JP3009724B2 - Thermoplastic resin composition for connectors - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition particularly suitable for producing connectors. More specifically, the present invention provides
An object of the present invention is to provide a thermoplastic resin composition which is particularly suitable for preparing a connector in which toughness is hardly reduced by heating.

Technical Background of the Invention Connectors used as connection terminals for electric circuits have conventionally been manufactured from thermosetting resins such as phenolic resins, but recently, instead of thermosetting resins, molding processes have been used. Easy thermoplastic resins are being used. Aliphatic polyamides such as polycapramid (nylon 6) and polyhexamethylene adipamide (nylon 66) are used as such thermoplastic resins.

However, since such an aliphatic polyamide has a high absorptivity, a connector formed of such an aliphatic polyamide varies in size, electric resistance value, and the like due to absorption of water. In particular, when the connector is warped, there is a problem that the connector cannot be incorporated into the device.

By the way, as the above polyamide, an aromatic polyamide is known in addition to the above aliphatic polyamide. The aromatic polyamide is a polyamide obtained by using an aromatic dicarboxylic acid as a dicarboxylic acid component and polycondensing the aromatic dicarboxylic acid with a diamine. Since such an aromatic polyamide has a low water absorption unlike an aliphatic polyamide, the use of this aromatic polyamide causes a decrease in dimensional accuracy and a variation in electric resistance due to water absorption in the connector as described above. Problem is solved.

However, when examining the connector formed from the aromatic polyamide in more detail, when the connector is exposed to a high temperature, the aromatic polyamide may be thermally degraded. It was found that the toughness was reduced. Such a connector having reduced toughness has a problem that it is difficult to smoothly incorporate it into a device because of its low elasticity.

Especially recently, electronic parts such as connectors are often soldered by infrared reflow method etc. and incorporated into the device, and if the toughness of the connector decreases due to heating in cases such as those used in the engine room of automobiles In addition, the workability and the durability in the assembly process of the device are reduced.

On the other hand, various improvements have already been attempted for aromatic polyamides. Examples of such improvements include the compositions described in, for example, JP-A-60-144362. This is related to the application of the present applicant, and specifically, is a composition containing an aromatic polyamide and a specific modified α-olefin-based elastic polymer.

However, in the polyamide composition disclosed herein, heat resistance has been studied assuming an engineering plastic product manufactured by a general melt molding method, and the polyamide composition was exposed to a very high temperature like a connector. The characteristics of the case are not taken into account.

Object of the Invention The present invention aims to solve the above-mentioned problems in the prior art and to provide a thermoplastic resin composition particularly suitable for preparing a connector.

SUMMARY OF THE INVENTION The thermoplastic resin composition for a connector of the present invention comprises 20 to 100 mol% of a terephthalic acid component unit, 0 to 80 mol% of an aromatic dicarboxylic acid component unit other than terephthalic acid, and / or 4 to 20 carbon atoms. And a repeating unit consisting of a dicarboxylic acid component unit comprising 0 to 80 mol% of an aliphatic dicarboxylic acid component unit and a diamine component unit comprising an aliphatic diamine component unit and / or an alicyclic diamine component unit, and An aromatic polyamide having an intrinsic viscosity in the range of 0.5 to 3.0 dl / g measured in concentrated sulfuric acid at 30 ° C. and having a melting point of 280 ° C. or more; and at least two kinds derived from different α-olefins. 98: 2 to 60:40 substantially amorphous graft modified α-olefin random copolymer having repeating units
Characterized by the following weight ratio.

The thermoplastic resin composition for a connector of the present invention is a composition containing an aromatic polyamide and a specific graft-modified α-olefin random copolymer in a specific ratio. By blending the two in this way, the toughness of the connector hardly decreases even when exposed to a temperature of, for example, 150 ° C. or more for a long time.

Next, the thermoplastic resin composition for a connector of the present invention will be specifically described.

The thermoplastic resin composition for a connector according to the present invention comprises a specific polyamide and a specific graft-modified α-olefin random copolymer as shown below.

The polyamide constituting the composition of the present invention is composed of a repeating unit composed of a specific dicarboxylic acid component unit [A] and a specific aliphatic diamine component unit [B].

The specific dicarboxylic acid component unit [A] constituting the polyamide has a terephthalic acid component unit (a) as an essential component. Such a repeating unit having the terephthalic acid component unit (a) can be represented by the following formula [II-a].

However, in the above formula [II-a], R ¹ represents an alkylene group having 4 to 25 carbon atoms.

