JPS59187054A - Heat-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:A composition that is obtained by melt-kneading, under heating, an aromatic thermoplastic resin containing amide and imide groups and a crystalline polyaryl ketone resin, thus showing improved chemical resistance and water- absorbing properties, without any adverse effects on its heat resistance. CONSTITUTION:The objective composition is obtained by adding 0.1-40, preferably 1-35pts.wt. of a crystalline polyaryl ketone having major recurring units of the formula (Z, Z' and Z'' are divalent aromatic residue having at least one of six-membered carbon ring; Q is O, CO or direct bonding; n is 0-3) to 60-99.5, preferably 65-99pts.wt. of an aromatic thermoplastic resin containing amide and/or imide groups. The formed products of the resultant composition are preferably heat treated at a high temperature ranging from 50 deg.C lower than the glass transition point the thermoplastic resin to the transition point.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-resistant thermoplastic resin composition with improved chemical resistance and water absorption properties.

Aromatic thermoplastic resins containing amide groups and/or imide groups, such as aromatic polyamideimide resins, aromatic polyetherimide resins, and aromatic polyamide resins,
Electrical/electronic equipment parts, space/aviation equipment parts, etc. that have excellent heat resistance and mechanical properties and are used at high temperatures.
It is used in a wide range of applications, including automobile parts and office equipment parts. However, all of these aromatic thermoplastic resins do not necessarily have sufficient chemical resistance and water absorption properties, and molded products cannot be used when used in polar organic solvent environments or in high temperature and high humidity atmospheres. caused stress cracks,
The reality is that it can cause problems such as blistering and deformation, so its uses are limited.

Therefore, the present inventors have investigated the heat resistance of aromatic thermoplastic resins containing amide groups and/or imide groups, such as aromatic polyamide-imide resins, aromatic polyetherimide resins, and aromatic polyamide resins. As a result of extensive research in order to improve chemical resistance and water absorption properties without sacrificing the properties, we discovered that heating and melt-mixing crystalline polyarylketone resin is extremely effective.
We have arrived at the present invention.

That is, the present invention is directed to the use of aromatic thermoplastic resins containing more than 60 parts by weight of amide groups and/or imide groups.
Parts by weight or less and general formula % formula %) (wherein Z, Zl, Z" are divalent aromatic residues containing at least one carbon 6-membered ring, Q is O, CO or a direct bond, n is an integer from 0 to 3) as a main structural unit. Provides a heat-resistant thermoplastic resin composition obtained by heat-melting and mixing 011 parts by weight or more and less than 40 parts by weight of a crystalline polyarylketone resin whose main structural unit is a repeating unit of It is.

The aromatic thermoplastic resin containing an amide group and/or an imide group used in the present invention contains an amide group and/or an imide group as a part of the linking group of the aromatic nucleus constituting its main chain, and It has thermoplastic characteristics, typical examples of which are aromatic polyamide-imide resin,
Examples include aromatic polyetherimide resins and amorphous aromatic polyamide resins.

These resins will be explained in more detail below.

The polyamide-imide resin (hereinafter abbreviated as FAI resin) used as one of the aromatic thermoplastic polymers of the present invention has a repeating unit represented by the general formula as a main constituent unit, and has 5D to 1
00 (preferably 50 to 100) molty, and other aromatic polymers that may have the following (■) general formula (2) in an amount less than 70 (preferably 50) molty. It has thermoplastic properties.

Some of the imide bonds in structures (1) and (2) include the amic acid bond I 1 as its ring-closed precursor. Here, Ar is a trivalent aromatic group containing at least one carbon 6-membered ring, and the divalent one is due to the fact that two carbonyl groups are bonded to adjacent carbon atoms in the benzene ring of Ari. For example, it is possible to specifically list structures such as .

Ar' can be a divalent group containing at least one 6-membered carbon ring (in the formula, Y represents 0, S, Co, 802,80, an alkyl group having 1 to 6 carbon atoms).

Ar// is an aromatic group connected to a tetravalent carbonyl group containing at least one carbon 6 negative ring, two of which are bonded to adjacent carbon atoms in the benzene ring of the Ar" group. R is a divalent aromatic and/or alicyclic residue, and specific examples include CHs -OH2℃-CH2-1-<E>-CH , -■-1, etc. These PAI resins can be produced by reacting a combination of polar compounds such as dimethylformamide, dimethylacetamide, N-)'fk pyrrolidone, and cresol. The introduction of the structural unit (It) polyamide unit and/or (2) polyimide unit, which can be partially copolymerized as necessary to the structural unit (1) as the structural unit (
This can be achieved by substituting and reacting the raw materials during the production of the PAI resin in step 1).

Among them, a typical FAI resin is sold by Amoco, Inc. in the United States, and has the following molecular structure. These manufacturing methods are described in British Patent No. 1,056,5 filed by Standard Oil Company.
No. 64, US Patent No. 3,661,862, and the like.

The aromatic polyetherimide resin (hereinafter abbreviated as PEI resin) used as one of the aromatic thermoplastic polymers of the present invention has a repeating unit represented by the general formula as a main unit, and has two main units: an ether bond and an imide bond. It is an aromatic polymer composed of as an essential bonding unit. Ar%Ar' and R here are the same as those shown in the above formulas (1) and (n). A typical example thereof is one having the following structural formula.

The amorphous aromatic polyamide resin (hereinafter abbreviated as FA resin) used as one of the aromatic thermoplastic polymers of the present invention is an aromatic polymer whose main constituent unit is a repeating unit represented by the general formula. Both R and Ar' here are the same as those defined in formula (II)) and have thermoplastic properties. A typical example thereof is one having the following structural formula.

This is a polymer represented by a crystalline polyarylketone tree used in the present invention. Here Z, Z'.

z it:+ is a divalent aromatic residue containing at least one carbon 6-membered ring, for example, Q is O, CO or a direct bond, and n represents an integer from 0 to si.

In particular, a typical crystalline polyarylketone resin is a polyetheretherketone resin (hereinafter referred to as
(abbreviated as PEEK resin), manufactured by British Imperial
It is commercially available from Chemical Industries, Inc. The method for its production is disclosed in European Patent No. 1879 and the corresponding Japanese Patent Application Laid-Open No. 54-90296, in which 150-
4,4'-difluorobenzo 7 under the temperature condition of 400℃
, produced by reacting enone and hydroquinone.

In addition to the aryl ketone structural unit as a main component, other copolymerized units can be partially introduced into the crystalline polyaryl ketone resin used in the present invention, if necessary. The method for producing these copolymers is disclosed in British Patent No. 141442.
It is disclosed in the specification of No. 1, Japanese Patent Application Laid-Open No. 52-58000, etc.

The composition of the present invention is an aromatic thermoplastic resin containing an amide group and/or an imide group (hereinafter referred to as heat-resistant thermoplastic resin) exceeding 60 parts by weight and not more than 99.9 parts by weight,
Preferably 65 to 99 parts by weight and 0.1 to 40 parts by weight of crystalline polyarylketone resin, preferably 1
It is prepared by heat-melting and mixing ~35 parts by weight. If the amount of the crystalline polyarylketone resin blended is less than 0.1 part by weight, the effect of improving the chemical resistance and water absorption properties of the heat-resistant thermoplastic resin is undesirable. Further, if the amount is 40 parts by weight or more, the excellent mechanical strength inherent to the heat-resistant thermoplastic resin decreases, which is not preferable.

The composition of the present invention may further contain at least 70% by weight of at least one filler, if necessary. Examples of the fillers used include (a) wear resistance improvers: graphite, carborundum, silica powder, molybdenum disulfide, fluororesin, etc.; (b) reinforcing agents: glass fiber, carbon fiber, boron fiber. , fluoride carbide twill fibers, carbon whiskers, asbestos fibers, asbestos fibers, etc., (C) flame retardant improvers such as antimony ditrioxide, magbasium carbonate, calcium carbonate, etc., (d) electrical property improvers. : Clay, mica, etc. (e) Tracking resistance improver:
Asbestos, silica, graphite, etc. (f) Acid resistance improver: barium sulfate, silica, calcium metasilicate, etc.
(b) Thermal conductivity improvers: Metal powders such as iron, zinc, aluminum, copper, etc. (h) Others Nigaras beads, glass spheres, calcium carbonate, alumina, Merck, diatomaceous earth, hydrated alumina, mica, shirasu balloons , asbestos, various metal oxides, inorganic pigments, and other synthetic and natural compounds that are stable at 350°C.

In preparing the composition of the present invention by heating, melting, and mixing,
Equipment used to melt blend additional rubbers or plastics can be utilized, such as thermal o-A/, /<nary mixers, gravebenders, extruders, and the like. The mixing operation is continued until a homogeneous formulation is obtained.

Mixing temperature 11t 340-400 (preferably 350-3
80)°C is appropriate. The crystalline polyarylketone resin, heat-resistant thermoplastic resin, and fillers added as necessary can be separately fed to a melt mixer, or these raw materials can be fed in advance to a mortar. It is also possible to pre-mix using a Henschel mixer, ball mill, ribbon blender, etc. and then supply it to a melt mixer. In addition, when melt-mixing a three-component system, in addition to the method of melt-blending the crystalline polyarylketone resin, heat-resistant thermoplastic resin, and filler all at once, there is also a method in which the crystalline polyarylketone resin and the filler are melt-blended in advance. It is also possible to utilize a two-stage blending method, in which a master pellet is produced by melt-blending a material and a heat-resistant thermoplastic resin.

Although the composition of the present invention can be formed into a homogeneous melt blend and subjected to injection molding or extrusion molding, it can also be applied to other compression molding, sintering molding, etc.

When the molded article obtained by molding the composition of the present invention is heat-treated at a high temperature below the glass transition temperature of the heat-resistant thermoplastic resin and above the glass transition temperature -50°C, chemical resistance, water absorption properties, mechanical properties and The effect of further improving heat resistance can be obtained.

The molded article obtained by molding the composition of the present invention has excellent properties such as heat resistance, mechanical properties, electrical properties, sliding properties, and solvent resistance properties, and can be used for many purposes. can do.

For example, compositions useful for automobile parts, electric/electronic parts, water supply and distribution equipment parts, sliding members, etc. can be designed and formulated.

Hereinafter, the present invention will be further explained in detail by giving examples.

It should be noted that the values of "ch", "ratio" and "parts" shown in the present examples indicate weight %, weight ratio and parts by weight, respectively, unless otherwise specified.

Further, the chemical resistance and water absorption properties in this example were measured by the following method.

Chemical resistance was determined by fixing one end of a 12 x 60 x 3 M rectangular parallelepiped test piece, applying a constant load of 200 (immediate/ca) to the other end, and attaching a cotton cloth saturated with a polar organic solvent to the fixed part.
The time required for the test piece to break was measured.

The water absorption properties were determined based on ASTM D-570 by completely immersing a 12x100x3U rectangular parallelepiped test piece, which had been completely dried in advance, in distilled water at 23°C and 100°C.
After 24 hours, take it out and wipe the entire surface with a dry cloth.
The weight increase was measured.

Examples 1 to 4 and Comparative Examples 1 to 2 PEEK resin (manufactured by Imperial, Chemical, Industries, Ltd., glass transition temperature 143°C, melting point 664°C) and FAI resin represented by the formula (manufactured by Amoco Corporation "Torlon 4203")
L'') was triblended with the composition shown in Table 1, and then fed to a Brabender Grastograph Extruder at a processing temperature of 550 to 660°C and a screw rotation speed of 50 rl.
) m to obtain homogeneous melt-blended pellets.

Next, the homogeneous melt blend pellets obtained above were heated to a temperature of 666.
A molded test piece was prepared by compression molding at 1001 F/ca at a temperature of 1001 F/ca, and the mechanical properties, chemical resistance and water absorption properties were measured, and the results shown in Table 1 were obtained.

As is clear from the results in Table 1 below, in the case of Examples 1 to 4,
Compared to Comparative Example 1 in which no PEEK resin was added, the effect of improving chemical resistance and water absorption properties is remarkable.

As the amount of PEEK resin added increases in the order of Examples 6 and 4, the chemical resistance and water absorption properties are improved, but the bending stress and impact strength are slightly lowered accordingly. Then, as shown in Comparative Example 2, the amount of PEEK resin added was 60
%, undesirable effects such as large decreases in bending stress and impact strength occur.

PEI resin (General Electric Company J!
! 70 parts of ``Ultem-1000'') and 30 parts of the same PEEK resin as in Example 1 were triblended using a ribbon blender, and then a 401 Jg extruded rock equipped with a full-flight screw with a compression ratio of 2.6 was prepared. (processing temperature 290 to 660°C) and melt-kneaded to obtain a uniform blended composition pellet.

Next, the pellets with the uniform composition were put into an injection molding machine (barrel temperature: 640-370°C, injection pressure: 1000 NF/cr).
lt1 (mold temperature: 150° C.) to prepare physical property test pieces, and the chemical resistance, water absorption properties and mechanical properties were measured, and the results shown in Table 2 were obtained.

As is clear from the results in Table 2 in the margin below, the composition of Example 5 to which PEEK resin was added had particularly good chemical resistance and It showed excellent improvement effects in terms of water absorption properties.

It is shown in Example 6 and Comparative Example 4, and the relative viscosity is 1.20 (solvent: chloroform,
Polymer concentration: D, 5. lii'/dl, measurement temperature = 30
After tri-blending a PEI resin with the characteristics of A uniformly blended pellet was obtained by melt-kneading.

Next, the temperature of the uniformly mixed pellet t-i was 370°C.

After forming a molded test piece by compression molding at a pressure of 50 m/d, physical properties were measured, and the results shown in Table 6 were obtained. As can be seen from the results, the composition of this example had physical properties that were higher than those of the PE resin alone in Comparative Example 4.
In particular, it showed excellent improvement effects in terms of chemical resistance and water absorption properties.

Example 7 and Comparative Example 5 Synthesized by low-temperature solution polymerization using acid chloride method Logarithmic viscosity 0.45 (polymer concentration: o, 5ti,
Solvent: N-methylpyrrolidone, measurement temperature: 30°C)
AI resin and synthesized formula m/n = 70/
50 molti) crystalline polyarylketone copolymer resin (glass transition temperature 163°C, melting point 340m?)
After tri-blending with the composition shown in the table, the mixture was melt-kneaded in the same manner as in Example 1 to obtain a uniformly blended pellet.

Next, the uniformly mixed pellet was heated at a temperature of 370'C and a pressure of 50°C.
Niri/cI! After compression molding was performed to create a molded test piece, physical properties were measured, and the results shown in Table 3 were obtained. As can be seen from the results, the composition of this example showed excellent improvement effects, particularly in terms of chemical resistance and water absorption properties, compared to the physical properties of the PAI resin of Comparative Example 5 alone.

Example 8 and Comparative Example 6 4.4'-2,2-propylbis (shown by the formula synthesized by solution polymerization from an equimolar mixture of p-phenyleneoxyfudianiline and isophthalic acid dichloride, logarithmic viscosity 1.17 (Solvent dimethylformamide, polymer concentration: 115%, measurement temperature: 30°C) PA resin having the characteristics of A homogeneous blend pellet was obtained by melt-kneading using the method.

Next, the uniformly mixed pellet was heated at a temperature of 66o1 and a pressure of 1ooK.
After forming a molded test piece by compression molding with y/ad, the physical properties were measured, and the results shown in Table 6 were obtained. As can be seen from the results, the composition of this example showed excellent improvement effects, particularly in terms of chemical resistance and water absorption properties, compared to the physical properties of the PA resin of Comparative Example 6 alone.

Example 9 and Comparative Example 7 FA resin having the characteristics of logarithmic viscosity t05 (polymer concentration 20.5 mm, solvent dimethylformamide, measurement temperature = 60 ° C.) expressed by the formula synthesized by solution polymerization and Example 6 The same polyarylketone resin was triblended with the composition shown in Table 6, and then melt-kneaded in the same manner as in Example 1 to obtain a uniformly blended pellet.

Next, the uniformly mixed pellet was heated to a temperature of 660℃ and a pressure of 50℃.
/crA to create a molded test piece, and then its physical properties were measured, and the results shown in Table 6 were obtained. As can be seen from the results, the composition of this example showed excellent improvement effects, particularly in terms of chemical resistance and water absorption properties, compared to the physical properties of the PA resin of Comparative Example 7 alone.

Claims (1)

[Scope of Claims] More than 60 parts by weight and not more than 99.9 parts by weight of an aromatic thermoplastic resin containing an amide group and/or imide group and a general formula % (wherein Z, Zl, Z" are at least A crystalline polymer whose main structural unit is a repeating unit of a divalent aromatic residue containing one carbon six-membered ring, Q is O, CO or a direct bond, and n is an integer from 0 to 3. A heat-resistant thermoplastic resin composition obtained by heat-melting and mixing 0.1 parts by weight or more and less than 40 parts by weight of an aryl ketone resin.