this was reached, the internal pressure was slowly released, and finally the polymerization was carried out under a reduced pressure of ?00 Torr for 7 hours, and then extruded into chips.

Aromatic polyamide (C) with relative viscosity ηrela, λ and glass transition point Tg / 27°C obtained in this way Bisphenol A type polycarbonate with molecular weight 2900θ (manufactured by Mitsubishi Kasei ■, trade name Nipperex 70JOA) (D ) Hydrogenated styrene-butadiene block copolymer (manufactured by SHELL, trade name: Kraton QI&!;
0) The above resins (A), (B), (C) and (D) were adjusted to the composition ratios shown in Table 1 [23θ to 300% in an extruder]
The resin composition obtained by melt-kneading within the range of 12 °C
After drying at a temperature of 0° C. for 6 hours, injection molding was performed under the conditions shown in Table 7.

Example D The resins (A), (B), and (C) were blended in the composition shown in Table 1, and the same operations as in Examples 1 to 3 were carried out to obtain the resulting composition as shown in Table 7. Injection molding was performed under these conditions.

Comparative example! Using nylon 6 (relative viscosity: 5), which is an aliphatic polyamide, instead of the aromatic polyamide, and with the composition of Rin-7, the same operations as in Examples 1 to 3 were carried out under the conditions shown in Table 1. Injection molding was performed.

The injection molded article of the resin composition thus obtained was evaluated for tensile strength, elongation, Izod impact strength, chemical resistance and μ heat resistance, and the results are shown in Table C.

The measurement conditions are as follows. (1) Tensile strength, elongation According to ASTM D-AJg.

(2) Iz o d impact value using a 77 g inch thick test piece, ASTM [)-2!
Measurements were carried out at temperatures of 23°C and -30°C according to 1.

(3) Chemical resistance A 1% bending strain was applied to a type 7 dumbbell test piece described in ASTM D-Aj, and the specimen was immersed in gasoline at 23°C.
After standing for a period of time, the bending strain was released, and after wiping off the gasoline, the tensile strength and elongation were measured according to ASTM D-4, 7ff.

(4) Heat resistance ASTM D-7? , 2, the heat distortion temperature (H
DT) was measured. The applied stress is /ξ69/cIrL2
It is.

As is clear from the results in Table 71 and Table A, a ternary resin composition of polyphenylene ether, aromatic polyamide, aromatic polycarbonate, and a resin containing a styrenic polymer, typified by rubber-modified styrenic resin. The composition has excellent moldability, mechanical properties, chemical resistance, and heat resistance.

〔Effect of the invention〕

As described above, the composition of the present invention does not undergo phase separation even when manufactured by conventional methods, has excellent molded product appearance and mechanical properties, and has excellent chemical resistance and heat resistance, so it has commercial value. It has a high value.

Claims (2)

[Claims] (1) (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1, R^2, R^3, R^4 and R^5
is a hydrogen atom, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and at least one of them is always a hydrogen atom. 20 to 90% by weight of a polyphenylene ether resin obtained by oxidative polymerization of one or more phenolic compounds represented by (B) 5 to 60% by weight of aromatic polyamide and (C) 5 to 70% by weight of aromatic polycarbonate. A resin composition consisting of %. (2) A resin composition obtained by further blending 0.5 to 80 parts by weight of a styrene polymer to 100 parts by weight of the resin composition according to claim 1.