The specific dicarboxylic acid component unit [A] does not need to be all the component unit represented by the above-mentioned [II-a]. Instead of the above terephthalic acid component unit (a), another dicarboxylic acid component unit [A] is used. It may have a component unit.

Other carboxylic acid component units other than the terephthalic acid component include an aromatic dicarboxylic acid component unit (b) other than terephthalic acid and an aliphatic dicarboxylic acid component unit (c).

Examples of the aromatic dicarboxylic acid component unit (b) other than terephthalic acid include an isophthalic acid component unit, a 2-methylterephthalic acid component unit, and a naphthalenedicarboxylic acid component unit. When the polyamide used in the present invention contains an aromatic dicarboxylic acid component unit other than terephthalic acid, such a component unit is particularly preferably an isophthalic acid component unit.

Among such aromatic dicarboxylic acid component units (b) other than terephthalic acid, a repeating unit having an isophthalic acid component unit particularly preferred in the present invention is represented by the following formula [II-
b].

However, in the above formula [II-b], R ¹ represents an alkylene group having 4 to 25 carbon atoms.

Further, the aliphatic dicarboxylic acid component unit is usually derived from an aliphatic dicarboxylic acid having an alkylene group having 4 to 20, preferably 6 to 12 carbon atoms. Examples of the aliphatic dicarboxylic acids used to derive such aliphatic dicarboxylic acid component units (c) include succinic acid, adipic acid, azelaic acid and sebacic acid.

When the polyamide has an aliphatic dicarboxylic acid component unit, such a component unit is particularly preferably an adipic acid component unit.

As another dicarboxylic acid component unit constituting the dicarboxylic acid component unit [A], a repeating unit having a repeating unit containing an aliphatic dicarboxylic acid component unit (c) can be represented by the following formula [III].

However, in the above formula [III], R ¹ has the same meaning as described above, and n represents an integer of 4 to 20, preferably 6 to 12.

A dicarboxylic acid component unit [A] as described above,
The repeating unit constituting the polyamide is formed from the diamine component unit [B].

Here, the diamine component unit [B] has 6 to 18 carbon atoms.
From aliphatic alkylenediamines.

Specific examples of such an aliphatic alkylenediamine component include 1,4-diaminobutane, 1,6-diaminohexane, trimethyl-1,6-diaminohexane, 1,7-diaminoheptane, and 1,8-diaminooctane. , 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane.

In particular, in the present invention, as the diamine component unit, a component unit derived from a linear aliphatic alkylenediamine is preferable, and as such a linear aliphatic alkylenediamine, 1,6-diaminohexane, 1,8-diaminooctane , 1,10-diaminodecane, 1,12-diaminododecane, and mixtures thereof are preferred. Furthermore, among these,
1,6-Diaminohexane is particularly preferred.

Terephthalic acid component unit (a) in all dicarboxylic acid components (100 mol%) of the polyamide used in the present invention
Is 20 to 100 mol%, the content of the aromatic dicarboxylic acid component unit (b) other than terephthalic acid is 0 to 80 mol%, and the content of the aliphatic dicarboxylic acid component unit (c) is The percentage is from 0 to 80 mol%.

Furthermore, in the present invention, the aliphatic diamine component unit constituting the polyamide is a linear aliphatic alkylenediamine component unit having 4 to 20 carbon atoms, particularly 5 to 7 carbon atoms, such as an alkylenediamine component unit. When the alkyl chain is short, the amount of the repeating unit containing the terephthalic acid component unit is 40 to 85% by mole, and the amount of the repeating unit containing the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit is 15 to 40% by mole. Or the repeating unit containing an aliphatic dicarboxylic acid component unit in an amount of 15 to 55 mol%, and further comprising a repeating unit containing an aromatic dicarboxylic acid component unit other than a terephthalic acid component unit and an aliphatic dicarboxylic acid component unit. It is preferred that the total of the repeating units is contained in an amount of 15 to 55 mol%.

Further, the alkyl chain has an intermediate length as in the case where the aliphatic diamine component unit constituting the polyamide is a straight-chain aliphatic alkylenediamine component unit having 6 to 11 carbon atoms, particularly 6 to 10 carbon atoms. When it has, the aromatic dicarboxylic acid component unit has a repeating unit containing a terephthalic acid component unit in an amount of 65 to 100 mol%, and the repeating unit containing an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit has 35 It is preferable that a repeating unit containing an aliphatic dicarboxylic acid component unit is contained in an amount of 0 to 35 mol% in an amount of not more than mol%.

