JPS6239629A - Polyamide-imide and use thereof - Google Patents

Abstract

PURPOSE:A polyamide-imide, containing terephthaloylalkylenediamine units, isophthaloylalkylenediamine units and specific imide bond-containing units and having heat resistance, impact resistance and sliding characteristics at the same time. CONSTITUTION:A polyamide-imide consisting of (A) 0-90mol% terephthaloylalkylenediamine component units expressed by formula I, (B) 10-90mol% isophthaloylalkylenediamine component units expressed by formula II, (C) 3-95mol% imide bond component units expressed by formula III and (D) 0-95mol% imide bond-containing component units expressed by formula IV (X1-X4 are positive integers 6-20) within 90/10-0/100 molar ratio range of the components (A) to (B) and 97/3-5/95 molar ratio range of the total of the components (A) and (B) to the component (C) and having 0.3-4dl/g intrinsic viscosity measured in concd. sulfuric acid at 30 deg.C and >=0.1 melt flow rate (MFR) under 10kg load at 360 deg.C when components insoluble in concd. sulfuric acid at 30 deg.C are contained.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to polyamide-imide and Regarding the composition. More specifically, the present invention relates to polyamide-imide having excellent heat resistance properties, sliding properties, impact resistance, moldability, etc.

[Conventional technology]

Various melt-formable polyamides or polyamide-imides made of aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, and tridilytic acid and aliphatic alkylene diamines have been proposed. For example, the present inventors have proposed a polyamideimide produced from phthalic acid, tridilytic acid, and aliphatic alkylene diamine in Japanese Patent Application Laid-Open No. 58-98552, and in Japanese Patent Publication No. 49-36
No. 959, JP-A No. 59-5 Mohegei 4-G Polyamide produced from moss hexamethylene diamine and terephthal or isophthalic acid, 2.11.4-) Rimethyl hexamethylene diamine Polyamides (Trogamide ■), which are produced from terephthalic acid and terephthalic acid, have been proposed.

Although these polyamides or polyamide-imides have excellent melt moldability, thermoplastic resins with even better heat resistance, impact resistance, and sliding properties are required for applications such as molding materials and sliding materials. It is being

[Problems to be solved by the invention] The present inventors have proposed Fi! Considering that polyamide or polyamide-imide, which is used as a material for type 2 or sliding material, is in such a situation, we are working diligently to develop a new polyamide-imide with improved heat resistance, impact resistance, and sliding properties. investigated. As a result, a polyamide consisting of the terephthaloyl-alkylene diamine component unit (a), the isophthaloyl-alkylene diamine component unit fb), the specific imide bond-containing component unit (c), and other imide bond-containing component units (a) as necessary. The inventors have discovered that the polyamide imide is a new polyamide-imide that achieves the above-mentioned objectives, and that the new polyamide-imide can be used as a molding material or a sliding material that is poor in heat resistance, impact resistance, and sliding properties, and has thus arrived at the present invention.

[Means for solving the neck point] and [effect] According to the present invention, the isophthaloyl alkylene diamine component unit (b) represented by the terephthaloyl alkylene diamine represented by the general formula (1')
), an imide bond-containing component unit (c) represented by the general formula (i!!') and/or an imide bond-containing component unit (d) represented by the general formula (i!!'), [in the formula,
x1, x2, x3 and x4 are positive integers from 6 to 20], the composition of each component is (a) component O to 90 mol%;
(b) the component is 10 to 90 mol %, (c) the component is solid or 95 mole %, (d) the QtE content is Q to 95 mol %
% by mole, the mole ratio of (feed component/component (b)) is in the range of 90/10 to O/100, and [(
The molar ratio of a) component (b) component) / (fc) component (d) component] is in the range of 9715 to 5/95, and (11) the intrinsic viscosity measured in concentrated sulfuric acid at 50 ° C. 560 if [η] is in the range of 0.5 to ddl/g or contains components insoluble in concentrated sulfuric acid at 50°C.
℃, load 1akti'''c measured MFR is 0.111
;/1 A polyamide-imide characterized by [3 minutes or more, be done.

The terephthaloyl alkylene diamine component unit fa) constituting the polyamideimide of the present invention has the formula -S [in the formula x1
represents an integer from 6 to 20], and the content thereof must be in the range of 0 to 90%.
Preferably 20 to 85 mol%, particularly preferably 30
The content ranges from 80% to 80% by mole. (a) When the content of the component unit is more than 90 moles, the flexibility decreases and the impact resistance significantly decreases.

Moreover, the isophthaloyl alkylene diamine component unit (b) constituting the polyamideimide of the present invention is.

an inphthaloyl alkylene diamine component unit represented by the general formula C1l') [wherein X2 represents an integer of 6 to 20],
Its content needs to be in the range of 10 to 90 mol%, preferably 10 to 80 mol%, particularly preferably 20 to 70 mol%. The content of the inphthaloyl alkylene diamine component unit is 10
If it is less than 90 mol% or more than 90 mol%, tensile strength, bending strength, isot impact strength, heat aging resistance, etc. will decrease.

The imide bonding component unit (c) constituting the polyamide-imide of the present invention is an imide bonding component unit represented by the general formula (1) [wherein X represents an integer of 6 to 20], and the (c) ) component, preferably 5 to 60 mol%, particularly preferably 1
It ranges from 0 to 40 mol%. When the content of component (C) is less than 3 molar percentages, the impact resistance is reduced, and when it exceeds 95 molar percentages, the heat resistance properties of the polyamide-imide are reduced.

The imide bond-containing component unit (d) constituting the polyamide-imide of the present invention is an imide bond-containing component unit represented by the general formula m [wherein x4 represents an integer of 6 to 20]; The content of E component must be in the range of 0 to 95 mol/%, preferably 0 to 50 7 mol/%, particularly preferably O to 20 mol %.

When the content of the component 1d) exceeds 95 mol%, the heat resistance properties of the polyamide-imide deteriorate.

The content of each component constituting the polyamide-imide of the present invention is within the above range, and the molar ratio of (a) Ffi: min/(h) component is within the range of 90/10 to 0/100. required, preferably E35/15 to 20/
80, especially preferred B Cl/20 to 40/
6 It is within the range of Q. In addition, in the polyamide-imide, the molar ratio of [component (a) + component (b) 1 / (component (c) and component (d))] needs to be in the range of 9715 to 5/95, and is preferably is 9575~50/
70, particularly preferably 90/10 to d O/'60
is within the range of In the polyamideimide, (a) a
If the molar ratio of component/component (b) is greater than 90/10, the impact resistance, heat aging resistance, etc. of the polyamide-imide will decrease; + [
a) If the molar ratio of E component is larger than 97/filtration, the impact resistance and flexibility of the polyamideimide will decrease, and it will be 5/9.
If it is less than 5, the heat resistance properties such as the heat distortion temperature of the polyamide-imide will decrease.

When the polyamide-imide of the present invention is dissolved in concentrated sulfuric acid, [η] measured at 50°C in concentrated sulfuric acid is 0.277 to 4.
It is necessary to be in the range of 617g, preferably O
=S to s, 5dd/heal, particularly preferably in the range 0.5 to 5d//g. When the polyamideimide of the present invention contains components insoluble in concentrated sulfuric acid.

MP'R measured at 360℃ and load 10kq is 0.1
g/l It is necessary that it is 0 min or more, preferably 1 g 710 min or more. The polyamideimide of the present invention may have crystallinity and may be immaculate. The crystallization rate increases as the content of the terephthaloyl alkylene diamine component unit (a) represented by the general formula (I) constituting the polyamide-imide increases.The crystallization rate of the polyamide-imide of the present invention is usually 0. 0 to 50%, preferably 0 to 55
This is the range of the arc.

When the polyamideimide of the present invention has crystallinity, its melting point is usually 250 to 560°C, preferably 250°C to 560°C.
It is in the range of 80 to 350°C. The softening temperature of the polyamideimide of the present invention is usually 150 to 570°C, preferably 160 to 50°C.

÷ Standing RSJ-+117 Go 11 S Piha O--Muta 1 Uraki The alkylene diamine component unit represented by the general formula [I] or the order is an alkylene diamine component unit having 6 to 20 carbon atoms, and specifically Specifically, 1,6-diaminohexane, 1,7-diaminohexane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1.12-
Diaminododecane, 1,15-diaminotridecane, 1
．． 11-diaminotetradecane, 1.15-diaminopentadecane, 1.16-diaminoundecane, 1.17
-diaminoundecane, 1.18-diaminooctadecane, 1.19-noaminononadecane, 1.20-diaminoefsan, etc. can be represented by Wl. These alkylene diamine components may be contained alone or in a mixture of two or more. Among these alkylene diamine components, it is preferable that the number of carbon atoms is in the range of 6 to 16, and it is particularly preferable that the alkylene diamine component has # prime number of 6.

The polyamide-imide of the present invention has component (a), component (b), component (c), and component (a) ri randomly arranged and bonded to form a chain structure. Here, the chain structure is not limited to a linear structure, but may also be a branched structure or a crosslinked structure formed between different molecules. The formation of a branched structure or a crosslinked structure is the imide bond-containing component unit (
d) formed via. The polyamide-imide of the present invention includes a binary polycondensate consisting only of (b) 11i1E component and (c) component, (a) component, (b) component, and (C) component.
A ternary polycondensate consisting of components, a ternary polycondensate consisting of components (b), (c) and (d), component Ta), (
b) 151 minutes - There is a quaternary polycondensate from components (c) and (d). Among the polyamideimides of the present invention,
Polyamideimides having a linear or branched structure, ie, a substantially linear structure, are preferred.

Further, the molecular terminal of the polyamide of the present invention is (a) E portion,
It may be any of the alkylene diamine component, terephthalic acid component, isophthalic acid component, carboxyphthalic acid component, and pyromellitic acid imide component constituting component (b), component (c), or component (d).

When the molecular terminal is the alkylene diamine component, the terminal amine group may be acylated with a lower carboxylic acid or may form a salt. In addition, when the molecular terminal is a terephthalic acid component, an isophthalic acid component, or a carboxyphthalic acid component, the terminal carboxyl group may be esterified with a lower alcohol, amidated with an amine, or with a salt. may be formed, or may form an acid anhydride.

The polyamide-imide of the present invention is obtained by polycondensing the corresponding diamine with an acid chloride such as terephthalic acid chloride, isophthalic acid chloride, trinoliftic anhydride and, if necessary, pyromellitic anhydride dichloride by a solution polymerization method or an interfacial polymerization method. , first synthesize the corresponding polyamic acid, then dehydrate and ring-close it by heating,
The method of converting to the polyamideimide of the present invention may be adopted, or the corresponding diamine and terephthalic acid, isophthalic acid, trimellitic acid (trimellitic anhydride may also be used)
If necessary, it can also be synthesized by a solution of carboxylic acid such as pyronolitic acid (or pyronolitic anhydride) in the presence or absence of a solvent such as water, phenol, cresol, or terphenyl, or by a melt polycondensation method. It is possible, and after producing the oligomer by the above method,
It is also possible to employ a method in which a method of increasing the molecular weight by solid phase polymerization is used in combination. Furthermore, it is also possible to adopt a method in which the oligomer is subjected to a melt polycondensation reaction under heating using a kneader such as an extruder or a kneader to form a polymer.

This polyamide is included in the polyamideimide of the present invention.

There is no problem even if it contains polyamic acid before dehydration, which corresponds to imide. The amount is usually less than 50 mole percent, preferably less than 10 mole percent, per polyimide-forming functional group. Further, when synthesizing the polyamideimide of the present invention, catalysts such as phosphoric acid, sodium hypophosphite, octyl phosphate, tristridecyl phosphite, stabilizers, etc. can also be added.

The method for determining the composition of the constituent components of the polyamide-imide of the present invention, and the method for measuring the softening temperature, melting point, intrinsic viscosity [η] and crystallinity are shown below.

(1) Composition of the constituent components of polyamide-imide Perform elemental analysis of carbon, hydrogen, and nitrogen atoms in polyamide-imide, determine their content, and calculate the sum of the content of carbon atoms and hydrogen atoms and the content of nitrogen atoms. The composition of the constituent components of the polycondensate was determined from the ratio.

(2) Using a melting point measuring device made by Nio Co., Ltd. as a softening temperature sample, polyamide ground into fine powder in a mortar was measured at the center of two preparations (approximately
IC'M), raise the temperature at a heating rate of 2°C per minute, observe the temperature at which the polyamide begins to dissolve and the temperature at which the entire amount dissolves, and calculate the average value between these temperatures to calculate the softening of the polyamide-imide. Temperature.

(5) Melting point The melting point was determined by differential thermal analysis of the resin using MJ-800-EY manufactured by Rigaku Denki Co., Ltd. at a heating rate of 10° C. per minute.

(4) Intrinsic viscosity [η] /d (1,0,770tr, /d at resin temperature 0.500
(1,1,00 g/a (l of 96% by weight concentrated sulfuric acid solution)
The relative viscosity at 0°C is measured using an Ubbelohde viscometer, the specific viscosity is determined, and the plot is calculated from these points.
η] was calculated. Note that the solution was prepared at 0°C.

(5) Crystallization rate Wide angle (2
It was determined by performing X-ray analysis of θ near 0° to 5″).

The polyamide-imide of the present invention can be used as a molding material, a sliding material, a fiber fitting agent, an adhesive, and various other uses. Conventionally known polymer stabilizers, plasticizers, mold release agents, lubricants, fillers, etc. can be added to the polyamide as required. Examples of polymers include polyamides such as nylon 6.6 and nylon 6, polyesters, polyethers, and α-olefin elastomers such as maleated ethylene propylene copolymers.

The composition for a molding material of the present invention comprises the polyamideimide [
A] and a filler (Bl).The filler is an organic or inorganic compound having various forms such as powder, plate, fiber, or cloth.
Specifically, silica, alumina, silica alumina, talc, diatomaceous earth, clay, kaolin, quartz, glass, mass power, gelaphite, molybdenum disulfide, nanatsuko, red iron oxide, titanium dioxide, zinc oxide, a! Powdered and plate-like inorganic compounds such as reminium, copper and stainless steel, glass fibers, carbon fibers - boron fibers, ceramic fibers, carbon fibers, boron fibers, ceramic fibers, asbestos fibers,
Fibrous inorganic compounds such as stainless steel t@fiber or secondary processed products such as cross-like products thereof, polyparaphenylenethenephthalamide, polysitaphenyleneterephthalamide, polyparaphenylene isophthalamide,
Bolizo tough 22 shin isofta! Reamide, a condensate of diaminodiphenylene ether and terephthalic acid (isophthalic acid), a wholly aromatic polyamide such as a condensate of p(m)-ami7benzoic acid, diaminodiphenylnylic acid + )V
,! : Heterocyclic-containing F compounds such as wholly aromatic polyamideimides, wholly aromatic polyimides, polynitzimidazole, polyimiguzophenanthroline, etc., such as condensates with tri7litic anhydride or pyrosolidic anhydride, Examples include secondary processed products of polytetrafluoroethylene sodium, such as powder, plate, fiber, or cloth, and two or more of these may also be used as a mixture.

These fillers treated with silane coupler, titanium coupler, etc. can also be used.

Among the fillers described above, it is preferable to use silica, silica-alumina, alumina, titanium dioxide, graphite, molybdenum disulfide, and polytetrafluoroethylene as the powder filler, particularly graphite, molybdenum disulfide, and polytetrafluoroethylene. It is preferable to use fluoroethylene because it improves the wear resistance of the molded article obtained from the composition, such as the coefficient of dynamic friction, taper wear, and limit pv value. The average particle diameter of such a filler is usually in the range of 0.1 mμ to 200 μm, and preferably in the range of 1 mμ to 100 μm because the above-mentioned abrasion resistance is significantly improved. It is usually in the range of more than 0 to 200 parts by weight, preferably in the range of more than 100 parts by weight, and particularly preferably in the range of 0.5 to 50 parts by weight.

Among the fillers, examples of organic fibrous fillers include polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaphenylene isophthalamide fiber, and polyparaphenylene terephthalamide fiber-diaminodiphenyl ether. When wholly aromatic polyamide fibers such as fibers obtained from condensation products with terephthalic acid and sophthalic acid are used, mechanical properties such as tensile strength and izod impact strength of molded articles obtained from the composition are improved. , thermal deformation mrK, and other heat resistance properties are improved.Furthermore, among the fillers, glass fibers, carbon fibers, or boron m fibers are preferably used as inorganic fibrous fillers. Molded body glue obtained from the composition [preferable because it improves mechanical properties such as tensile strength, bending strength-flexural modulus, heat resistance properties such as heat distortion temperature, chemical and physical properties such as water resistance, etc. The average length of the organic or inorganic fibrous filler is usually in the range of 0.1 to 20 mm, especially 1
When it is in the range of 10 mm to 10 mm, the moldability of the composition is improved, and the heat resistance properties such as heat distortion temperature and mechanical properties such as tensile strength and bending strength of the molded article obtained from the composition are improved. This is preferable because it becomes like this. The blending ratio of the organic or inorganic fibrous filler is 10% of the polyamide.
It is usually in the range of 5 to 200 parts by weight, preferably in the range of 5 to 180 parts by weight, and particularly preferably in the range of 10 to 150 parts by weight.

The polyamide-imide produced by the method of the present invention can be molded by conventional melt molding, such as compression molding, injection molding, or extrusion molding. This will be specifically explained using examples. The method for preparing the test piece and the evaluation method for each performance are shown below.

In addition, the following abbreviations used in the table below indicate the following compounds, respectively.

TA: Terephthalic acid A: Isophthalic acid TC: Trimellitic anhydride 06DA: 1,6-diamithexane (Preparation of test piece and evaluation method of each physical property) Polyamideimide was crushed with a crusher (52-hour bath) and 100° C
After drying for 12 hours at 1 lmmHg, the polyamide-imide was molded into 100 kg in a nitrogen atmosphere using a press molding machine.
After hot pressing at a temperature 20"QJ higher than the softening temperature under a pressure of /cm, cold pressing at a temperature of 20°C,
Compression molded plates with a regular thickness of 7 mm to 10 mm were produced. After cutting these molded plates to the dimensions of each test piece listed in Table 1, they were placed in an atmosphere of 23°C and 65% humidity for 96 hours.
After leaving it alone, I gave up on the test.

In addition, filler compound products are made by combining a predetermined amount of pulverized and dried polyamide with a predetermined amount of filler using a single screw extruder (L/D=28.2
0o+mφ) and mixed to obtain a strand of approximately 6 mL. The test pieces were prepared using fillers (II polyamide-imide Example 1 t/7), 99.68 g (0.50 M) of V acid, 49.30 g (0.30 M) of isophthalic acid, and 21 g (0.30 M) of trizolitic acid. .02 g (0.1M), 116.21 g (1,OOM) of hexadiene diamine, 0.65 g of tristridecyl phosphite and 7.0 g of ion-exchanged water.
4 and 11 were placed in an autoclave, and after sufficient N2 substitution, the temperature was raised to 280°C over 2 hours with stirring.

After further allowing the reaction to proceed for 1 hour at 280"C in a sealed pot, stirring was stopped and the pressure difference from the bottom of the autoclave was 1
The reaction mixture was taken out at 00 kq/L near n2. A lower condensate was obtained by drying and operating overnight at 100"C and 100 mmHg in N2. This lower condensate (77) (conc H
2SO4 at 30°C) was 0.1 dl/g. This low-order condensate was processed using a twin-screw extruder (screw diameter 53 mm-L).
/D=42, Barrel temperature (℃) 30/240/260/
280/2811/RO001500152015201
520, 4th and 6th zones are vented to atmosphere, rotation speed 8
0 rpm, oligomer feeding rate 2kq/hr, exhaust N
2 purges) to advance the melt condensation, and [η] is 1.
10dl/g (in cone H2SO4, 50"C)
, a polymer with a softening temperature of 287"C was obtained. The results are shown in Table 2.
It was shown to.

Examples 2 to 5, Comparative Examples 1 to 5 Polyamideimide was synthesized by the method described in Example 1 except that the charging ratio of the acid component was changed as shown in Table 2. The results are shown in Table 2.

Example 6 In Example 1, instead of performing melt polycondensation using a twin-screw extrusion tower, a lower condensate synthesized in the same manner as in Example 1 was subjected to solid phase polymerization under conditions of 250'C11 mmHH.
I went there and got the polymer. The results are shown in Table 2.

Example 7 In Example 1, the charging composition of the ingredients was changed to the composition shown in Table 2, and 1 g of phosphorus MO was used instead of tristridecyl phosphite, and the melt polycondensation temperature was changed using an extruder. (barrel humidity) 50/260/2 F
30/JDo1500152015201520('C
) A polymer was synthesized by the method described in Example 1, except that The results are shown in Table 1.

Comparative Example 4 2, d, d-) Table 2 shows the performance of a polyamide (Trogamide T■, manufactured by Guinamit Nobel) consisting of linochylhexa7,000 diamine and terephthalic acid.

[For] Compositions for molding materials Examples 8 to 11, Comparative Examples 5 and 6 The polymers and fillers listed below were used in the ratios listed in Table 5, under the temperature conditions listed in Table 5, using a screw extruder. The composition was prepared by melt blending.

The results are shown in Table 5.

Examples 12 to 14 Compositions were prepared by the method described in Example 8, except that the fillers listed in Table 4 were used in the molds listed in Table 4 instead of using glass fibers on the day of the examples.

The results are shown in Table 4.

Comparative Row 7 The same method as in Example 12 was carried out except that the polymer described in Comparative Example 1 was used instead of the polymer described in Example 12 to prepare a composition.

The results are shown in Table 4.

Claims (2)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼Terephthaloylalkylenediamine component unit (a) represented by [I], general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] Isophthaloyl alkylene diamine component unit (b), general formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [III] Imide bond component unit (c) and/or general formula represented by [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] The imide bond-containing component unit (d) represented by [in the formula,
x_1, x_2, x_3 and x_4 are positive integers of 6 to 20], wherein the composition of each component (i) is 0 to 90 mol% of component (a);
, component (b) is 10 to 90 mol%, component (c) is 3
Component (d) is in the range of 0 to 95 mol%, and the molar ratio of component (a)/component (b) is 90/
10 to 0/100, and the molar ratio of [component (a) + component (b)]/[component (c) + component (d)] is in the range of 97/3 to 5/95. , and (ii) if the intrinsic viscosity [η] measured in concentrated sulfuric acid at 30°C is in the range of 0.3 to 4 dl/g, or if it contains components insoluble in concentrated sulfuric acid at 30°C, 360°C under load. A polyamide-imide characterized by: MFR measured at 10 kg is 0.1 or more. (2) [A] General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Terephthaloyl alkylene diamine component unit (a) represented by [I], general formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [II] Isophthaloyl alkylene diamine component unit (b), general formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [III] Imide bond component unit (c) and / Or the general formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] The imide bond-containing component unit (d) represented by [in the formula,
x_1, x_2, x_3 and x_4 are positive integers of 6 to 20], wherein the composition of each component (i) is 0 to 90 mol% of component (a);
, component (b) is 10 to 90 mol%, component (c) is 3
Component (d) is in the range of 0 to 95 mol%, and the molar ratio of component (a)/component (b) is 90/
10 to 0/100, and the molar ratio of [component (a) + component (b)]/[component (c) + component (d)] is in the range of 97/3 to 5/95. , and (ii) at 360°C if the intrinsic viscosity [η] measured in concentrated sulfuric acid at 30°C is in the range of 0.3 to 4 dl/g or contains components insoluble in concentrated sulfuric acid at 30°C, Load 10k
A polyamide-imide composition for a molding material, comprising: a polyamide-imide represented by the following, and [B] a filler, having an MFR measured in g of 0.1 or more.