JP3029038B2 - Plastic composition - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a plastic composition for forming a radiator tank or a plumbing member of an automobile, and a radiator tank or a plumbing member, and more particularly to a heat resistance and a chemical resistance. The present invention also relates to a plastic composition for forming an automobile radiator tank or plumbing member and a radiator tank or plumbing member.

Technical background of the invention and its problems In general, polycaprolactam (6-nylon), polyhexamethylene adipamide (6,6-nylon), polyhexamethylene azelite (6,9-nylon), polyhexamethylenese Aliphatic polyamides represented by vasamide (6,10-nylon), polyhexamethylene dodecanoamide (6,12-nylon), polylauric lactam (12-nylon), etc. Compared with plastic resins, they are superior in strength, rigidity, heat resistance, wear resistance, etc., and are widely used as various engineering plastics as engineering plastics.

However, aliphatic polyamides such as those described above are required to be used in the field of engineering plastics that require even higher performance, such as heat resistance properties such as melting point, glass transition point, and heat distortion temperature, and rigidity, tensile strength, and bending strength. Mechanical properties such as water resistance, boiling water resistance, salt water resistance, and chemical resistance are not sufficient. For this reason, its use has been limited.

Therefore, in applications where aliphatic polyamides cannot be used, other resins are inevitably used.

Such engineering plastics with excellent heat resistance, mechanical properties, and physical and chemical properties include, for example,
PPS (polyphenylene sulfide resin), PES (polyether sulfone), PEEK (polyether ether ketone), PSF (polysulfone), PEI (polyetherimide) and the like have been used, and more recently, for example, polytetrafluoroethylene ( Brand name: Teflon), polyparaphenylene terephthalimide (brand name: Kevlar), polyimide (trade name: Kapton) composed of a condensate of 4,4'-diaminophenyl ether and pyromellitic anhydride, polyphenylene sulfide, etc. It is used.

However, among these engineering plastics, polytetrafluoroethylene, polyparaphenylene terephthalamide, the polyamide resin, and the like are materials having excellent heat resistance, mechanical properties, and physical and chemical properties. Cannot be performed. Further, polyphenylene sulfide, polyacetal, and the like have a problem that heat resistance such as melting point, glass transition point, and heat deformation temperature, and mechanical properties such as impact resistance and abrasion resistance are inferior.

By the way, from the viewpoint of energy saving by weight reduction, plastics which are lighter than metal materials and have excellent moldability have been widely used as automobile parts. Automotive parts molded from these plastics cover a wide range, for example, bumpers, vehicle body panels, tanks, and the like, and the characteristics required for each part are very different.

As one of such automobile parts, a cooling water storage tank for an automobile radiator (hereinafter referred to as an automobile radiator tank) has excellent heat resistance and chemical resistance, as well as water resistance, and has excellent mechanical properties. It is required to have a target strength.

In other words, the engine cooling water returned from the engine water jacket may rise to 80 ° C or higher depending on the use environment.Also, since the radiator is usually installed near the engine in the engine room, the high temperature at high temperatures Rigidity is required.

In addition, since the cooling water returned at a high temperature and the cooling water when cooled to a low temperature coexist in the automobile radiator tank, it is desired that the coefficient of thermal expansion does not change at any temperature.

In recent years, antifreeze (long life coolant) such as an aqueous solution of polyethylene glycol has been widely used as an engine cooling water for preventing freezing. If the antifreeze is used for a long time in a state where the antifreeze is contained, a radiator tank machine is required. There is a problem that the mechanical strength is reduced. Further, in a cold region, there is a problem that stress cracks occur in the radiator tank due to calcium chloride sprayed on the road as an antifreezing agent. It must also have excellent properties in terms of chemical resistance to such antifreeze and road deicers.

However, in automotive radiator tanks that require such high performance, none of the above-mentioned conventional materials has been satisfied, and furthermore, heat resistance, mechanical properties and physicochemical properties, especially heat resistance properties However, there was still room for improvement.

Object of the Invention The present invention is to solve the problems associated with the prior art as described above, melting point, glass transition point, heat resistance such as heat deformation temperature, tensile strength, bending strength, resistance to heat. Mechanical properties such as impact strength, physical and chemical properties such as water resistance, boiling water resistance, salt water resistance, saturated water absorption, chemical resistance, etc., fluidity of melt molded products, melt compression moldability, melt injection moldability, An object of the present invention is to provide a plastic composition for forming a radiator tank for an automobile and a member for surrounding water, which is excellent in molding properties such as melt extrusion moldability, particularly, heat resistance and chemical resistance.

SUMMARY OF THE INVENTION The plastic composition for forming a radiator tank or for forming a plumbing member according to the present invention comprises: (A) (a) 40 to 100 mol% of a terephthalic acid component unit, and (b) an aromatic dicarboxylic acid other than terephthalic acid. A dicarboxylic acid component unit composed of 0 to 40 mol% of component units and / or (c) 0 to 60 mol% of aliphatic dicarboxylic acid component units; and [B] an aliphatic alkylenediamine component unit and / or an alicyclic alkylenediamine. Consisting of repeating units consisting of component units, and having an intrinsic viscosity measured in concentrated sulfuric acid at 30 ° C.
When the melting point is in the range of 0.5 to 3.0 dl / g and the melting point is 293 ° C. or more, the polyamide is composed of a polyamide and a fibrous inorganic filler, and the polyamide is a main component.

Further, the plastic composition according to the present invention can include a filler in addition to the polyamide.

Further, the radiator tank or the plumbing member of the present invention is characterized by being formed from the above plastic composition.

The plastic composition according to the present invention and the radiator tank or the water supply member are made of a polyamide composed of the specific repeating unit as described above,
Excellent in mechanical properties, physicochemical properties, molding properties, etc., and especially excellent in heat resistance and chemical resistance.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the plastic composition for forming a radiator tank of an automobile or a member for surrounding water according to the present invention will be specifically described.

Polyamide The polyamide used in the present invention is composed of a repeating unit composed of a specific dicarboxylic acid component unit [A] and an aliphatic alkylenediamine component unit and / or an alicyclic alkylenediamine component unit [B].

In the present invention, the specific dicarboxylic acid component unit [A] constituting the polyamide used contains a terephthalic acid component unit (a) as an essential component. Such a repeating unit of the polyamide containing 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 aliphatic alkylene group, preferably an aliphatic alkylene group having 4 to 25 carbon atoms and / or an alicyclic alkylene group.

The specific dicarboxylic acid component unit constituting the polyamide used in the present invention may contain other dicarboxylic acid component units in addition to the above terephthalic acid component unit (a).

As other dicarboxylic acid component units other than the terephthalic acid component, there are an aromatic dicarboxylic acid component unit other than terephthalic acid and an aliphatic dicarboxylic acid component unit.

Accordingly, examples of aromatic dicarboxylic acid component units other than terephthalic acid used in the present invention include component units derived from isophthalic acid (IA), phthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, and the like. Can be. When the polyamide of the present invention contains an aromatic dicarboxylic acid component unit other than terephthalic acid, such a component unit is preferably an isophthalic acid or naphthalenedicarboxylic acid component unit, and particularly preferably an isophthalic acid component unit.

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

In the formula [II-b], R ¹ represents an aliphatic alkylene group, preferably an alkylene group having 4 to 25 carbon atoms and / or an alicyclic alkylene group.

Furthermore, in the present invention, the aliphatic dicarboxylic acid component unit used is not particularly limited in the number of carbon atoms, but is usually derived from an aliphatic dicarboxylic acid having an alkylene group of 4 to 20, preferably 6 to 12. . Examples of the aliphatic dicarboxylic acid used to derive such an aliphatic dicarboxylic acid component unit (c) include succinic acid, adipic acid (AA), azelaic acid, sebacic acid, decanedicarboxylic acid, and undecanedicarboxylic acid. And dodecanedicarboxylic acid. When the polyamide of the present invention contains an aliphatic dicarboxylic acid component unit, such a component unit is particularly preferably an adipic acid component unit.

Such a repeating unit containing the aliphatic dicarboxylic acid component unit (c) can be represented by the following formula [III].

However, in the above formula [III], n is usually 4 to 2
Represents an integer of 0, preferably 6 to 12. R ¹ is the same as described above.

The diamine component unit used in the present invention together with the dicarboxylic acid component as described above to constitute the polyamide is a component unit derived from an aliphatic alkylenediamine component unit and / or an alicyclic alkylenediamine component unit. Among the aliphatic alkylenediamine component units, component units derived from aliphatic alkylenediamines having 4 to 18 carbon atoms are preferred.

Specific examples of such an aliphatic alkylenediamine component unit include 1,4-diaminobutane 1,6-diaminohexane, trimethyl-1,6-diaminohexane 1,7-diaminoheptane, 1,8-diaminooctane, Linear alkylenediamines such as 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and 1,4-diamino-1,1-dimethylbutane, 1 , 4-Diamino-1-ethylbutane, 1,4-diamino-1,2-dimethylbutane, 1,4-diamino-1,3-dimethylbutane, 1,4-diamino-1,4-dimethylbutane, 1, 4-diamino-2,3-dimethylbutane, 1,2-diamino-1-butylethane, 1,6-diamino-2,5-dimethylhexane, 1,6-diamino-2,4-dimethylhexane, 1,6 -Diamino-3,3-dimethylhexane, 1,6-diamido No-2,2-dimethylhexane, 1,6-diamino-2,2,4-trimethylhexane, 1,6-diamino-2,4,4-trimethylhexane, 1,7-diamino-2,3-dimethyl Heptane, 1,7-diamino-2,4-dimethylheptane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-2,2-dimethylheptane, 1,8-diamino-1,3 -Dimethyloctane, 1,8-diamino-1,4-dimethyloctane, 1,8-diamino-2,4-dimethyloctane, 1,8-diamino-3,4-dimethyloctane, 1,8-diamino-4 1,5-dimethyloctane, 1,8-diamino-2,2-dimethyloctane, 1,8-diamino-3,3-dimethyloctane, 1,8-diamino-4,4-dimethyloctane, 1,6-diamino Derived from a branched chain alkylenediamine such as -2,4-diethylhexane, 1,9-diamino-5-methylnonane. Mention may be made of the component units.

Among such linear or branched chain alkylenediamine component units, straight-chain alkylenediamine component units are preferred, and in particular, 1,6-diaminohexane, 1,8-diaminooctane, Component units derived from one or more compounds of linear alkylenediamines such as 10-diaminodecane and 1,12-diaminododecane are preferred, and 1,6-diaminohexane component units are more preferred. Is preferred.

The alicyclic diamine component unit usually has 6 to 6 carbon atoms.
It is a component unit derived from a diamine of about 25 and containing at least one alicyclic hydrocarbon ring.

As such alicyclic diamine component units, specifically, for example, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis ( Aminomethyl) cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,4'-diamino-3,3'-dimethyldicyclohexylpropane 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3 '-Dimethyl-5,5'-dimethyldicyclohexylpropane, α-α'-bis (4-aminocyclohexyl) -p-
Diisopropylbenzene, α-α'-bis (4-aminocyclohexyl) -m-
Diisopropylbenzene, α-α'-bis (4-aminocyclohexyl) -1,4
-Cyclohexane, α-α'-bis (4-aminocyclohexyl) -1,3
-Component units derived from an alicyclic diamine such as cyclohexane.

Among these alicyclic diamine component units, bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, and 4,4′-diamino-3,3′-dimethyldicyclohexylmethane are preferred, and bis (amino) is particularly preferred. Component units derived from alicyclic diamines such as 4-aminocyclohexyl) methane, 1,3-bis (aminocyclohexyl) methane, and 1,3-bis (aminomethyl) cyclohexane are preferred.

The polyamide used in the present invention contains 40 to 100 mol% of terephthalic acid component units (a) in 100 mol% of all dicarboxylic acid component units; and 0 to 40 mol of aromatic dicarboxylic acid component units (b) other than terephthalic acid. And a repeating unit containing the aliphatic dicarboxylic acid component unit (c) in an amount of 0 to 60 mol%.

In addition, the above-mentioned repeating unit is derived from a divalent aromatic carboxylic acid other than terephthalic acid represented by the above-mentioned main component unit, terephthalic acid component unit, and further isophthalic acid component unit, as the aromatic dicarboxylic acid component unit. In addition to the component unit and the aliphatic dicarboxylic acid component unit described above, a small amount of trimellitic acid, contains a repeating unit containing a component unit derived from a tribasic or higher polycarboxylic acid such as pyromellitic acid. 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%.

The polyamide as described above has an intrinsic viscosity [η] measured in concentrated sulfuric acid at a temperature of 30 ° C., usually 0.5 to 3.0 dl / g, preferably
The range is 0.5 to 2.8 dl / g, particularly preferably 0.6 to 2.5 dl / g. Moreover, the melting point of this polyamide is 293 ° C. or higher. When a radiator tank or the like is formed using a polyamide having such a melting point, a molded article having excellent heat resistance and the like can be obtained.

The polyamide used in the present invention has the formula [II-
a], a polyamide containing a repeating unit represented by the formula [II-b] and the formula [III],
A polyamide having a repeating unit represented by the formula [II-a] as a main repeating unit, a polyamide having a repeating unit represented by the formula [II-b] as a main repeating unit, and a polyamide having the formula [III] It may be a polyamide mixture comprising a polyamide having the repeating unit represented as a main repeating unit.

When the polyamide used in the present invention is a mixture,
Among these mixtures, a polyamide having a repeating unit represented by the formula [II-a] as a main repeating unit and a polyamide having a repeating unit represented by the formulas [II-b] and / or [III] as a main repeating unit Preferably, the composition comprises: In this case, the content of the polyamide having a repeating unit represented by the formula [II-a] as a main repeating unit is usually 30.
% By weight or more.

Further, in this case, a polyamide having the repeating unit represented by the formula [II-b] as a main repeating unit, and a polyamide having the formula [II-b]
The mixing ratio with the polyamide mixture having the repeating unit represented by I] as a main repeating unit is a weight ratio, usually 0:
It is 100 to 40:60, preferably 0: 100 to 30:70.

The polyamide used in the present invention has a much higher glass transition temperature (T
g). That is, the glass transition temperature of the polyamide used in the present invention is usually 70 to 150 ° C., preferably 80 ° C.
140140 ° C., and the glass transition temperature is usually 20 to 100 ° C. higher than that of a conventional polyamide such as 6,6-nylon. Therefore, it can also be used in applications that come into contact with a high-temperature heat exchange medium, such as a radiator tank, which has been difficult to use with conventional polyamides.

Further, since the polyamide used in the present invention has a specific structure, it naturally has a high flexural modulus at a high temperature, and, of course, has a high temperature after water absorption, which has been a problem of the conventional polyamide. The decrease in flexural modulus is small.

FIG. 1 shows an example of the relationship between the change in the bending strength of the polyamide used in the present invention and the change in the bending strength of the polyamide when water is absorbed, with respect to the temperature in the absolutely dry state.

In FIG. 1, the broken line shows the change curve of the bending elastic modulus with respect to the temperature of the polyamide in a completely dry state, and the solid line shows the bending with respect to the temperature of the polyamide after water absorption treatment in 100 ° C. water for 4 days. It is a change curve of an elastic modulus. In FIG. 1, "a" indicates an example of the polyamide used in the present invention, "b" indicates an example of commercially available 66 nylon, and "c" indicates an example. Shown is a commercially available MXD6 nylon. The nylons are all glass fiber reinforced formulations.

As is clear from FIG. 1, the conventional polyamide and the like have low heat resistance. That is, cooling water near 100 ° C. generally flows into the radiator tank. Such a temperature is a value close to the use upper limit temperature of a conventionally used polyamide resin. On the other hand, the polyamide used in the present invention is, as shown in FIG.
Up to about 0 ° C, the flexural modulus of 60 × 10 ³ kg / cm ² or more is maintained.

Moreover, the polyamide used in the present invention hardly decreases the usable temperature of the resin even if it absorbs water. On the contrary,
"B" and "c" such as nylon conventionally used
In addition, in addition to the inherently low use limit temperature, the usable temperature is significantly reduced due to water absorption.

 Table 1 shows the relationship between the water absorption and the glass transition temperature.

As is clear from Table 1 above, the polyamide (aromatic polyamide (a)) used in the present invention has a higher glass transition point at the time of absolute drying than a conventionally used polyamide (for example, 66 nylon). . Furthermore, the glass transition point at the time of water absorption is also high.

Furthermore, since the polyamide used in the present invention has a high glass transition point, the rate of dimensional change accompanying a temperature change in a high temperature region is small.

Table 2 shows an example of the thermal expansion coefficient of the polyamide used in the present invention. The values are for glass fiber reinforced products.

The numbers in parentheses in Table 2 above are the linear expansion coefficients of 66 nylon measured under the same conditions.

As described above, the polyamide used in the present invention has a smaller variation in linear expansion coefficient in a high temperature region than the conventional polyamide.

For this reason, the radiator tank manufactured using such a polyamide has a change in flexural modulus or a coefficient of linear expansion even under severe temperature conditions such as contact with high-temperature cooling water and low-temperature outside air. It has the characteristic that cracks and the like hardly occur due to the difference due to the temperature difference.

Moreover, the polyamide used in the present invention is less prone to cracks on the contact surface with calcium chloride even when continuously contacted with calcium chloride in a state where bending stress is applied,
The polyamide used in the present invention also has completely different properties from aliphatic polyamides such as nylon 66 conventionally used in terms of chemical resistance to calcium chloride and the like.

Therefore, the radiator tank manufactured by using the above-mentioned polyamide has an excellent property that it is particularly excellent in heat resistance and hardly generates a crack even when it comes into contact with calcium chloride or the like as an antifreezing agent. .

Such polyamide (or polyamide composition)
Can be manufactured using conventional techniques.

Filler The plastic composition according to the present invention contains polyamide as an essential constituent component as described above, and optionally includes an organic or inorganic filler, an antioxidant, and an ultraviolet absorber in addition to these essential components. , Light protection agents, heat stabilizers, phosphite stabilizers, peroxide decomposers, basic auxiliaries, nucleating agents, plasticizers, lubricants, antistatic agents, flame retardants, pigments, dyes, etc. good.

Among the fillers described above, examples of organic or inorganic fillers include various fillers having powder, granular, plate, fibrous, needle, cross, and mat shapes. , Specifically, silica, alumina, silica alumina, talc, diatomaceous earth, clay, kaolin, glass,
Mica, graphite, molybdenum disulfide, gypsum,
Bengala, titanium dioxide, zinc oxide, aluminum,
Powdered or plate-like inorganic compounds such as copper and stainless steel, glass fiber, carbon fiber, boron fiber, ceramic fiber, asbestos fiber, stainless steel fiber, wollastonite, potassium titanate, etc. Secondary processed products such as cloth, polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, condensate of diaminodiphenyl ether with terephthalic acid (isophthalic acid), para ( Wholly aromatic polyamides such as condensates of (meth) aminobenzoic acid, wholly aromatic polyamide-imides such as condensates of diaminodiphenyl ether with trimellitic anhydride or pyromellitic anhydride, wholly aromatic polyesters, wholly aromatic polyimides, poly Ntsu imidazole, heterocyclic ring-containing compounds such as poly-imidazo phenanthroline, polytetrafluoroethylene powder, plate,
Secondary processed products such as fibrous or cloth-like materials can be given.

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.

Among the fillers, specific examples of the powdery filler include silica, silica alumina, alumina, titanium dioxide, graphite, molybdenum disulfide, and polytetrafluoroethylene.

The average particle size of such a powdery filler is usually 0.1 to 2
It is preferably in the range of 00 μm, preferably 1 to 100 μm. When the average particle size is in such a range, the abrasion resistance of the polyamide composition is remarkably improved.

Such a powdery filler is contained in an amount of usually 200 parts by weight or less, preferably 100 parts by weight or less, particularly preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the polyamide. ing.

Further, among the fillers, as the organic fibrous filler, specifically, polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaphenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, Examples thereof include wholly aromatic polyamide fibers such as fibers obtained from a condensate of diaminodiphenyl ether and terephthalic acid or isophthalic acid. When using such fibrous fillers,
It is preferable because the mechanical properties such as tensile strength and Izod impact strength and the heat resistance such as heat deformation temperature of the molded article obtained from the polyamide composition are improved.

Further, among the fillers, specific examples of the inorganic fibrous filler include glass fiber, carbon fiber, and boron fiber. When such fibers are used, tensile strength, bending strength, mechanical properties such as flexural modulus of a molded article obtained from the polyamide composition,
Heat resistance such as heat distortion temperature, and physical and chemical properties such as water resistance are preferably improved.

The average length of the organic or inorganic fibrous filler as described above is usually in the range of 0.1 to 20 mm, preferably 0.3 to 6 mm. When the average length of the fibrous filler is in such a range, the moldability of the polyamide composition is improved,
In addition, heat resistance such as heat distortion temperature, and mechanical properties such as tensile strength and bending strength of a molded article obtained from the polyamide composition are preferably improved.

The organic or inorganic fibrous filler is polyamide 10
0 parts by weight, usually in an amount of 200 parts by weight or less, preferably in an amount of 5 to 180 parts by weight, more preferably in an amount of 5 to 150 parts by weight to the plastic composition for forming a vehicle radiator tank of the present invention. It is desirable to be included.

It should be noted that the polyamide composition of the present invention may be blended with another resin within a range that does not impair the above excellent properties.

Examples of such resins include polyolefin, PPS
(Polyphenylene sulfide), PPE (polyphenyl ether) and the like, and modified products thereof.

The plastic composition for forming an automobile radiator tank according to the present invention is prepared by a method such as mixing and kneading the above-mentioned fillers or other resins as necessary while maintaining each component of the above-mentioned polyamide composition in a molten state. can do. At this time, a usual kneading device such as an extruder or a kneader can be used.

Using the composition according to the present invention as described above, a radiator tank for an automobile can be manufactured by utilizing a usual melt molding method, for example, a compression molding method, an injection molding method or an extrusion molding method.

Further, the composition of the present invention can be used as a resin composition for forming a water component around a radiator tank in addition to the above-described radiator tank.

In addition to these, examples of the water supply parts include a pump impeller (pumping impeller), a pump head cover, a flange, and a pump casing.

Such plumbing parts and the like can be manufactured using the same method as that for the radiator tank described above.

Further, the plastic composition according to the present invention is used for various purposes as an engineering plastic by a usual molding method, in addition to the radiator tank as described above. For example, the resin composition of the present invention can be used as a resin composition for forming a chemical pump or the like in addition to the above-described radiator tank and water supply member. In particular, as an engineering plastic for forming a molded article used under severe temperature conditions in which one surface of a molded product wall is in contact with a high-temperature liquid and the other surface is in contact with a low-temperature liquid or gas. It can be suitably used.

Effects of the Invention Since the plastic composition according to the present invention is made of a specific polyamide as described above, its melting point, glass transition point, heat resistance such as heat deformation temperature, tensile strength, bending strength, impact resistance, dynamic friction coefficient, Mechanical properties such as Taber friction, physical and chemical properties such as water resistance, boiling water resistance, salt water resistance, saturated water absorption, chemical resistance, etc., fluidity of melt molded products, melt compression moldability, melt injection moldability, Molding characteristics such as melt extrusion moldability,
Among them, it is particularly excellent in heat resistance and chemical resistance.

Example 1 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist.

Granulation method Using a conventional vented twin-screw granulator (for example, PCM45 of Ikegu Iron Works Co., Ltd., TEX44 of Nippon Steel Works Co., Ltd.), the polyamide resin (aromatic polyamide (A) )) Insert 60 copies, and from the side feeder,
Forty parts of glass fibers (for example, chopped strands having a diameter of 13 μm and a length of 3 mm) were charged and granulated at a cylinder temperature of 340 ° C.

This polyamide (a) contains 35 mol% of terephthalic acid (TA) component units as dicarboxylic acid component units and 15 mol% of aromatic dicarboxylic acid component units other than terephthalic acid (isophthalic acid (IA) component units). Hexamethylenediamine as a diamine component unit in an amount of 50 mol%.

The intrinsic viscosity (measured in concentrated sulfuric acid at 30 ° C.) [η] of this polyamide is 1.1 dl / g, and the glass transition temperature is 125 ° C.

The obtained granules are injected into an injection molding machine (Toshiba IS-55-EPN)
And injection molding under the conditions of a cylinder temperature of 330 ° C. and a mold temperature of 120 ° C. to obtain a 3.2 × 12.7 × 127 mm test piece A of 4 × 12
A test piece B of 0 × 130 mm was formed.

Test Method [Water Resistance] The test piece A was immersed in 100 ° C. for 4 days, and the water absorption (% by weight) was determined from the weight change before and after the water absorption test.
The bending test was performed at -40 to -150 ° C according to ASTM D790.
The temperature range was as follows.

[Linear Expansion Coefficient] A test piece of about 3 × 10 × 3.2 mm was cut from the test piece A in the resin flow direction and the direction perpendicular to the resin flow. The test piece was annealed at 150 ° C. for 1 hour. The linear expansion coefficient was measured by TMA (Thermal Mechancal Analyzer).

[LLC resistance] Nissan genuine long life coolant 50%
Immerse in an aqueous solution at 110 ° C for 1000 hours. The weight change rate before and after the test, the flexural strength retention rate, and the flexural modulus retention rate were measured.

[Calcium chloride resistance] 4 × 10 × in the direction perpendicular to the resin flow from the test piece B
It was obtained by cutting a 120 mm test piece. After immersion in water at 80 ° C. for 24 hours, a strain having a bending strain of 4 mm was applied to the center at a span of 100 mm. A saturated calcium chloride aqueous solution was applied to the surface of the test piece. After repeating a heat cycle of 100 ° C. for 2 hours, room temperature and 1 hour for 10 times, the presence or absence of cracks on the test piece surface was visually determined.

Table 3 shows the results of the above-mentioned water resistance (absorption rate), LLC resistance and calcium chloride resistance.

Comparative Example 1 A test piece A was prepared in the same manner as in Example 1 except that the following polyamide (aromatic polyamide (b)) was used instead of the polyamide resin (aromatic polyamide (a)). , B were molded and the same test as in Example 1 was performed.

 Table 3 shows the results.

[Synthesis of aromatic polyamide (b)] 1,6-diaminohexane 255.6 g (2.2 M), terephthalic acid (TA) 109.6 g (0.66 M), adipic acid (AA) 225.1 g
(1.54M) and sodium hypophosphite 0.47g (4.
4 × 10 ⁻³ M) and 146 ml of ion-exchanged water were charged into a 1.0 reactor, and after purging with nitrogen, reacted at 250 ° C. and 35 kg / cm ² for 1 hour. After the completion of the reaction, the solution was withdrawn to a receiver at a pressure set lower than the reactor by about 10 kg / cm ² , to obtain 510 g of polyamide having an intrinsic viscosity [η] of 0.18 dl / g (concentrated sulfuric acid, 30 ° C.).

Next, after drying this polyamide, it was melt-polymerized at a cylinder set temperature of 310 ° C. using a twin-screw extruder to obtain an aromatic polyamide having an intrinsic viscosity [η] of 1.13 dl / g (concentrated sulfuric acid, 30 ° C.). .

The molar percentage of terephthalic acid component units in this aromatic polyamide was 30%, and the melting point was 281 ° C.

Comparative Examples 2 and 3 Specimens A and B were prepared in the same manner as in Example 1 except that the polyamide shown in Table 3 was used instead of the aromatic polyamide (a).

Using the obtained test pieces A and B, tests were conducted in the same manner as in Example 1 for water resistance (absorption rate), LLC resistance, and calcium chloride resistance. The results are shown in Table 3.

Examples 2 to 4 Comparative Examples 1 to 4 were the same as Comparative Example 1 except that the mole% of the terephthalic acid component unit and the adipic acid component unit constituting the aromatic polyamide was changed as shown in Table 3.

 Table 3 shows the results.

MXD6 is a polyamide formed from meta-xylene diamine and adipic acid (AA).

[Brief description of the drawings]

FIG. 1 is a graph showing an example of a relationship between a change in bending strength of a polyamide with respect to a temperature in a completely dry state and a change in bending strength of a polyamide with respect to a temperature in a water absorbing state.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 77/00-77/12 C08K 3/00-13/08

Claims (3)

(57) [Claims] (1) (A) (i) a terephthalic acid component unit of 40 to 10
A dicarboxylic acid component unit consisting of 0 mol% and 0 to 40 mol% of an aromatic dicarboxylic acid component unit other than terephthalic acid and / or 0 to 60 mol% of an aliphatic dicarboxylic acid component unit; and (ii) an aliphatic alkylenediamine It is composed of a repeating unit consisting of a component unit and / or an alicyclic alkylenediamine component unit, and has an intrinsic viscosity of 0.5 to 3.0 dl / g measured in concentrated sulfuric acid at 30 ° C.
And a polyamide having a melting point of 293 ° C. or higher, and (B) a fibrous inorganic filler, wherein the polyamide (A) is a main component and a water for forming a radiator tank or water. A plastic composition for forming a surrounding member. 2. A plastic composition for forming a radiator tank or water supply member, wherein a filler is added to the polyamide according to claim 1. 3. A radiator tank or plumbing member formed from the plastic composition according to claim 1.