Furthermore, when the aliphatic diamine component unit constituting the polyamide has a relatively long alkyl chain such as a linear aliphatic alkylenediamine component unit having 10 to 18 carbon atoms, a terephthalic acid component unit is used. A repeating unit having an amount of 75 to 100 mol%, an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit of 25 mol% or less, and a repeating unit containing an aliphatic dicarboxylic acid component unit of 0 to 25 mol%. It is preferably contained in an amount of mol%.

By balancing the diamine component unit and the dicarboxylic acid component unit as described above, the heat resistance of the molded body is improved.

In the above polyamide, the aromatic dicarboxylic acid component unit is derived from a divalent aromatic carboxylic acid other than terephthalic acid represented by the terephthalic acid component unit as the main component unit and the isophthalic acid component unit. A repeating unit having a tribasic or higher polybasic carboxylic acid component unit such as a small amount of trimellitic acid or pyromellitic acid, in addition to the repeating unit having an aliphatic dicarboxylic acid component unit and the above-described aliphatic dicarboxylic acid component unit. May be. The content of the repeating unit containing the component unit derived from such a polycarboxylic acid in the polyamide used in the present invention is usually 0 to 5 mol%.

For such polyamides, the intrinsic viscosity [η] measured at a temperature of 30 ° C. in concentrated sulfuric acid is usually 0.5 to 3.0 dl / g,
Preferably 0.5 to 2.8 dl / g, particularly preferably 0.6 to 2.5 dl / g
In the range.

Further, the polyamide used in the present invention has the above-mentioned formula [II
-A], a polyamide containing a repeating unit represented by the formula [II-b] as a main repeating unit, and a polyamide containing a repeating unit represented by the formula [II-b] as a main repeating unit;
And a polyamide having a repeating unit represented by the following formula as a main repeating unit. When the polyamide used in the present invention is a mixture, among these mixtures, a polyamide having the repeating unit represented by the formula [II-a] as a main repeating unit and a polyamide having the formula [II-b] as a main repeating unit are used. Polyamide having a large repeating unit and / or
Alternatively, the composition is preferably a composition comprising a polyamide having [III] as a main repeating unit. In this case, the formula [II
-A] is usually 50% by weight or more, preferably 60% by weight or more, having a repeating unit represented by -a] as a main repeating unit. Further, in this case, the formula [II-
b] The compounding ratio of the mixture of the polyamide having the repeating unit represented by the main repeating unit and the polyamide having the repeating unit represented by the formula [III] as the main repeating unit is usually 50: 50 to 100: 0, preferably 60:40
~ 95: 5.

The polyamide used in the present invention has a higher melting point than the aliphatic polyamide conventionally used. That is, the melting point of the polyamide used in the present invention is usually 280 ° C.
As described above, the temperature is preferably 290 to 340 ° C. Furthermore, the glass transition temperature in the amorphous part of the polyamide used in the present invention is usually 110 ° C. or higher.

By using a polyamide having a melting point and a glass transition temperature of an amorphous part in the above-mentioned range, even when the connector is exposed to a high temperature, the resin does not enter a molten state. Further, since the above polyamide has excellent moldability, the use of this polyamide facilitates the production of a molded article. Further, since the polyamide has a glass transition temperature of 110 ° C. or higher in an amorphous portion, cracks and the like hardly occur even when exposed to a high temperature.

Since this polyamide has a specific structure, it shows a low value with respect to the water absorption which has been a problem of the conventional aliphatic polyamide.

As described above, it has been found that the above polyamide has good heat resistance, but once heated to a high temperature and cooled, its toughness tends to decrease. Such a decrease in toughness appears as a decrease in elongation in the connector. And, in the connector with the reduced elongation,
When connecting the connector, there arises a problem that the positions of the connection pins do not match, and the connector itself becomes difficult to fit.

In the resin composition of the present invention, a specific graft-modified α-olefin random elastic copolymer is blended with the above polyamide.

The graft-modified α-olefin random elastic copolymer constituting the composition of the present invention is a graft-modified product of a copolymer in which two types of repeating units derived from different α-olefins are randomly arranged, and More specifically, a graft-modified ethylene / α-olefin copolymer rubber prepared using ethylene as a base monomer (a), and a graft-modified propylene / α-olefin copolymer rubber prepared using propylene as a base monomer (b)
Can be exemplified.

The graft-modified α-olefin random elastic copolymer has a low density (generally, d = 0.935 g / cm ³ or less) or is amorphous, and has a crystallinity of 4% as measured by an X-ray diffraction method. Or less, preferably 3% or less, particularly preferably 0%. Therefore, this graft-modified α-
Many of the olefin random elastic copolymers do not show a clear melting point and have a low density, so this graft-modified α-olefin random elastic copolymer is soft,
The tensile modulus of this elastic copolymer is usually 0.1 kg /
cm ² ~20000kg / cm ^2, preferably in the range of ^{1kg / cm 2 ~15000kg / cm 2} .

