JPH01319532A - Polyamide resin and composition - Google Patents

Abstract

PURPOSE:To obtain a polyamide resin having excellent mechanical properties, chemical and physical properties, heat-resistance and moldability, especially impact resistance and flexural strength by adding a specific amount of a monohydroxy aromatic dicarboxylic acid component to an aromatic dicarboxylic acid component. CONSTITUTION:The objective polyamide resin is produced by compounding (A) an aromatic dicarboxylic acid component consisting of 50-98mol% of aromatic dicarboxylic acid component and 2-50mol% of 8-12C monohydroxy aromatic dicarboxylic acid component with (B) a 6-18C aliphatic alkylenediamine component at a molar ratio of 1:0.9-1.1. The polyamide resin is compounded with a filler to obtain a polyamide resin composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to polyamide resins and compositions, and more specifically, they have excellent mechanical properties, chemical and physical properties, heat resistance, and moldability, and in particular have excellent bending strength. and a polyamide resin and composition with excellent impact resistance.

[Conventional technology]

In general, thermoplastic resins such as polyolefins, polyesters, and polyamides have excellent moldability and can be easily melt-molded such as compression molding, injection molding, and extrusion molding. Even in all the properties of heat resistance, they are not satisfactory as engineering plastics, and they are used in various general-purpose molding fields by taking advantage of each property.

On the other hand, as engineering plastics with superior mechanical properties, chemical and physical properties, and heat resistance,
polytetrafluoroethylene known as Teflon®, polyparaphenylene terephthalamide known as Kevlar®, and 4,4′-diaminodiphenyl ether and pyromellitic anhydride known as Kapton®. Polyimides consisting of condensates, polyhexamethylene adipamide known as 6,6-nylon, and poly(2,2,4-1-limethylhexamethylene terephthalamide 1-) known as Torogami FT (f registered trademark). ), polyphenylene sulfite,
Polyacetal and the like are used for various purposes. However, among these, polytetrafluoroethylene, polyparaphenylene terephthalamide, and the above-mentioned polyimils have excellent mechanical properties, chemical and physical properties, and heat resistance, but cannot be melt-molded, so they cannot be used effectively. The field is severely limited. On the other hand, polyphenylene sulfite, polyhexamethylene adipamide, poly(2゜2.4-1~limethylhexamethylene terephthalamide), polyacetal, etc. all have the advantage of being able to be melt-molded. However, on the other hand, polyphenylene sulfite has poor heat resistance properties such as melting point, glass transition point, and heat distortion temperature, and mechanical properties such as impact strength and abrasion resistance.
, 4,4-trimethylhexamethylene terephthalamide), etc., all have high tensile strength, bending strength,
It is inferior in mechanical properties such as limit PV value and abrasion resistance, chemical properties such as chemical resistance, boiling water resistance, and saturated water absorption, and heat resistance properties such as glass transition point and heat distortion temperature. Furthermore, polyacetal is inferior in mechanical strength such as bending strength, impact strength, and abrasion resistance, and in heat resistance properties such as melting point and heat distortion temperature.

In order to solve the above-mentioned problems with conventional engineering plastics, we developed a new plastic that consists of an aromatic dicarboxylic acid component unit whose main component is terephthalic acid component unit, and an aliphatic alkylene diamine component unit having 6 to 8 carbon atoms. Polyamide resin has mechanical strength, chemical and physical properties,
It has been proposed as having excellent heat resistance and formability, and especially excellent sliding properties (Japanese Patent Application Laid-open No. 60-158
No. 220).

However, the bending strength and impact resistance of this polyamide resin were not necessarily satisfactory. [Problems to be Solved by the Invention] The purpose of the present invention is to solve the above-mentioned problems by improving mechanical properties and impact resistance. Polyamides 1 to 1 have excellent chemical and physical properties, heat resistance, and moldability, and especially have excellent bending strength and impact resistance.
The present invention provides resins and compositions.

[Means to solve the problem]

The present invention relates to the following polyamide resin and composition.

(1) (a) Aromatic dicarboxylic acid component unit is 50 to 98
and (b) aromatic dicarboxylic acid component units having 2 to 50 mol% of monohydroxy aromatic dicarboxylic acid component units having 8 to 12 carbon atoms. A polyamide resin consisting of an aliphatic alkylene diamine component unit.

(2) (A) (a) aromatic dicarboxylic acid component unit is 5
Aromatic dicarboxylic acid component units in the range of 0 to 98 mol%, and monohydroxy aromatic dicarboxylic acid component units having 8 to 12 carbon atoms in the range of 2 to 50 mol%;
(b) a polyamide resin comprising an aliphatic alkylene diamine component unit having 6 to 18 carbon atoms; and (B) a polyamide resin composition comprising a filler.

The aromatic dicarboxylic acid component unit (a) constituting the polyamide resin of the present invention is composed of an aromatic dicarboxylic acid component unit (al) other than monohydroxy aromatic dicarboxylic acid, and a monohydroxy aromatic dicarboxylic acid component unit (from aJ to Therefore, it is necessary that the monohydroxy aromatic dicarboxylic acid component unit (a2) is included in the aromatic dicarboxylic acid component unit (a). Specifically, component units such as terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, and naphthalene dicarboxylic acid can be exemplified, and one type or two or more types of these can be used. Among these, terephthalic acid component units, isophthalic acid component units, or naphthalene dicarboxylic acid component units, particularly terephthalic acid component units and isophthalic acid component units, are preferably used.Moreover, as monohydroxyaromatic dicarboxylic acid component units (a2), Specifically, component units such as 5-hydroxyisophthalic acid and 3-hydroxy-1,8-naphthalene dicarboxylic acid can be exemplified, and one type or two or more types of these can be used.

Among these, 5-hydroxyisophthalic acid component units are particularly preferably used.

In the present invention, among the aromatic dicarboxylic acid component units (a), the aromatic dicarboxylic acid component m-position (a□) accounts for 50 to 98 mol%, and the monohydroxy aromatic dicarboxylic acid component units (a2) is required to be in the range of 2 to 50 mol%. Aromatic dicarboxylic acid component unit (a
), aromatic dicarboxylic acid component units (a,) are 50
If it is less than mol%, the resin molded product has a tensile strength,
1110 is inferior in mechanical properties such as strength, heat resistance properties such as heat distortion temperature, and chemical and physical properties such as chemical resistance and water resistance.

In the present invention, the aromatic dicarboxylic acid component unit (a) may contain a small amount of polyhydric carboxylic acid component units such as adipic acid, sebacic acid, 1 helimeryl acid 1-acid, and pyromellitic acid 1-acid.

In the polyamide resin according to the present invention, the aliphatic alkylene diamine component unit (b) is a linear or branched alkylene diamine component unit having 6 to 18 carbon atoms. Specific examples of such alkylene diamine component units include:
For example, 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-],]4-dimethylbutane 1,4-diamino-2,3-dimethylbutane, 1,2-diamino-1-methylethane, 1,6-
Cyamitzhexane, 1,7-diaminohebutane, 1,8
-diaminooctane, 1,6-diamitwo-2,5-dimethylhexane, 1,6-diamitwo-2,4-dimethylhexane, 1,6-diamitwo-3,3-dimethylhexane, 1,6-diamitwo-2,2-dimethyl hexane,
1,9-diaminononane, 1,6-diamitwo 2.2
．． 4-1-dimethylhexane, 1,6-diamitsu2.
4.4-1~limethylhexane, 1,7-diamy2,3-dimethylhebutane, 1,7-diamy2,4
-Dimethylhebutane, 1,7-diami2,5-dimethylhebutane, (1), 7-diami2,2,2-dimethylpebutane, (2).

10-diaminodecane, 1,8-diamino-1,3-dimethyloctane, ■, 8-diamino-1,4-dimethyloctane, 1,8-diamino-2,4-dimethyloctane, core 8-diamino-3, 4-dimethyloctane, 1,8-diamino-4,5-dimethyloctane, ]
, ]8-diamino-2,2-dimethyloctane 1,8
-Diamino-3,3-dimethyloctane,],]8-diamino-4,4-dimethyloctane 1,6-diamino-2,4-diethylhexane, 1,9-diamino-5-
Methylnonane, 1,11-diaminoundecane, 1,1
Examples include component units such as 2-diaminododecane. These can be used alone or in combination of two or more. Among these, component units of 1,6-siamitsuhexane, 1,8-diaminooctane, 1,10-diaminodecane, ],]]2-diaminododecane or a mixture of these component units are particularly preferably used.

In the polyamide resin of the present invention, the composition of the aromatic dicarboxylic acid component unit (a) is preferably selected depending on the number of carbon atoms in the aliphatic alkylene diamine component unit (b).

That is, as the number of carbon atoms in 1. aliphatic alkylene diamine component unit -8=(b) increases from 6 to 18, the composition of the aromatic dicarboxylic acid component unit (a) changes to the aromatic dicarboxylic acid component unit (a). It is preferable to increase the proportion of In this way, the aliphatic alkylene diamine component unit (
By selecting the composition of the aromatic dicarboxylic acid component unit (a) according to the number of carbon atoms in b), the resulting polyamide resin has particularly excellent moldability, as well as mechanical properties such as bending strength and abrasion resistance. Also, a molded product having excellent heat resistance properties such as heat aging resistance and heat distortion temperature can be obtained.

The component ratio of the aromatic dicarboxylic acid component unit (a) and the aliphatic alkylene diamine component unit constituting the polyamide resin of the present invention is 1:0.9 to 1.1 in molar ratio, but the molar ratio is The ratio is preferably 1:0.9 to 1.2.

The polyamide resin of the present invention comprises an aromatic dicarboxylic acid component unit (a) consisting of an aromatic dicarboxylic acid component unit (a) and a monohydroxy aromatic dicarboxylic acid component unit (a2), and an aliphatic alkylene diamine component unit ( b) is a polyamide resin randomly bonded with a structural unit substantially represented by the following general formula [I], and a general formula [■]
It has a structure in which the structural units represented by are arranged irregularly in a linear manner in a molar ratio of 50 to 98:2 to 50.

[In the formula, R represents an alkylene group having 6 to 18 carbon atoms, and Ar
1 represents an aryl group other than a monohydroxy-substituted aryl group having 6 to 10 carbon atoms. Further, Ar2 represents a monohydroxy-substituted aryl group having 6 to 1 carbon atoms. ] The polyamide resin of the present invention is soluble in concentrated sulfuric acid at a temperature of 50°C, and has an intrinsic viscosity [η] of 0.5 to 4.0801 g when measured in concentrated sulfuric acid at a temperature of 30°C. Preferably 0.6 to 3.5 dΩ/g, particularly preferably 0.7
~3.0dll/g, glass transition point [Tg] 80~2
The temperature is preferably 40°C, preferably in the range of 100 to 200°C.

Such a concentrated sulfuric acid-soluble polyamide can be obtained by a conventionally well-known method.

For example, Polymer Revietis, 10.
Condensation Polymers by
Interfacial, and 5olutj, o
n Methods (by P. Il. Morgan,
Intersc]ence Publishers(1
965)), Makromol, Chem, 4
7.93-113 (196])), a diacid halide of an aromatic dicarboxylic acid, which is a constituent unit of the polyamide resin described above, and an aliphatic alkylene diamine are polycondensed by a solution method. You can get it by doing this. It can also be obtained by interfacial polymerization.

Alternatively, it can be obtained by polycondensing the aromatic dicarboxylic acid and an aliphatic alkylene diamine or a nylon salt thereof by a melt method in the presence or absence of a solvent such as water. Furthermore, it can also be obtained by polycondensing the polyamide oligomer obtained by the former method by an in-phase polymerization method, or by polycondensing the polyamide oligomer in a heated molten state under shearing conditions using a cross-wire means.

The polyamide resin of the present invention contains not only the above-mentioned concentrated sulfuric acid-soluble polyamide, but also a polyamide that has substantially the same range of structural units as this concentrated sulfuric acid-soluble polyamide, but is insoluble in concentrated sulfuric acid at 50°C. Good too. here 5
Polyamide that is insoluble in concentrated sulfuric acid at 0°C is obtained by crushing the polyamide, heating and stirring a 1% by weight concentrated sulfuric acid solution of the polyamide that has passed through 32 meshes at 50°C for 10 hours.
Filtered through a 2G glass filter at a temperature of 50°C,
Refers to polyamide from which the soluble portion has been removed. Such concentrated sulfuric acid-insoluble polyamide has a melt viscosity at 360°C and a load of 2.16 kg (
AFR) is usually 20g/]O min or less, preferably 5g
/10 minutes or less, particularly preferably O, ], g/10 minutes or less.

Such concentrated sulfuric acid-insoluble polyamide can be produced as a by-product during the production of the concentrated sulfuric acid-soluble polyamide. Furthermore, by selecting the reaction conditions, the amount produced can be intentionally increased. Therefore, in such a case, a mixture of a polyamide soluble in concentrated sulfuric acid and a polyamide insoluble in concentrated sulfuric acid can be obtained. Furthermore, if necessary, by further crosslinking the polyamide soluble in concentrated sulfuric acid or the mixture thereof with the polyamide insoluble in concentrated sulfuric acid, the polyamide can be made into a polyamide insoluble in concentrated sulfuric acid.

Therefore, methods for producing concentrated sulfuric acid-insoluble polyamide or a mixture of concentrated sulfuric acid-soluble polyamide and concentrated sulfuric acid-insoluble polyamide include, for example, a method of further homopolymerizing the above-mentioned concentrated sulfuric acid-soluble polyamide, and a method of producing concentrated sulfuric acid-soluble polyamide by melt polycondensation. In this case, the polycondensation temperature is increased to a higher temperature.
For example, the final temperature is about 340°C or higher, and the molar ratio of alkylene diamine and aromatic dicarboxylic acid is 1.0.
Examples of 3 or 2 include a method of polycondensing these, and a method of polycondensing polyamines and polycarboxylic acids with trifunctionality or more in combination with alkylene diamines and aromatic dicarboxylic acids. .

When producing the concentrated sulfuric acid soluble polyamide or the concentrated sulfuric acid insoluble polyamide, catalysts and stabilizers such as phosphoric acid, hypophosphite, octyl phosphate, and tristridecyl phosphite can be used.

In the polyamide 1 to resin according to the present invention, the concentrated sulfuric acid-insoluble polyamide is preferably contained in an amount of 1000 parts by weight or less per 100 parts by weight of the concentrated sulfuric acid-soluble polyamide. In particular, according to the invention, 2 to 1000 parts by weight, preferably 3 to 600 parts by weight of concentrated sulfuric acid-insoluble polyamide per 100 parts by weight of concentrated sulfuric acid soluble polyamide,
Particularly preferably, when the content is in the range of 5 to 400 parts by weight, I
A product with excellent mechanical strength such as II-chip strength can be obtained.

Here, the ratio of concentrated sulfuric acid soluble polyamide to concentrated sulfuric acid insoluble polyamide in the polyamide resin is determined by the following method. That is, a 1% by weight concentrated sulfuric acid solution of the polyamide mixture ground through 32 meshes was heated with stirring at a temperature of 50°C for 10 hours, cooled to room temperature, and filtered through a 2G glass filter to obtain the polyamide as a precipitate. and polyamide, which is obtained by precipitating polyamide contained in the filtrate with water, are collected and dried, and their respective weights are measured.

The polyamide resin composition according to the present invention is a mixture of the above-mentioned polyamide resin and a filler such as carbon black, asbestos, glass fiber, kaolin, talc, silica, silica alumina, etc. It is formulated with 200 pieces of precious oil. By blending such a filler, it is possible to improve the abrasion resistance such as the dynamic friction coefficient, taper friction, and critical pv value of the molded product, as well as the mechanical properties such as tensile strength, till L strength, and flexural modulus, and heat distortion temperature. A resin composition having excellent chemical and physical properties such as heat resistance and water resistance can be obtained. In addition to the components listed in item 1, the resin composition of the present invention includes an antioxidant, an ultraviolet absorber, a photoprotector, a phosphite stabilizer, a peroxide decomposer, a basic adjuvant, a nucleating agent, and a plasticizer. It is also possible to incorporate lubricants, antistatic agents, flame retardants, pigments, dyes, etc. Furthermore, other polymers can be blended into the resin composition of the present invention within a range that does not impair its physical properties. The blending ratio of these additives is within an appropriate range.

〔Effect of the invention〕

According to the present invention, since a monohydroxy aromatic dicarboxylic acid component unit is added to the aromatic dicarboxylic acid component unit,
Polyamide resins and compositions can be obtained that have excellent mechanical properties, chemical and physical properties, heat resistance, and moldability, and particularly excellent impact resistance, and can therefore be widely used as molding materials.

〔Example〕

Examples of the present invention will be described below.

Glass transition point (Tg) of polyamide resin in Examples
, melting point (Tm) and intrinsic viscosity [η] are shown below.

(],) Glass transition point (Tg), melting point (Tm) MODEL DSC-2 manufactured by PerkinElmer Differential Scanning Calorimetry i-
It is determined by performing differential thermal analysis of the resin using No. 1 at a heating rate of 10° C. each time.

(2) Intrinsic viscosity [η] Resin concentration 0.500g/dQ, 0.770g/dff,
1. OOg/dQ(7) 96% by weight concentrated sulfuric acid solution at 30°C
The relative viscosity at is measured using an Ubbelohde viscometer to determine the specific viscosity, and [η] is determined by plotting from these points.

The method for preparing the test piece and the evaluation method for each performance in this example are as follows.

(Preparation of test piece and evaluation method of physical properties) Polyamide resin was heated at 120°C and 10mmHg for 12 hours.
After drying for 10 hours, it was molded using a press molding machine in a nitrogen atmosphere for 10 hours.
2 from the melting point of the polyamide composition under a pressure of 0 kg/aJ
After hot pressing at a temperature higher than 0'C, cold pressing is performed at a temperature of 20C to produce a compression molded plate having a thickness of 2 mm. After cutting these molded plates to the dimensions of each test piece listed in Table 1, they were heated at 120°C, 110C11O, in a nitrogen atmosphere.
The sample was dried for 12 hours under the following conditions and tested according to the test method shown in Table 1.

Table 1 Examples: 164.47 g (0,990 M) of terephthalic acid, 1.47.53 g (0,810 M) of 5-hydroxyisophthalic acid, and 5.45 g (2) of 1,6-diamithexane (
1,854M) was charged into an IQ autoclave with 61g of ion-exchanged water and 0.38g (0,0036A) of sodium hypophosphite, and after sufficient N2 substitution, the mixture was heated for 3 minutes with stirring.
The temperature was raised to 250°C over time. After further reacting for 1 hour at 250'C in a sealed state, stirring was stopped and the reaction mixture was extracted from the bottom of the autoclave at a differential pressure] of OJ/cJ. The mixture was dried overnight at 80° C., ]000 mm 11 in N, to obtain a lower condensate.

[η] of this low-order condensate (in 1 sulfuric acid, 30°C) is 0.1
It was 0dfl/g. This low-order condensate was processed using a twin-screw extruder (
Screw diameter 30mm, L/D = 42, 3rd, 4th, and 6th zones of the barrel are open to atmosphere vent h, rotation speed 50r
pm, oligomer supply rate 2 kg/hr, exhaust gas N, purge) to proceed with melt condensation to obtain a polymer.

Examples 2 to 6 Polymers were produced by the method described in Example 1, except that the ratios of dicarboxylic acid component units, diamine component units, and each dicarboxylic acid component unit were changed.

Comparative Example 1 Terephthalic acid 89.71 g (0,540 M), 5-hydroxyisophthalic acid 229.48 g (1,260 M) and 1,6-diamithexane 215.45 g (1,8
The polymer was prepared as described in Example 1, except that 54M) was used.

Comparative Examples 2 to 6 Polymers were produced by the method described in Example 1, except that the order of dicarboxylic acid components and the ratio of diamine component units to each dicarboxylic acid component unit were changed.

Table 2 shows the components, physical properties, and characteristics of Example 1 and Comparative Example. Abbreviations in Table 2 indicate the following compounds.

TA: Terephthalic acid A: Isophthalic acid 5-111A: 5-hydroxyisophthalic acid C6D
A: 1,6-cyamitsuhexane C1oDA: 1
, 10-diaminodecane Examples 7 to 8 40 fl (% by weight) of glass fiber was added to the polymer produced by the method described in Examples 3 and 4 to prepare a resin composition.

The components and characteristic values of Examples 7-8 and 3-4 are summarized in Table 3.

Claims (1)

[Claims] (1) (a) Aromatic dicarboxylic acid component unit is 50 to 98
and (b) aromatic dicarboxylic acid component units having 2 to 50 mol% of monohydroxy aromatic dicarboxylic acid component units having 8 to 12 carbon atoms; A polyamide resin consisting of an aliphatic alkylene diamine component unit. (2) (A) (a) The aromatic dicarboxylic acid component units are in the range of 50 to 98 mol%, and the monohydroxy aromatic dicarboxylic acid component units having 8 to 12 carbon atoms are in the range of 2 to 50 mol%. A polyamide resin composition comprising a polyamide resin comprising a certain aromatic dicarboxylic acid component unit, (b) an aliphatic alkylene diamine component unit having 6 to 18 carbon atoms, and (B) a filler.