JPH03237161A - Polyamide composition - Google Patents

Abstract

PURPOSE:To obtain a composition excellent in heat resistance, mechanical characteristics, water, chemical resistance, etc., by blending a specific polyamide with a specified amount of an epoxy resin. CONSTITUTION:A polyamide composition obtained by blending (A) 100 pts.wt. polyamide composition, composed of (A1) aromatic dicarboxylic acid component units composed of terephthalic acid component units and aromatic dicarboxylic acid component units other than the above-mentioned component units and/or 4-25C aliphatic dicarboxylic acid component units and (A2) diamine component units composed of aliphatic diamine component units and/or alicyclic diamine component units and having >=0.5dl/g intrinsic viscosity with (B) 0.5-40 pts.wt., preferably 1-30 pts.wt. epoxy resin (e.g. bisphenol A diglycidyl ether expressed by the formula II) having diglycidyl ether type terminal groups expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to polyamide compositions, and more particularly to polyamide compositions that have improved physical and chemical properties such as heat resistance, mechanical properties, water resistance, and chemical resistance, especially tensile elongation. This invention relates to improved polyamide compositions.

Technical background of the invention and its problems JP-A-59-155428 and JP-A-80-18392
Crystalline polyamides containing aromatic dicarboxylic acid units such as No. 7 have superior heat resistance, mechanical strength, water resistance, and chemical resistance compared to aliphatic polyamides; Because it is smaller than polyamide-based polyamides, molded products using it have the disadvantage of being hard and brittle. By the way, a method is known in which a modified olefin polymer is blended for the purpose of improving the toughness of polyamide. (For example, Tokuko Sho 5
5-44108, it is possible to increase the elongation by applying it to a polyamide containing special acid units, but the heat resistance and mechanical strength, which are characteristics of the polyamide, have to be sacrificed considerably.

By the way, JP-A-63-202655 discloses that 100 parts by weight of nylon 46 resin and 1 to 100 parts by weight of phenoxy resin.
A resin composition in which parts by weight are blended has been proposed.

It is stated that the composition maintains the excellent properties of nylon 46 resin, such as tensile strength, and has better moldability than nylon 46 resin.

Furthermore, the publication states that by blending an epoxy resin into the composition, stability of melt viscosity, hydrolysis resistance, etc. can be improved.

That is, the invention described in JP-A-83-202655 was made mainly for the purpose of improving the moldability of aliphatic nylon 46 resin, and the publication describes There is no mention of how to significantly improve the elongation of aromatic polyamides while maintaining excellent properties such as mechanical strength.

Purpose of the Invention The present invention is an attempt to solve the problems associated with the prior art as described above. The object is to provide polyamide compositions with increased toughness.

Summary of the Invention The polyamide composition according to the present invention comprises the following polyamide (A) and 0.05 parts by weight based on 100 parts by weight of the polyamide.
5 to 40 parts by weight of epoxy resin (B), and the polyamide (A) contains terephthalic acid component units, aromatic dicarboxylic acid component units other than terephthalic acid component units, and/or carbon atoms 4 to 2.
an aromatic dicarboxylic acid component unit (a) consisting of an aliphatic dicarboxylic acid component unit of No. 5, and a diamine component unit (b) consisting of an aliphatic diamine component unit and/or an alicyclic diamine component unit, Polyamide (measured in a sulfuric acid at 30°C)
A) is characterized by having an intrinsic viscosity [η] of 0.5d (1/g or more).

Furthermore, in a preferred embodiment of the present invention, the aromatic dicarboxylic acid component units (a) constituting the polyamide (A) in the composition include 30 to 100 mol% of terephthalic acid component units, and aromatic dicarboxylic acid component units other than terephthalic acid component units. It is composed of 0 to 70 mol% of group dicarboxylic acid component units and O to 70 mol% of aliphatic dicarboxylic acid component units having 4 to 25 carbon atoms.

Since the polyamide composition according to the present invention contains the above-mentioned epoxy resin (B) together with the above-mentioned specific polyamide (A), this polyamide composition has heat resistance properties, impact resistance strength, etc. It has excellent mechanical properties, physical and chemical properties such as water resistance and chemical resistance, and molding properties such as stretchability and fluidity, and is particularly excellent in stretchability.