The melt index (measured at 190 ° C.) of the graft-modified α-olefin random elastic copolymer is usually 0.1 to 30 g / 10 min, preferably 1.0 to 20 g / 10 min, particularly preferably 2.0 to 15 g / 10 min. Within minutes. Further, the value of Mw / Mn measured by GPC is usually 5.5 or less, preferably
It is 4.5 or less, particularly preferably 3.5 or less.

Further, the glass transition temperature (Tg) of such a graft-modified α-olefin random elastic copolymer is usually
-150 to + 50 ° C, preferably in the range of -80 ° C to -20 ° C. The intrinsic viscosity [η] of this graft-modified α-olefin random elastic copolymer measured at 135 ° C in decalin
Is usually in the range of 0.2 to 10 dl / g, preferably 1 to 5 dl / g. Its density is usually in the range of 0.82 to 0.935 g / cm ³ , preferably 0.84 to 0.92 g / cm ³ .

Representative examples of such a graft-modified α-olefin random elastic copolymer include (a) a graft-modified ethylene / α-olefin copolymer rubber, and (b) a graft-modified propylene / α-olefin copolymer. This will be described in more detail by taking the combined rubber as an example.

The α-olefin constituting the above-mentioned graft-modified ethylene / α-olefin copolymer rubber (a) is usually an α-olefin having 3 to 20 carbon atoms, for example, propylene, butene-1, pentene-1, Hexene-1, 4
-Methylpentene-1, octene-1, decene-1 and mixtures thereof. Of these, propylene and / or butene-1 are particularly preferred.

The α-olefin constituting the graft-modified propylene / α-olefin copolymer rubber (b) is usually an α-olefin having 4 to 20 carbon atoms, for example, butene-1, pentene-1, hexene-1, Mention may be made of 4-methylpentene-1, octene-1, decene-1 and mixtures thereof. Of these, butene-1 is particularly preferred.

The α-olefin random copolymer constituting the graft-modified α-olefin random elastic copolymer is a component unit derived from a diene compound within a range that does not impair the characteristics of the α-olefin random elastic copolymer. And other component units other than those derived from α-olefins.

For example, the component units permitted to be included in the α-olefin random elastic copolymer include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, and 6-methyl- 1,5-heptadiene and 7
Component units derived from a chain non-conjugated diene such as -methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-
Component units derived from cyclic non-conjugated dienes such as ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and 6-chloromethyl-5-isopropylenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-
Component units derived from diene compounds such as ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene; and component units derived from a cyclic olefin component. The content of the diene component unit as described above in the α-olefin random elastic copolymer constituting the graft-modified α-olefin random elastic copolymer used in the present invention is usually 10 mol% or less, preferably 5 mol% or less.

In the above graft-modified ethylene / α-olefin copolymer rubber (a), the molar ratio of ethylene to α-olefin (ethylene / α-olefin) is α-olefin.
Although it depends on the type of olefin, it is generally 1/99 to
It is 99/1, preferably 50/50 to 95/5. The molar ratio is
When the α-olefin is propylene, 50/50 to 9
0/10 is preferred, and when the α-olefin is an α-olefin having 4 or more carbon atoms, 80/20 to 95/5
It is preferred that

Examples of the ethylene / α-olefin copolymer forming such a graft-modified ethylene / α-olefin copolymer rubber (a) include ethylene / propylene copolymer and ethylene / butene-
2-component systems such as 1-copolymer, ethylene-4-methylpentene-1 copolymer, ethylene / hexene-1 copolymer, ethylene / octene-1 copolymer and ethylene / decene-1 copolymer Copolymer; ethylene / propylene / 1,4-hexadiene copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 2,5 -Norbornadiene copolymer, ethylene / butene-1 / dicyclopentadineene copolymer, ethylene / butene-1 ·
1,4-hexadiene copolymer and ethylene butene
A multi-component copolymer such as a 1.5-ethylidene-2-norbornene copolymer can be used.

In the graft-modified propylene / α-olefin copolymer rubber (b), the molar ratio of propylene to α-olefin (propylene / α-olefin) is α-olefin.
Although it depends on the type of olefin, it is generally 50 / 50-9
It is preferably 5/5. When the α-olefin is 1-butene, the molar ratio is preferably 50/50 to 90/10, and the α-olefin is α-olefin having 5 or more carbon atoms.
When it is an olefin, it is preferably 80/20 to 95/5.

The graft-modified α-olefin random elastic copolymer used in the present invention is obtained by converting the above-mentioned unmodified α-olefin random elastic copolymer to an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or an unsaturated carboxylic acid. It is formed by graft modification using an acid derivative.

Examples of the unsaturated carboxylic acids used herein include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2.2.1] Hept-5-ene-2,5-dicarboxylic acid (Nadic acid ^™ ) and methyl-endocis-bicyclo [2.2.1] Hept-5-ene-2,5-dicarboxylic acid (Methylnadic acid ^™) ). Preferred examples of the unsaturated maleic anhydride include maleic anhydride, citraconic anhydride, nadic anhydride and methylnadic anhydride. further,
Examples of the unsaturated carboxylic acid derivatives include the above-mentioned unsaturated carboxylic acid acid halide compounds (eg, maleyl chloride), imide compounds (eg, maleimide), ester compounds (eg, monomethyl maleate, dimethyl maleate, glycidyl maleate) Can be mentioned.

The above graft modifiers can be used alone or in combination.

Among such graft modifiers, unsaturated carboxylic anhydrides are preferably used, and maleic anhydride or nadic anhydride is particularly preferred.

As a method of graft-polymerizing the unmodified α-olefin random elastic copolymer with such a graft modifier as described above, for example, suspending or dissolving in an α-olefin random elastic copolymer and a solvent, A method in which a graft modifier is added to this suspension or solution to cause a graft reaction, a method in which a mixture of the α-olefin random elastic copolymer and the graft modifier is melted to cause a graft reaction, and the like can be mentioned. .

In such a graft reaction, the amount of the graft modifier used is set in consideration of its reactivity, but generally, the unmodified α-olefin random elastic copolymer 10 is used.
Grafting is carried out by mixing 1 to 10 parts by weight with respect to 0 parts by weight.

By performing the graft reaction in this manner, the graft modifier is 0.01 to 10 parts by weight, preferably 0.1 part by weight, per 100 parts by weight of the unreacted α-olefin random elastic copolymer.
Graft modified α graft-polymerized at a ratio of 5 to 5.0 parts by weight
An olefin random elastic copolymer can be obtained.

When such a graft reaction is performed, the use of a radical initiator can improve the grafting efficiency. Known radical initiators such as organic peroxides, organic peresters and azo compounds can be used as the radical initiator used here. When a radical initiator is used, the amount is usually 0.01 to 20 parts by weight based on 100 parts by weight of the unmodified α-olefin random elastic copolymer.

In the present invention, among the above-mentioned graft-modified α-olefin graft elastic copolymers, an ethylene content of 35 to 50 mol% and a substantially amorphous graft-modified ethylene / propylene random copolymer rubber or By using the graft-modified ethylene / α-olefin random copolymer rubber, a decrease in the toughness of the connector due to thermal deterioration can be efficiently suppressed.

The above-mentioned graft-modified α-olefin random elastic copolymer usually comprises the above-mentioned graft-modified ethylene / α-olefin copolymer rubber (a) and the graft-modified propylene / α-olefin copolymer rubber (b) alone. Or in combination, the above-mentioned graft-modified α-olefin random elastic copolymer contains other polymers or copolymers within a range that does not impair the properties of the graft-modified α-olefin random elastic copolymer. May be.

Examples of such another polymer or copolymer include an aromatic vinyl hydrocarbon / conjugated diene copolymer or a hydride thereof. Specifically, such an aromatic vinyl hydrocarbon / conjugated diene copolymer or a hydride thereof includes styrene / butadiene copolymer rubber, styrene / butadiene / styrene copolymer rubber, and styrene / isoprene block copolymer. Examples include a coalesced rubber, a styrene / isoprene / styrene block copolymer rubber, a hydrogenated styrene / butadiene / styrene block copolymer rubber, and a hydrogenated styrene / isoprene / styrene block copolymer rubber.

The thermoplastic resin composition for a connector of the present invention contains the above-mentioned polyamide-modified α-olefin random elastic copolymer of polyamide in a weight ratio of 98: 2 to 60:40. By blending both in this way,
A connector formed from the composition of the present invention can be used, for example,
It is possible to effectively suppress a decrease in toughness after heating to about 150 ° C. and then cooling to room temperature. In particular, in the present invention, the thermoplastic resin composition for a connector containing both at a weight ratio of 95: 5 to 60:40 exhibits a very small change in the elongation of the connector under the above conditions. Therefore, by using this composition, it is possible to obtain a connector in which the decrease in toughness due to heating is small.

The value of the heat distortion temperature (high load; 18.6 Kg) of the composition of the present invention is usually in the range of 70 to 140 ° C., preferably 80 to 120 ° C., and is extremely high heat resistance while being thermoplastic. Show.

The thermoplastic resin composition for a connector of the present invention is composed of a specific polyamide and a graft-modified α-olefin elastic copolymer as described above, and furthermore, the composition of the present invention has a property that does not impair the properties. , In addition to the above components, inorganic fillers, organic fillers, heat stabilizers, weathering stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, natural oils, synthetic Additives such as oils and waxes may be included.

For example, preferred examples of the fibers used as the inorganic filler include glass fibers and boron fibers. Glass fiber is particularly preferred as such a fibrous filler. By using glass fiber,
A connector formed from the thermoplastic resin composition for a connector has improved mechanical properties such as tensile strength, bending strength and flexural modulus, and heat resistance such as heat distortion temperature. The average length of the above glass fiber is usually 0.1-20 mm,
Preferably it is in the range of 0.3 to 6 mm and the aspect ratio is usually in the range of 10 to 2000, preferably 30 to 600. It is preferable to use glass fibers having an average length and an aspect ratio within such ranges. By incorporating such a glass fiber, the moldability of the composition of the present invention is improved, and a connector having particularly good heat resistance such as heat distortion temperature, mechanical strength such as tensile strength and bending strength is obtained. Can be. Such glass fibers are usually in an amount of 200 parts by weight or less, preferably in an amount of 5 to 180 parts by weight, more preferably 5 to 150 parts by weight, based on 100 parts by weight of the resin component in the composition of the present invention. Parts are blended.

In addition to the above-mentioned inorganic fibrous filler, in the present invention,
Various fillers having a shape such as powder, powder, plate, needle, cloth, and mat can be used. Examples of such fillers include silica, silica alumina,
Alumina, titanium dioxide, talc, diatomaceous earth, clay, kaolin, glass, mica, gypsum, Bengal,
Powdery or plate-like inorganic compounds such as zinc oxide, polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, condensates of diaminodiphenyl ether with terephthalic acid (isophthalic acid) Wholly aromatic polyamides such as condensates of para (meth) aminobenzoic acid, wholly aromatic polyamide-imides such as condensates of diaminodiphenyl ether with trimellitic anhydride or pyromellitic anhydride, wholly aromatic polyesters, wholly aromatic Heterocycle-containing compounds such as polyimide, polybenzimitazole and polyimidazophenanthroline, and powdered, plate-like, fibrous or cloth-like secondary products formed from polytetrafluoroethylene and the like. In Wear.

These fillers can be used as a mixture of two or more. Further, these fillers can be used after being treated with a silane coupling agent or a titanium coupling agent. The average particle size of such a powdery filler is generally in the range of 0.1 to 200 μm, preferably 1 to 100 μm.

Such a powdery filler is usually a total of polyamide and the graft-modified α-olefin random elastic copolymer, that is, generally 200 parts by weight or less based on 100 parts by weight of the resin component in the composition. It is preferably used in an amount of up to 100 parts by weight, particularly preferably in an amount of from 0.5 to 50 parts by weight.

In addition, a heat-resistant resin may be added to the resin composition of the present invention as long as the properties of the composition of the present invention are not impaired. Examples of such heat resistant thermoplastics include:
Examples include PPS (polyphenylene sulfide), PPE (polyphenyl ether), PES (polyether furfon), PEI (polyether imide), and LCP (liquid crystal polymer), and further include modified products of these resins. Can be. Particularly, in the present invention, polyphenylene sulfide is preferable. The content of such a heat-resistant thermoplastic resin is usually less than 50% by weight, preferably 0 to 40% by weight.

The thermoplastic resin composition for a connector of the present invention can be prepared by mixing and melting the above polyamide, a graft-modified α-olefin random elastic copolymer, and if necessary, an additive and another resin. For example, it can be prepared by a method in which the polyamide and the graft-modified α-olefin random elastic copolymer are maintained in a molten state while the filler or other resin is mixed and kneaded as necessary. At this time, a usual kneading device such as an extruder or a kneader can be used.

By kneading in this manner, usually, the graft-modified α-olefin random elastic copolymer is finely dispersed in the polyamide. A so-called polymer alloy is formed.

Using the thermoplastic resin composition for a connector prepared as described above, a connector having a desired shape is produced by utilizing a usual melt molding method, for example, a compression molding method, an injection molding method or an extrusion molding method. can do.

For example, the resin composition of the present invention, the cylinder temperature is 350
A connector can be manufactured by putting it into an injection molding machine adjusted to about 300 ° C., melting it, and introducing it into a mold having a predetermined shape.

Effect of the Invention The thermoplastic resin composition for a connector of the present invention is a composition containing an aromatic polyamide and a specific graft-modified α-olefin random copolymer in a specific ratio. By blending the two in this way, the toughness of the connector is less likely to decrease even when exposed to a temperature of, for example, 150 ° C. or more for a long time.

Therefore, a connector formed from such a resin composition has a reduced toughness even when the connector itself is exposed to a considerably high temperature, for example, when soldering is performed by an infrared reflow method. Because it is less, the connector can be incorporated well,
Poor contact at the connector portion is unlikely to occur. The durability of the connector itself is also improved.

By using the composition of the present invention, it is possible to produce a connector having good toughness as described above,
Moreover, even by suppressing such a decrease in toughness, other excellent properties inherent to the aromatic polyamide, such as properties such as mechanical strength and low water absorption, do not decrease.

Next, the present invention will be described in more detail with reference to Examples of the present invention. However, the present invention should not be construed as being limited by these Examples.

Synthesis Example 1 Two kinds of polyamides (polyamide A and polyamide B) were prepared as described below.

Preparation of Polyamide A 254 g (2.19 mol) of 1,6-diaminohexane, 247 g (1.49 mol) of terephthalic acid and 106 g of isophthalic acid, and 0.45 g (4.25 × 10 ⁻³ mol) of sodium hypophosphite as a catalyst
And 148 ml of ion-exchanged water were charged into a 1-liter reactor and, after purging with nitrogen, reacted at 250 ° C. and 35 kg / cm ² for 1 hour. The molar ratio of terephthalic acid to isophthalic acid is 7
It is 0:30.

After one hour, the reaction product generated in the reactor is connected to the reactor and the pressure is set to about 10 kg / cm ² , and is withdrawn to a receiver. The intrinsic viscosity (measured in concentrated sulfuric acid at 30 ° C) 545 g of polyamide having [η] of 0.10 dl / g was obtained.

Next, this polyamide was dried and melt-polymerized at a cylinder set temperature of 330 ° C. using a twin-screw extruder to obtain an aromatic polyamide having an intrinsic viscosity [η] of 1.1 dl / g.

The content of the terephthalic acid component valley in this aromatic polyamide was 71 mol%, and the melting point was 320 ° C.

The composition and properties of this polyamide A are as follows.

Terephthalic acid component unit content in dicarboxylic acid component unit: 70 mol% Isophthalic acid component unit content: 30 mol% Intrinsic viscosity: 1.1 dl / g (measured in concentrated sulfuric acid at 30 ° C) Melting point: 320 ° C Glass transition temperature: 125 ° C. Preparation of Polyamide B An aromatic polyamide was prepared in the same manner as in the preparation of Polyamide A, except that the mixing ratio of terephthalic acid: isophthalic acid was changed to 55:45.

The composition and properties of this polyamide B are as follows.

Terephthalic acid component unit content in dicarboxylic acid component unit: 55 mol% Isophthalic acid component unit content: 45 mol% Intrinsic viscosity: 1.1 dl / g (measured in concentrated sulfuric acid at 30 ° C) Melting point: 315 ° C Glass transition temperature: 100 ° C. Synthesis Example 2 Six types of modified (co) polymers (modified elastic copolymer a, modified elastic copolymer b, modified elastic copolymer c, modified elastic copolymer d, A modified elastic copolymer e and a modified polymer f) were obtained.

Preparation of Modified Elastic Copolymer a First, ethylene and butene-1 were copolymerized according to a conventional method to obtain a random elastic copolymer. (Density: 0.935g /
cm ³ ) 1 part by weight of maleic anhydride is added to 100 parts by weight of the random elastic copolymer, and a graft modification reaction is performed in a molten state to obtain a graft-modified random copolymer a.
I got (Maleic acid graft amount 1% by weight, density 0.935g
/ cm ³ ) Preparation of Modified Elastic Copolymer b First, ethylene and 4-methylpentene-1 were copolymerized according to a conventional method to obtain a random elastic copolymer.

1 part by weight of maleic anhydride is blended with 100 parts by weight of the random elastic copolymer, and a graft modification reaction is performed in a molten state to obtain a graft-modified random copolymer b.
I got (Maleic acid graft amount 1% by weight, density 0.920g
/ cm ³ ) Preparation of Modified Elastic Copolymer c First, a random elastic copolymer was obtained by copolymerizing ethylene and propylene with a diene according to a conventional method.

1 part by weight of maleic anhydride is added to 100 parts by weight of the random elastic copolymer, and a graft modification reaction is performed in a molten state to obtain a graft-modified random copolymer c.
I got (Maleic acid graft amount 1% by weight, density 0.87
0) Modified elastic copolymer d Bondfast (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a copolymer of ethylene and glycidyl methacrylate, was used.

Preparation of Modified Elastic Copolymer e First, a random elastic copolymer was obtained by copolymerizing ethylene and butene-1 according to a conventional method.

The crystallinity of the random elastic copolymer measured by the X-ray diffraction method was 0%, and it was confirmed that the random elastic copolymer was non-crystalline.

One part by weight of maleic anhydride is blended with 100 parts by weight of the random elastic copolymer and a graft modification reaction is performed in a molten state to obtain a graft-modified random copolymer e.
I got

Preparation of Modified Polymer f The intrinsic viscosity [η] measured in decalin at 135 ° C. is 3.7 dl / g
High-density polyethylene [Mitsui Petrochemical Industry Co., Ltd.
5kg of pellets of Hyzex 8000F], acetone 25
g of maleic anhydride and 2 g of organic peroxide [manufactured by NOF CORPORATION, Perhexin 25B] were added and mixed well, and then mixed with a twin-screw extruder “PCM45, manufactured by Ikega Iron Works Co., Ltd.” The cylinder temperature was set at 250 ° C. to carry out an oil dropping reaction, and then pelletized to pelletize.

The resulting resin had a maleic anhydride content of 0.96% by weight.

Examples 1 to 5 and Comparative Example 1 80 parts by weight of the polyamide A prepared in Synthesis Example 1 above,
Graft-modified copolymer (af) 20 described in Synthesis Example 2
After kneading parts by weight, the mixture was pelletized.

The modified (co) polymer used and the numbers of Examples and Comparative Examples have the following relationship.

Graft-modified random elastic copolymer a ... Example 1 Graft-modified random elastic copolymer b ... Example 2 Graft-modified random elastic copolymer c ... Example 3 Graft-modified random elastic copolymer d ... Example 4 Graft modified Random elastic copolymer e: Example 5 Graft-modified polymer f: Comparative example 1 Using the pellets thus obtained, ASTM type IV,
A test piece having a thickness of 2 mm was prepared, and the tensile strength at break (TS) and the elongation at break (ie, toughness, EL) of this test piece were measured.
Was measured.

Next, the test piece prepared in the same manner was heated at 150 ° C. for 24 hours, and then the tensile strength at break (TS) and the elongation at break (that is, toughness, EL) were measured.

 Table 1 shows the results.

Examples 6-7 and Comparative Example 2 80 parts by weight of the polyamide B prepared in Synthesis Example 2 above,
After kneading 20 parts by weight of the graft-modified copolymer (b and c) described in Synthesis Example 2, the mixture was pelletized.

The modified (co) polymer used and the numbers of Examples and Comparative Examples have the following relationship.

Graft-modified random elastic copolymer c: Example 6 Graft-modified random elastic copolymer b: Example 7 Graft-modified polymer f: Comparative example 2 Using the pellets thus obtained, an ASTM type IV test of 2 mm thickness Specimens were prepared and the tensile strength at break (TS) and elongation at break (ie, toughness, EL) were measured for the specimens.

Next, the test piece prepared in the same manner was heated at 150 ° C. for 24 hours, and then the tensile strength at break (TS) and the elongation at break (that is, toughness, EL) were measured.

 Table 2 shows the results.

As is clear from the comparison between the examples shown in Tables 1 and 2 and the comparative examples, the molded article, that is, the connector was heated by using the thermoplastic resin composition for a connector of the present invention. The decrease in the elongation at break due to this is reduced. Therefore, the connector formed from the composition of the present invention hardly decreases in good elasticity even when heated, and the required toughness is maintained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 77/00-77/12 C08L 51/06 H01R 13/46 H01R 13/533

Claims (1)

(57) [Claims] (1) a terephthalic acid component unit of 20 to 100 mol%,
Aromatic dicarboxylic acid component units other than terephthalic acid 0 to 80
A dicarboxylic acid component unit composed of 0 to 80 mol% of an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms, and a diamine component composed of an aliphatic diamine component unit and / or an alicyclic diamine component unit. An aromatic polyamide having an intrinsic viscosity of 0.5 to 3.0 dl / g measured in concentrated sulfuric acid at 30 ° C. and a melting point of 280 ° C. or higher, and A substantially non-crystalline, graft-modified α-olefin random elastic copolymer having at least two types of repeating units derived from an α-olefin is prepared from 98: 2 to 60:40.
A thermoplastic resin composition for a connector, characterized by containing at a weight ratio of: