JPH06313102A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in flowability during molding, dimensional stability, mechanical properties, especially toughness, and resistance to thermal deterioration. CONSTITUTION:The title composition comprises 3-97wt.% polyamide containing units represented by formula I (wherein R is a 4-18C aliphatic group or the group represented by formula II) as an essential component and having a relative viscosity of 1.2-5.0 and 97-3wt.% aromatic polycarbonate having an average mol.wt. of 15,000-80,000.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention, in addition to excellent fluidity,
The present invention relates to a resin composition having a mechanical property, particularly excellent toughness and a small deterioration in physical properties upon absorbing water.

[0002]

2. Description of the Related Art Polyamides containing aromatics are excellent in heat resistance such as high melting point, in addition to having a feature that they have smaller water absorption than polyamides not containing aromatics. However, compared with nylon 6 and nylon 66, which are typical aromatic-free nylons, there is a problem that the toughness, particularly the impact resistance at low temperatures, is low.

As a means for improving the low toughness of aromatic polyamides, there have been proposed general elastomers and methods of mixing or copolymerizing aromatic polyamides with polyamide elastomers (Japanese Patent Laid-Open No. 2-67362). (Kaihei 2-6555, Japanese Patent Laid-Open No. 1-98665, Japanese Patent Laid-Open No. 63-179960).

[0004]

However, although the toughness, especially the impact resistance at low temperature is improved by the above-mentioned method, the mechanical properties, heat resistance, and molding There is a new problem that the liquidity is reduced.

Therefore, the present inventors obtain a resin composition that is tough even at low temperatures without losing the inherent characteristics of aromatic polyamide such as fluidity, mechanical properties (especially excellent mechanical properties when absorbing water), and heat resistance. As a result of intensive studies, they have found that the above object can be achieved by containing a specific amount of an aromatic polycarbonate and a polyamide containing an aromatic, and have reached the present invention.

[0006]

That is, the present invention is as follows.
(A) Polyamide 3-97% by weight containing the following component (I) as an essential component and having a relative viscosity of 1.2-5.0.
And (B) 97-3% by weight of an aromatic polycarbonate having an average molecular weight of 15,000-80,000, and a resin composition.

[0007]

[Chemical 5] (In the formula, R is an aliphatic group having 4 to 18 carbon atoms or

[Chemical 6] Represents a polyamide resin used in the present invention,
(I) An essential component is a terephthalamide unit synthesized from an aliphatic alkylenediamine having 4 to 18 carbon atoms or metaxylylenediamine and terephthalic acid.

The polyamide resin used in the present invention may be composed only of the above-mentioned component (I) or may be a copolymer with another copolymerizable polyamide-forming component.

Other polyamide-forming components preferably used in the present invention include the above-mentioned (II) or (III)
Is mentioned.

The component (II) is an aliphatic alkylenediamine or metaxylylenediamine having 4 to 18 carbon atoms and an isophthalamide unit synthesized from isophthalic acid, or an aliphatic alkylenediamine having 4 to 18 carbon atoms or meta. It is a condensate composed of xylylenediamine and an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, and the component (III) is a lactam having 6 to 19 carbon atoms or an aliphatic aminocarboxylic acid having 6 to 19 carbon atoms. It is a component unit.

Specific examples of the aliphatic alkylenediamine having 4 to 18 carbon atoms include 1,4-diaminobutane and 1,5.
-Diaminopentane, 1,6-diaminohexane, 1,
7-diaminoheptane, 1,8-diaminooctane,
1,9-diaminononane, 1,10-diaminodecane,
1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane , 1,18-diaminooctadecane and the like.

Specific examples of the aliphatic dicarboxylic acid having 2 to 20 carbon atoms include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and undecanedioic acid. Dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid,
Octadecanedioic acid etc.

Specific examples of lactams having 6 to 19 carbon atoms include ε-caprolactam, ζ-enanthlactam and η.
-Capryl lactam, ω-laurolactam and the like.

Specific examples of the aliphatic aminocarboxylic acid having 6 to 19 carbon atoms include 6-aminocaproic acid and 11
-Aminoundecanoic acid, 12-aminododecanoic acid and the like. The aromatic polyamide resin of the present invention has (I) as an essential component. The structure is not necessarily limited as long as it is a polyamide having a terephthalamide unit of (I), but it is (I) / (II), a copolyamide of (I) / (III), or (I) / ( Preferred examples include copolymerized polyamides such as II) / (III). Specifically, hexamethylene adipamide / hexamethylene terephthalamide copolymer (66 / 6T, where T represents a terephthalic acid unit), hexamethylene terephthalamide / hexamethylene isophthalamide copolymer (6T
/ 6I, where I represents an isophthalic acid unit), caproamide / hexamethylene terephthalamide copolymer (6 / 6T), hexamethylene adipamide / octamethylene terephthalamide copolymer (66 / 8T), hexamethylene Adipamide / hexamethylene terephthalamide / hexamethylene isophthalamide copolymer (66/6
T / 6I), caproamide / hexamethylene terephthalamide / hexamethylene isophthalamide copolymer (6
/ 6T / 6I), dodecamethylene terephthalamide (1
2T), metaxylylene adipamide / hexamethylene terephthalamide copolymer (MXD6 / 6T, where MX
D represents a metaxylylenediamine unit) and the like.

The aromatic polyamide of the present invention is 160
It is preferable to have a melting point between -360 ° C, preferably 225-340 ° C, and more preferably 260-330 ° C.

The degree of polymerization of the polyamide resin of the present invention depends on the relative viscosity (1 g of polymer is dissolved in 100 ml of 98% concentrated sulfuric acid,
Measured at 25 ° C. The same shall apply hereinafter) is used in the range of 1.2 to 5.0. If the relative viscosity is less than 1.2, sufficient mechanical properties cannot be obtained, and if it exceeds 5.0, the viscosity is high and molding is difficult, which is not preferable.

The aromatic polycarbonate used in the present invention is obtained by producing a divalent phenol or its derivative as a raw material by a transesterification method or a phosgene method.

The dihydric phenol is represented by the following general formula.

[0019]

[Chemical 7] In the above formula, Ar represents an aromatic group such as a phenylene nucleus, a biphenylene nucleus and a naphthylene nucleus, and Z is an alkyl group such as methyl and ethyl, a halogenated alkyl group, an aryl group such as phenyl and naphthyl, a halogenated aryl group, benzyl, An aralkyl group such as phenylethyl, a halogenated aralkyl group, an alicyclic group, a halogen atom, Y represents an alkylene group such as methylene or ethylene, an alkylidene group such as ethylidene or isopropylidene, a tertiary amino group, O,
Examples include S, SO, SO2, CO, and amide groups. m and n are each an integer of 0-4. p is an integer of at least 1, q is 0 or 1, r is 0 or a positive integer,
When q is 0, r is also 0. Specific examples of the divalent phenol include bis (4-hydroxyphenyl) -methane, 1,1-bis (4-hydroxyphenyl) -ethane, 1,2-bis (4-hydroxyphenyl) -ethane, 2, 2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -propane, 2,2-bis (4-hydroxy-3-chlorophenyl) -propane, 2,2-bis (4- Hydroxy-3,
5-dichlorophenyl) -propane, 2,2-bis (4
-Hydroxy-3-bromophenyl) -propane, 2,
2-bis (4-hydroxy-3,5-dibromophenyl) -propane, 2,2-bis (4-hydroxy-3-)
Methylphenyl) -propane, 2,2-bis (4-hydroxy-3-methoxyphenyl) -propane, 1,4-
Bis (4-hydroxyphenyl) -cyclohexane,
1,1-bis (4-hydroxyphenyl) -cyclohexane, 1,2-bis (4-hydroxydiphenyl) -ethylene, 1,4-bis (4-hydroxyphenyl) -benzene, bis (4-hydroxydiphenyl)- Phenylmethane, bis (4-hydroxydiphenyl) -diphenylmethane, 1,1-bis (4-hydroxydiphenyl)
-2,2,2-trichloroethane, bis (4-hydroxyphenyl) -ketone, bis (4-hydroxyphenyl) -sulfide, bis (4-hydroxyphenyl)
-Sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, phenolphthalein, etc. Yes,
2,2-bis (4-hydroxyphenyl) -propane (commonly called bisphenol A) can be preferably used. You may use together 2 or more types of dihydric phenols. If it is a small amount, an alicyclic diol such as 1,4-cyclohexanediol, an aliphatic diol such as 1,6-hexanediol, an aromatic group-containing aliphatic diol such as p-xylene glycol, and the like are used as a divalent phenol. You may use together.

The aromatic polycarbonate used in the present invention has a viscosity average molecular weight in the range of 15,000 to 80,000, more preferably 18,000 to 40,000. If the average molecular weight is less than 15,000, sufficient mechanical properties cannot be obtained, and if it exceeds 80,000, the moldability becomes poor, which is not preferable.

The viscosity average molecular weight as referred to herein is obtained by converting the intrinsic viscosity obtained by measuring the methylene chloride solution at 20 ° C. using an Ostwald viscometer using the following Schnell's equation.

[Η] = 1.23 × 10 ⁻⁴ M ^0.83 (where [η] represents the intrinsic viscosity and M represents the viscosity average molecular weight) The resin composition of the present invention has improved mechanical properties. For this purpose, a compatibilizer may be added. Specific examples of the compatibilizer include epoxy compounds of bisphenol represented by glycidyl ether of bisphenol A, acid anhydrides such as benzenetetracarboxylic acid anhydride and dodecenylsuccinic anhydride, ethylene / methylmethacrylate-graft-maleic anhydride. , Ethylene / propylene-graft-maleic anhydride, styrene-ethylene-butadiene-styrene-block copolymer-graft-maleic anhydride, styrene-butadiene-styrene-block copolymer-graft-maleic anhydride, styrene-maleic anhydride Acid anhydride-containing copolymers typified by acid copolymers, ethylene / methyl methacrylate-graft-glycidyl methacrylate, ethylene / propylene-graft-glycidyl methacrylate, styrene-ethylene-
Butadiene-styrene-block copolymer-graft-
Glycidyl methacrylate, styrene-butadiene-styrene-block copolymer-graft-glycidyl methacrylate, ethylene-glycidyl methacrylate copolymer, glycidyl group-containing copolymer represented by methyl methacrylate-glycidyl methacrylate copolymer, phenoxy resin, Examples thereof include ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and oligomers thereof.

The amount of the compatibilizing agent is preferably 0 to 50 parts by weight with respect to 100 parts by weight of the resin composition comprising polyamide and aromatic polycarbonate.

The resin composition of the present invention is preferably melt-kneaded, and a known method can be used for melt-kneading. For example, using a Banbury mixer, rubber rolls, kneader, single-screw or twin-screw extruder, etc.
The composition can be obtained by melt-kneading at a temperature of 370 ° C.

The polyamide content in the resin composition of the present invention is 3 to 97% by weight, preferably 5 to 90% by weight, more preferably 10 to 80% by weight, still more preferably 20 to 50% by weight. If the polyamide content is less than 3% by weight, sufficient mechanical properties cannot be obtained, and if it exceeds 97% by weight, the toughness is low, which is not preferable.

In the present invention, various fillers can be added. The amount of the filler is 0 to 200 parts by weight, preferably 5 to 200 parts by weight, more preferably 15 to 150 parts by weight with respect to 100 parts by weight of the resin component, and preferably glass fiber, potassium titanate fiber, Gypsum fiber, brass fiber, stainless fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, talc, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, wollastonite, titanium oxide and other fibers Shape, powder, granular, or
Plate-shaped inorganic filler and other polymer fibers (carbon fiber, aramid fiber) and the like can be used. Among the above fillers, glass fiber is preferably used. The glass fiber can be selected from long fiber type, short fiber type chopped strand, milled fiber, etc., and the average fiber diameter of the glass fiber is 3 in terms of surface appearance of the molded product, improvement of moldability, etc. Above 15 μm, especially 5
It is preferably not less than 13 μm.

The length of the glass fiber is 30 or more and 10 ⁴
It is preferably less than μm, particularly preferably 1,000 or more and less than 4,000 μm.

The glass fiber may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or a coupling agent such as silane or titanate. , And may be treated with other surface treatment agents.

The composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol type, hydroquinone type, phosphite type and substitution products thereof, iodine, etc.) to the extent that the object of the present invention is not impaired. Copper oxide, potassium iodide, etc., UV absorbers (eg resorcinol-based, salicylate-based, benzotriazole-based, benzophenone-based, hindered amine-based, etc.), lubricants and mold release agents (montanic acid and its salts, its esters, its half esters) , Stearyl alcohol, stearamide and polyethylene wax), dyes (eg nigrosine etc.) and pigments (eg cadmium sulfide, phthalocyanine, carbon black etc.), colorants including plasticizers, antistatic agents etc. To give the specified characteristics. Can.

The thermoplastic resin composition of the present invention is used in switches, micro slide switches, DIP switches, switch housings, lamp sockets, binding bands, connectors, connector housings, connector shells, IC sockets, coil bobbins, Bobbin cover, relay, relay box, condenser case, motor internal parts, small motor case, gear cam, dancing pulley, spacer, insulator, fastener, buckle, wire clip, bicycle wheel, caster, helmet, terminal block, electric Tool housing, starter insulation, spoiler, canister, radiator tank, chamber tank, reservoir tank,
Fuse box, air cleaner case, air conditioner fan, terminal housing, wheel cover, intake / exhaust pipe, bearing retainer, cylinder head cover, intake manifold, water pipe impeller, clutch release, bearing hub, speaker diaphragm, heat resistant container, microwave oven parts , Rice cooker parts, electrical / electronic related parts such as printer ribbon guides, automobile / vehicle related parts, household / office electrical product parts,
It is useful for computer related parts, facsimile / copier related parts, machine related parts, and other various applications.

[0031]

The effects of the present invention will be described in more detail with reference to the following examples.

Examples 1 to 8 and Comparative Examples 1 to 6 For polyamides of various relative viscosities (ηr) shown in Table 2, bisphenol A type polycarbonates of various viscosity average molecular weights shown in Table 3 are shown in Table 1. Dry blending was carried out in the proportions shown in Table 1, and the mixture was melt-mixed and pelletized by a screw extruder. The melt viscosity of the pellets was measured by using a melt indexer at 340 ° C. at a shear rate of 10 sec ⁻¹ . The resulting pellets are then molded using a 5 ounce screw in-line injection molding machine and AST
M number 1 dumbbells and 1/4 inch wide Izod impact test specimens were made. At this time, the required minimum pressure (forming lower limit pressure: gauge pressure) was determined. For these test pieces,
Notched Izod impact test according to ASTM D-256, bending test according to ASTM D-790, ASTM
A tensile test was conducted according to D-638.

[0033]

[Table 1]

[Table 2] In the table, 66 represents a condensate of hexamethylenediamine and adipic acid, and 6T represents a condensate of hexamethylenediamine and terephthalic acid.

[0034]

[Table 3] As is clear from the results shown in Table 1, the resin composition of the present invention has not only a dramatic improvement in toughness as compared with the polyamide alone, but also a resin composition having a well-balanced molding fluidity and impact resistance. You can see that you can get it.

On the other hand, in Comparative Example 1 in which the ηr of the polyamide was out of the scope of the claims of the present invention, the amount of foaming in the molding machine was large and molding was impossible. Similarly, Comparative Example 2
Had a tensile elongation of 19% and extremely low toughness. Comparative Example 3 in which the molecular weight of the polycarbonate was out of the claimed range was also low in toughness. Comparative Example 4
Had a high melt viscosity and could not be molded. Polyamide / polycarbonate composition ratios are 1/99 and 9 respectively
In Comparative Examples 5 and 6 which are 9/1, no synergistic effect due to blending was obtained.

Examples 9 to 12 and Comparative Example 7 For polyamides having a relative viscosity of 2.54 shown in Table 5,
The bisphenol A type polycarbonate having a viscosity average molecular weight of 26,000 shown in Table 1 was dry blended at a ratio shown in Table 4, melt-mixed and injection-molded in the same manner as in Example 1, and air-balanced according to ASTM D-638. A tensile strength and tensile elongation test when absorbing water were performed. The results are shown in Table 4.

[0037]

[Table 4]

[Table 5] As is clear from the results in Table 4, the resin composition of the present invention containing an aromatic component in the polyamide gave good test results even at the time of atmospheric equilibrium water absorption.

On the other hand, the same test as in Examples 9 to 12 was carried out using N-66 in Comparative Example 7, but the tensile strength at the time of water absorption at atmospheric equilibrium was lower than that in Examples 9 to 12. It turns out to be big.

Examples 13 to 21 and Comparative Example 8 For the polyamides having the compositions shown in Table 7, polycarbonates having a viscosity average molecular weight of 26,000 shown in Table 1 were used.
After dry blending in the ratio shown in Table 1, melt mixing and injection molding were carried out in the same manner as in Example 1, and ASTM D-638 was performed.
According to the above, tensile strength and tensile elongation tests at atmospheric equilibrium water absorption were performed. The results are shown in Table 6.

[0040]

[Table 6]

[Table 7] 66 in the table represents a condensate of hexamethylenediamine and adipic acid. Similarly, 6T is a condensate of hexamethylenediamine and terephthalic acid, 6I is a condensate of hexamethylenediamine and isophthalic acid, 8T is a condensate of 1,8-diaminooctane and terephthalic acid, and MXD6 is metaxylylenediene. Condensation product of amine and adipic acid
T represents a condensate of 1,12-diaminododecane and terephthalic acid.

As is clear from the results shown in Table 6, the resin composition of the present invention having a hexamethylene terephthalamide component has good tensile strength and tensile elongation even at the time of atmospheric equilibrium water absorption.

[0042]

Since the resin composition obtained by the present invention is excellent in fluidity during molding, dimensional stability, mechanical properties, toughness and heat deterioration resistance, thin-walled molding materials such as connectors and coil bobbins, Suitable for materials such as automobile underhood.

Claims (4)

[Claims] 1. A polyamide 3-9 having (A) the following component (I) as an essential component and having a relative viscosity of 1.2-5.0.
7% by weight, and (B) average molecular weight 15,000-80,0
00-3 aromatic polycarbonate 97-3% by weight. [Chemical 1] (In the formula, R is an aliphatic group having 4 to 18 carbon atoms or Represents) 2. The resin composition according to claim 1, wherein the polyamide has a melting point between 160 and 360 ° C. 3. The resin composition according to claim 1, wherein the polyamide is a polyamide comprising (I) according to claim 1 and (II) and / or (III) below. [Chemical 3] (In the formula, R ′ represents a direct bond, an aliphatic group having 1 to 18 carbon atoms, or a metaphenylene group.) (In the formula, n represents an integer of 5-18) 4. The resin composition according to claim 3, wherein the polyamide has a melting point between 160 and 360 ° C.