DETAILED DESCRIPTION OF THE INVENTION The polyamide composition according to the present invention will be specifically described below.

The polyamide composition according to the present invention consists of polyamide (A) and epoxy resin (B).

The polyamide (A
) is a dicarboxylic acid component unit (a
) and diamine component unit (b).

That is, this dicarboxylic acid component unit (a) may consist only of terephthalic acid component units, or may consist of terephthalic acid component units and aromatic dicarboxylic acid component units other than terephthalic acid component units, It may consist of a terephthalic acid component unit and an aliphatic dicarboxylic acid component unit, preferably an aliphatic dicarboxylic acid unit having 4 to 25 carbon atoms, and further, a terephthalic acid component unit and an aromatic dicarboxylic acid component other than terephthalic acid. unit and aliphatic/carboxylic acid component unit preferably having 4 to 2 carbon atoms
5 aliphatic dicarboxylic acid units.

Specifically, aromatic dicarboxylic acid component units other than terephthalic acid component units include isophthalic acid,
Examples include component units derived from phthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid, and the like. Among the aromatic dicarboxylic acid component units other than these terephthalic acid component units, component units derived from isophthalic acid or naphthalene dicarboxylic acid are preferred,
Particularly preferred is an isophthalic acid component unit.

Further, the aliphatic dicarboxylic acid component unit is derived from an aliphatic dicarboxylic acid having preferably 4 to 25 carbon atoms, more preferably 6 to 12 carbon atoms, although the number of carbon atoms is not particularly limited. Examples of aliphatic dicarboxylic acids used to derive such aliphatic dicarboxylic acid component units include succinic acid, adipic acid, acelaic acid, sebacic acid,
Mention may be made of decanedicarboxylic acid, undecanecarboxylic acid and dodecanedicarboxylic acid. Among these, adipic acid is particularly preferred.

In the present invention, dicarboxylic acid component units (a), terephthalic acid component units, aromatic dicarboxylic acid component units other than terephthalic acid component units, and/or aliphatic dicarboxylic acid component units, preferably aliphatic dicarboxylic acid components having 4 to 25 carbon atoms. In the case of terephthalic acid component units, 3 terephthalic acid component units in 100 mol% of dicarboxylic acid component units.
It is contained in an amount of 0 to 100 mol%, preferably 30 to 80 mol%, and aromatic dicarboxylic acid component units other than terephthalic acid component units are 0 to 70 mol%, preferably 0 to 50 mol%, more preferably 0 It is desirable that it is contained in an amount of ~30 mol%. In addition, the aliphatic dicarboxylic acid component unit preferably contains 0 to 70 mol%, preferably 10 to 70 mol% of the aliphatic dicarboxylic acid component unit having 4 to 25 carbon atoms.
It is desirable that it be contained in an amount of .

If the dicarboxylic acid component unit (a) contains a terephthalic acid component unit, an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit, and/or an aliphatic dicarboxylic acid component unit in the above amounts, this An aromatic polyamide (A) consisting of a dicarboxylic acid component unit (a) such as and a diamine component unit (b) as described below.
The molded product obtained from the composition containing is particularly excellent in heat resistance properties such as heat distortion temperature, mechanical properties such as tensile strength, tensile elongation, and bending strength, and physicochemical properties such as chemical resistance and water resistance. ing.

Furthermore, in the present invention, the dicarboxylic acid component unit (a)
As such, a small amount, for example, about 10 mol% or less, of polyhydric carboxylic acid component units is contained together with the above-mentioned terephthalic acid component units and/or aromatic dicarboxylic acid component units other than terephthalic acid component units. It's okay.

Specific examples of such polyhydric carboxylic acid component units include tribasic acids and polybasic acids such as trimellitic acid and pyromellitic acid.

In the present invention, the diamine component unit (b) constituting the polyamide (A) may consist only of an aliphatic diamine component unit, or may consist of an aliphatic diamine component unit and an alicyclic diamine component unit. You can leave it there.

Such an aliphatic diamine component unit may be a linear alkylene cyamine component unit or a branched chain alkylene cyamine component unit. Among these aliphatic diamine component units, carbon number is 4.
A linear alkylene diamine component unit having 25 to 25 carbon atoms is preferred, and a linear alkylene diamine component unit having 6 to 18 carbon atoms is more preferred.

Specifically, such aliphatic diamine component units include, for example, 1.6-diamithexane, 1.7-diaminohbutane, 118-diaminooctane, 1.9-diaminononane, and 1.10-diaminohexane. aminodecane,
Examples include component units derived from linear alkylene diamines such as i, it-diaminoundecane and 1,12-diaminododecane.

The polyamide (A) used in the polyamide resin composition of the present invention has an intrinsic viscosity [η] measured in concentrated sulfuric acid at a temperature of 30°C of usually 0.5 d1)/g or more, preferably 0.6 dN/g. g or more, more preferably 0.7 to
3.0 dN/g, particularly preferably 0.8 to 1.5627 g
Use those within the range.

Such polyamide (A) can be produced, for example, using a conventionally known method.

For example, Polymer Reviews, 10. C
on-densation PolyIlers by
Interfacial and 5solution
Methods (by PJ, Morgan) Int
er-scjence Pub 5hers (1,96
5) ) Or Makromol, Chem,...
47.93-113 (1961), a diacid halide of an aromatic dicarboxylic acid capable of deriving the constituent unit of the polyamide (A) described above and a diamine are polycondensed by a solution method. Possibly polyamide (
A) can be obtained. Polyamide (A) can also be obtained by interfacial polymerization.

Alternatively, an aromatic dicarboxylic acid corresponding to the aromatic dicarboxylic acid component unit and a diamine or a polyamide salt thereof corresponding to the diamine component unit are melted in the presence or absence of a solvent such as water. Polyamide (A) can be obtained by polycondensation.

Furthermore, the polyamide (A) can also be obtained by generating an oligomer by using the above-mentioned solution method or the like, and then subjecting it to rough polycondensation by a solid phase polymerization method.

In addition, the diamine component units forming the polyamide (A) may include aromatic diamine component units in addition to the alkylene diamine component described above, and such aromatic diamine component units include: Specifically, for example, component units derived from aromatic diamines such as conventional xylylene diamine and p-xylylene diamine can be mentioned. These aromatic diamines can be used alone or in combination of two or more.

The epoxy resin (B) contained in the polyamide composition according to the present invention is a highly reactive three-membered ring epoxy compound.

Such epoxy resins (B) include epoxy resins with or groups bonded to the molecular ends of chain-like or branched chain molecules, or epoxy resins with two or more epoxy groups in the molecular chains other than the molecular ends. Examples include linear aliphatic epoxide type epoxy resins containing linear aliphatic epoxide type epoxy resins, and alicyclic epoxide type epoxy resins containing two or more epoxy groups in the molecular chain having an alicyclic structure. resin is used.

Glycidyl ether type.

Bisphenol A diglycidyl ether Bisphenol A diβ methyl glycidyl ether Bisphenol F diglycidyl ether Tetrahydroxyphenylmethane Tetraglycidyl ether Resolun glycidyl ether Halogenated bisphenol A diglycidyl ether Polyalkylene glycol diglycidyl ether such as cisyl ether and polypropylene glycol diglycidyl ether Hydrogenated bisphenol A glycicyl ether Diglycidyl ether of bisphenol A alkylene oxide adduct Epoquine urethane resin Glycerin triglycidyl ether Pentaerythritol cyclycidyl ether glycidyl ether・Ester type P-oxybenzoic acid chrycidyl ether ・Ester glycidyl ester type; Phthalic acid diglycidyl ester Tetrahydrophthalic acid diglycidyl ester Hexahydrophthalic acid diglycidyl ester Polyacrylic acid phosphorus ester Dimer acid diglycidyl ester Crisidyl Amine-type glycidyl aniline tetracricidylcyamino diphenylmethane tricidyl isocyanurate linear aliphatic epoxy resin epoxidized polybutadiene epoxidized Soyura alicyclic epoxy resin 3.4 epoxy-6 methylcyclohexyl methyl 3.4
Epoxy-6 methyl cyclohexane carboxylate 3.4 epoxy cyclohexine methyl (3,4-epoxycyclohexane) carboxylate bis (3,4-epoxy-6 methyl cyclohexyl methyl) adibate vinyl cyclohexene jepoxide dicyclobentadiene oxide bis (2,3-Epoxycyclobentyl) ether limonene dioxide The above-mentioned epoxy resins, such as phenolic or alcohol-based glycidyl ethers, glycidyl esters, and glycidyl amines, can be used for the corresponding polyhydric alcohols, polybasic acids, It can be prepared by reacting a polyamine with epichlorohydrin and removing hydrochloric acid.

Epoxidized olefins can be prepared by reacting a peracid, such as peracetic acid, with the double bonds of the olefin.

In the present invention, the following bisphenol compounds can also be used when preparing such an epoxy resin.

Specifically, as bisphenol compounds that can be used in the present invention, 1. L-bis-(4-hydroxyphenyl)ethane, 1.1-bis-(4-hydroxyphenyl)propane, 2.2-bis-(4-hydroxyphenyl)butane, 2.2-bis-(4-hydroxy phenyl)pentane, 2,2-bis-(4-hydroxyphenyl)-3-methylbutane, 2,2-bis-(4-hydroxyphenyl)hexane, 2,2-bis-(4-hydroxyphenyl)-4 -Methylpentane, 1,1-bis-
(4-hydroxyphenyl)cyclopentane, 1.1-
Bis-(4-hydroxyphenyl)cyclohexane, bis-(4-hydroxy-3-methylphenyl)methane,
l, 1-bis-(4-hydroxy-3-methylphenyl)ethane, 2.2-bis=(4-hydroxy-3-methylphenyl)propane, 2.2-bis-(4-hydroquine-3-ethyl phenyl)propane, 2,2-bis-(
4-hydroxy-3-1s.

propylphenyl)propane, 2,2-bis-(4-hydroxy-3-sec-butylphenyl)propane, bis-(4-hydroxyphenyl)phenylmethane, 1.
1bis-<4-hydroxyphenyl>=1-phenylethane, 1.1-bis-(4-hydroxyphenyl)-1
-Phenylpropane, bis-(4-hydroxyphenyl>diphenylmethane, bis-(4-hydroxyphenyl>dihenzylmethane), 4.4'-dihydroxydiphenyl ether, 4.4'-dihydroquine diphenyl sulfone, 4.4'-7hydroxy Examples include diphenyl sulfite and phenolphthalein.

In the present invention, among the above epoxy resins,
It is preferable to use a grindyl ether type epoxy resin, and among them, a phenolic epoxy resin is preferable, and it is particularly preferable to use an epoxy resin using bisphenol A as a main raw material.

The epoxy equivalent weight of such epoxy resin is usually 170
~3500.

In the polyamide composition according to the present invention, the polyamide (A) and epoxy resin (B) as described above are such that the epoxy resin (B) is 0% based on 100 parts by weight of the polyamide (A).
．． It is used in amounts of 5 to 40 parts by weight, preferably 1 to 30 parts by weight.

When the epoxy resin (B) is used in the above amount relative to 100 parts by weight of the polyamide (A), an effect of increasing elongation is exhibited, and the composition does not become extremely brittle.

The polyamide composition according to the present invention has polyamide (A) and epoxy resin (B) as essential components as described above, but in addition to these essential components, organic or inorganic filler may be added as necessary. , antioxidants, ultraviolet absorbers, photoprotectants, heat stabilizers, phosphite stabilizers, peroxide decomposers, basic adjuvants, nucleating agents, plasticizers, lubricants, antistatic agents, flame retardants , pigments, dyes, etc.

These fillers can also be used in combination of two or more. Further, these fillers can be treated as silane coupling agents or titanium coupling agents and used.

The amount of the organic or inorganic fibrous filler is usually 200 parts by weight or less, preferably 5 to 180 parts by weight, and more preferably 5 to 180 parts by weight, based on 1.00 parts by weight of the polyamide (A). Preferably, it is included in the polyamide composition of the present invention in an amount of 5 to 150 parts by weight.

The polyamide composition according to the present invention can be prepared by a method in which a filler is added while maintaining each component of the polyamide composition in a molten state. On this occasion,
An extruder, kneader, etc. can be used.

The polyamide composition according to the present invention as described above can be molded by conventional melt molding methods, such as compression molding, injection molding, or extrusion molding.

The polyamide composition according to the present invention can be used for various purposes such as engineering plastics by a normal molding method.

Effects of the Invention The polyamide composition according to the present invention consists of (A) polyamide and (B) epoxy resin in an amount of 0.5 to 40 parts by weight based on 100 parts by weight of the polyamide, and the polyamide (A) comprises: Terephthalic acid component unit, aromatic dicarboxylic acid component unit other than terephthalic acid component unit, and/or carbon number 4 to 2
an aromatic dicarboxylic acid component unit (a) consisting of an aliphatic dicarboxylic acid component unit of No. 5, and a diamine component unit (b) consisting of an aliphatic diamine component unit and/or an alicyclic diamine component unit, Intrinsic viscosity [η
] is in the range of 0.5 dll/g or more, so mechanical properties such as heat resistance and impact strength,
It has excellent physical and chemical properties such as water resistance and chemical resistance, and molding properties such as stretchability and fluidity, and is particularly excellent in tensile elongation.

[Examples] Next, the polyamide composition according to the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 A dicarboxylic acid component consisting of 70 mol% terephthalic acid and 30 mol% isophthalic acid, and hexamethylene diamine [η] -0,94 (l waste sulfuric acid, 30°C), melting point 32
100 parts by weight of polyamide at 7°C and 5 parts by weight of the following epoxy resin were supplied to a twin screw extruder set at 330°C to prepare a blend (bellet). Thereafter, a test piece was injection molded at a cylinder temperature of 330°C and a mold temperature of 120°C. The obtained test pieces were tested for the items listed in Table 1.

The results are shown in Table 2.

[Epoxy resin] Bisphenol A type epoxy resin with an evoquine equivalent of 2400 (manufactured by Mitsui Petrochemicals Co., Ltd., R, -309) Comparative example 1 Same as Example 1 except that no epoxy resin was used. .

The results are shown in Table 2.

Comparative example 2. Examples 2 to 3 Example 1 was carried out in the same manner as in Example 1 except that the amount of the epoxy resin was changed as shown in Table 2.

The results are shown in Table 2.

Example 4 The polyamide used in Example 1 was mixed with terephthalic acid 60
mol%, dicarboxylic acid component consisting of adipic acid 40 mol% and hexamethylene diamine [η]-1,13
The procedure was the same as in Example 1 except that polyamide having a melting point of 326° C. was used and the amount of epoxy resin was changed as shown in Table 2.

The results are shown in Table 2.

Comparative Example 3 The same procedure as Example 4 was carried out except that the epoxy resin was not used.

The results are shown in Table 2.

Example 5 The polyamide used in Example 1 was treated with terephthalic acid 7
0 mol%, a dicarboxylic acid component consisting of 20 mol% of picic acid, 10 mol% of isophthalic acid and [η]-1,07 consisting of hexamethylene diamine, a melting point of 338°C polyamide, and an amount of epoxy resin. The procedure was the same as in Example 1 except that the values were changed as shown in Table 2.

The results are shown in Table 2.

Comparative Example 4 The same procedure as Example 5 was carried out except that no epoxy resin was used.

The results are shown in Table 2.

table

Claims (4)

[Claims] (1) Consists of (A) polyamide and (B) epoxy resin in an amount of 0.5 to 40 parts by weight based on 100 parts by weight of the polyamide, and the polyamide (A) comprises terephthalic acid component units, terephthalic acid component units Aromatic dicarboxylic acid component unit other than that and/or carbon number 4 to 2
an aromatic dicarboxylic acid component unit (a) consisting of an aliphatic dicarboxylic acid component unit of No. 5, and a diamine component unit (b) consisting of an aliphatic diamine component unit and/or an alicyclic diamine component unit, Intrinsic viscosity [η
] is in the range of 0.5 dl/g or more. (2) Aromatic dicarboxylic acid component units (a) include 30 to 100 mol% of terephthalic acid component units, 0 to 70 mol% of aromatic dicarboxylic acid component units other than terephthalic acid component units,
and 0 aliphatic dicarboxylic acid component units having 4 to 25 carbon atoms.
The polyamide composition according to claim 1, characterized in that it is composed of 70 mol%. (3) The epoxy resin (B) is an epoxy resin having a glycidyl ether type terminal group represented by formula (i); The polyamide composition according to claim 1. (4) Bisphenol A diglycidyl ether whose epoxy resin (B) is represented by formula (i-1); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(i-1) [However, formula ), n is an integer from 0 to 25. ] The polyamide composition according to claim 1, characterized in that: