JPH06220312A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing a polyester resin, a polyamide resin and a specific thermoplastic polymer at specific ratios, having excellent compatibility, heat-resistance, chemical resistance, etc., and useful as film, sheet and compound. CONSTITUTION:This resin composition contains (A) 95-5 pts.wt. (preferably 60-40 pts.wt.) of a polyester resin (e.g. liquid crystal polyester), (B) a polyamide resin (e.g. nylon 6) and (C) 0.1-10 pts.wt. of a thermoplastic polymer derived from (i) 100 pts.wt. in total of the components A and B (at a ratio of preferably 60/40 to 40/60) and (ii) 0.001-5 pts.wt. of an organic acid ammonium salt (preferably ammonium oxalate and/or ammonium succinate).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention improves the compatibility by adding a predetermined amount of a thermoplastic polymer having a polyester resin and a polyamide resin as main components and having a high affinity for both resins. The present invention relates to a thermoplastic resin composition used for a film sheet or a compound, which has good heat resistance, impact resistance, molding processability, and chemical resistance.

[0002]

2. Description of the Related Art Saturated polyester resins are generally rich in surface smoothness, although they may vary depending on their structure.
It has a glossy appearance. Crystalline polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) have a high melting point and a high degree of crystallinity, and are excellent in dimensional stability, transparency, toughness, electrical insulation and chemical resistance. It is widely used in films, molded products, etc., but has the drawback of poor impact resistance and boiling water resistance and a large specific gravity. On the other hand, amorphous polycarbonate (PC) and polyarylate (PAR) are excellent in heat resistance, mechanical properties and transparency, and are crystalline PE even in impact resistance.
It is considerably better than T and PBT, and it has electrical and electronic parts, O
Although it is used in applications such as A equipment and precision machinery, it has the drawback of poor solvent resistance. On the other hand, polyamide-based resins such as polyamide 6 and polyamide 66 are tough and have excellent chemical resistance, abrasion resistance, and lubricity, and are used in a wide range of applications such as clothing and textiles, but they have high water absorption and impact resistance. It has the disadvantage of poor performance. Generally heat resistant,
Since it is difficult to obtain a resin composition having good properties such as impact resistance, moldability, chemical resistance, etc. from a single resin, two or more types of resins capable of compensating for each defect A method called a polymer alloy is used. However, the compatibility between each resin is usually poor, and it is difficult to obtain a thermoplastic resin having the advantages of each resin because it is not possible to form an incompatible micro phase separation structure simply by mixing them. is there. As a method for improving the compatibility, a method of adding a compatibilizing agent having an affinity to any of the resins to be combined is generally performed, but in the case of polyester resin and polyamide resin, there is no suitable compatibilizing agent. The improvement effect was insufficient.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have conducted extensive studies to obtain a compatibilizer having an affinity for both polyester resins and polyamide resins, and as a result, the ammonium salts of organic acids have been added to polyester resins. When added and melt mixed, molecular chain scission occurs, and thermoplasticity obtained by further reacting the active intermediate having the carboxylic acid group generated at that time with a polyamide resin having a functional group capable of reacting It was found that the polymer has an effect of remarkably improving the compatibility between the polyester resin and the polyamide resin, and has completed the present invention.

[0004]

Means for Solving the Problems That is, the present invention provides (a) 95 to 5 parts by weight of polyester resin, (b) 5 to 95 parts by weight of polyamide resin, and (c) the polyester resin and the polyamide resin. Of 100 parts by weight,
(A) 80 to 20 parts by weight of polyester resin, (b) 20 to 80 parts by weight of polyamide resin, and (c) 100 in total of the polyester resin and the modified polyamide resin.
With respect to parts by weight, ammonium salts of organic acids, particularly preferably oxalic acid and / or ammonium succinate are added in an amount of 0.00
1 to 5 parts by weight, and 0.1 to 10 parts by weight of a thermoplastic polymer obtained by melting and reacting at 220 to 300 ° C. for 0.5 to 8 hours. It is about things. The polyester resin used in the thermoplastic resin composition and the thermoplastic polymer of the present invention is not particularly limited and is commercially available. For example, PET, PBT, aromatic PC, PAR, <
Liquid crystal polyesters commercially available under the names such as Zaider>, <Vectra>, <Rod Run> and the like can be mentioned. These resins or the copolyester resins obtained by using a plurality of raw material components may be used alone or in combination of two or more kinds. The polyamide resin used in the thermoplastic resin composition and the thermoplastic polymer of the present invention is not particularly limited and is commercially available. Hexamethylenediamine, decamethienediamine, dodecamethylenediamine, 1,3- Or diamines such as 1,4-bis (aminomethyl) cyclohexane, m- or p-xylenediamine such as aliphatic, alicyclic, aromatic and adipic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc. Polyamide resin produced from dicarboxylic acid such as aliphatic, alicyclic, aromatic, etc., or polyamide resin produced from lactam such as ξ-caprolactam and ω-dedecalactam, and a mixture thereof or a copolymerization of these components. Examples include polyamide resins. Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 6, 10), polyhexamethylene dodecamide (nylon 6, 12), poly Undecanamide (nylon 1
1), polydodecanamide (nylon 12), polyxylene adipamide, polyhexamethylene terephthalamide,
Examples thereof include polyphenylene phthalamide. These resins may be used alone or in combination of two or more.

In the present invention, the polyester resin (a) and the polyamide resin (b) are (a) :( b) =
95: 5 to 5:95 parts by weight, preferably 80:20 to 2
0:80 parts by weight, more preferably 70:30 to 30: 7
It is blended in the range of 0. The amount of polyamide resin blended is 5
If it is less than 5 parts by weight, the effect of improving chemical resistance and boiling water resistance becomes insufficient, and if the amount of the polyester resin compounded is less than 5 parts by weight, the effect of improving water absorption and impact resistance becomes insufficient. Become. The ammonium salt of an organic acid used in the thermoplastic polymer of the present invention is an important component that acts as a reaction catalyst for the polyester resin and the polyamide resin.
The organic acid ammoniums are not particularly limited and are commercially available, for example, ammonium oxalate,
Examples include ammonium succinate, ammonium tartrate, ammonium bioxalate, ammonium benzoate, and ammonium citrate. Among them, ammonium oxalate and ammonium succinate are in the temperature range just before kneading the materials (around 200 ° C at most). In the temperature range (250-300)
It is particularly preferred because it has the property of rapidly decomposing or sublimating at (° C). 80 to 20 parts by weight of the polyester resin (a), 20 to 80 parts by weight of the polyamide resin (b), and 100 parts by weight of the total amount of the polyester resin (a) and the polyamide resin (b) are mixed with an organic acid. Ammonium salts, particularly preferably 0.001 to 5 parts by weight of oxalic acid and / or ammonium succinate are added, and 220 to 3
The thermoplastic polymer of the present invention can be obtained by performing a melt reaction at 00 ° C for 0.5 to 8 hours. The reaction can be carried out in air, but since it causes coloration, it is preferably carried out under a nitrogen stream. In the present invention, the polyester resin (a) and the polyamide resin (b) are
(A) :( b) = 80: 20 to 20:80 parts by weight, preferably 70:30 to 30:70 parts by weight, more preferably 60:40 to 40:60 parts by weight. If the blending amount of the polyester resin is less than 20 parts by weight or the blending amount of the polyamide resin is less than 20 parts by weight, the effect of improving the compatibility is reduced. If the amount of the ammonium salt of an organic acid is less than 0.001 part by weight, the effect of promoting the reaction becomes insufficient, and if it exceeds 5 parts by weight, the characteristics are deteriorated. When the reaction temperature is lower than 220 ° C, the resin becomes difficult to melt, and when it exceeds 300 ° C, thermal decomposition starts. If the reaction time is less than 0.5 hours, the reaction between the resins becomes insufficient, and if it exceeds 8 hours, the reaction no longer proceeds. 0.1 to 10 parts by weight of a thermoplastic polymer is added to 100 parts by weight of a resin composition in which a polyester resin (a) and a polyamide resin (b) are mixed in a predetermined ratio, and a biaxial kneader or the like is used. By kneading with, it is possible to obtain a thermoplastic resin composition having good compatibility and a good appearance. If the blending amount of the thermoplastic resin composition is less than 0.1 part by weight, the effect of improving the compatibility becomes insufficient, and if the blending amount exceeds 10 parts by weight, the compatibility becomes too good and the properties deteriorate. ..

As described above, the thermoplastic polymer of the present invention has an effect of remarkably improving the compatibility between the polyester resin and the polyamide resin, because the ammonium salt of the organic acid is reacted. By acting as a catalyst, a reaction occurs between the polyester resin and the polyamide resin,
A reaction product having a polyester component and a polyolefin component in the same molecule acts as a surfactant to improve the compatibility of the polyester resin and the polyamide resin and to form an incompatible micro phase separation structure. It is thought that this is possible. The thermoplastic resin composition of the present invention further comprises other compounding agents such as talc, mica, calcium carbonate, wollastonite, or other inorganic fillers, or glass fibers, carbon fibers, etc., depending on the use and purpose. Reinforcing agents, flame retardants, flame retarding aids, antistatic agents, stabilizers, pigments, release agents, impact modifiers such as elastomers, and the like can be added. As a method for producing the thermoplastic resin composition of the present invention, a conventionally known method can be applied, and the raw materials of the thermoplastic resin composition of the present invention are collectively or divided and sufficiently mixed with a Henschel mixer. It can be obtained by further kneading with a twin-screw kneader.

[0007]

【Example】

<< Example 1 >> Polyester resin (Dianite R MA
-523V Mitsubishi Rayon Co., Ltd. 60 parts by weight, polyamide resin (UBE Nylon R 1013FB Ube Industries)
40 parts by weight of Co., Ltd. and 0.2 parts by weight of ammonium oxalate were placed in a stainless beaker equipped with a stirrer, evacuated and then replaced with nitrogen. After melt-reacting for 3 hours and then applying vacuum to remove the remaining ammonium oxalate, it was cooled to room temperature under a nitrogen stream and pulverized to obtain a thermoplastic polymer A of the present invention. Polyester resin (Dianite R MA
-523V Mitsubishi Rayon Co., Ltd. 60 parts by weight, polyamide resin (UBE Nylon R 1013FB Ube Industries)
(Manufactured by Co., Ltd.) 40 parts by weight and 5 parts by weight of the thermoplastic polymer A are put into a Henschel mixer and mixed at 800 to 1200 rpm for several minutes, and the resin temperature is set to 270 to 28 by a biaxial kneader.
Melt-kneading to make pellets under the condition of 0 ℃,
Thereafter, injection molding was performed, and the obtained test pieces were evaluated for tensile strength, tensile elongation, Izod impact strength, chemical resistance, and water absorption. The evaluation results are shown in Table 1. << Example 2 >> 40 parts by weight of aromatic polycarbonate resin (Panlite RL-1225 Teijin Chemicals Ltd.), polyamide resin (UBE Nylon R 1013FB Ube Industries Ltd.)
60 parts by weight) and 1 part by weight of ammonium succinate are put into a stainless beaker equipped with a stirrer, vacuum is applied and nitrogen is replaced, and a melting reaction is carried out for 2 hours under the condition that the resin temperature becomes 270 to 280 ° C. It was cooled to room temperature under a nitrogen stream and pulverized to obtain a thermoplastic polymer B of the present invention. Aromatic polycarbonate resin (Panlite RL-1225 Teijin Chemicals Ltd.) 40 parts by weight, polyamide resin (UBE Nylon R 1013FB Ube Industries Ltd.) 60 parts by weight, thermoplastic polymer B3 parts by weight in a Henschel mixer. Throw in,
The mixture was mixed at 800 to 1200 rpm for several minutes, melted and kneaded in a twin-screw kneader under conditions such that the resin temperature was 270 to 280 ° C. to prepare pellets, and then injection molding was performed. The tensile strength, tensile elongation, Izod impact strength, chemical resistance and water absorption were evaluated. The evaluation results are shown in Table 1. << Examples 3 to 4 >> The mixture preblended with the composition shown in Table 1 was melt-kneaded in the same manner as in Example 1, and the characteristics thereof were evaluated after molding. The evaluation results are also shown in Table 1.

Comparative Example 1 90 parts by weight of a polyester resin (Dianite R MA-523V manufactured by Mitsubishi Rayon Co., Ltd.), a polyamide resin (UBE Nylon R 1013FB)
Ube Industries, Ltd.) 10 parts by weight and ammonium oxalate 0.1 parts by weight were put into a stainless beaker equipped with a stirrer, evacuated and then replaced with nitrogen. The resin temperature was 270-2.
After performing a melting reaction for 2 hours under the condition of 80 ° C. and then applying a vacuum to remove the remaining ammonium nitrate,
It was cooled to room temperature under a nitrogen stream and pulverized to obtain a thermoplastic polymer C. Polyester resin (Dianite R MA-
523V Mitsubishi Rayon Co., Ltd. 60 parts by weight, polyamide resin (UBE Nylon R 1013FB Ube Industries Ltd.)
40 parts by weight) and 5 parts by weight of the thermoplastic polymer C are put into a Henschel mixer and mixed for several minutes at 800 to 1200 rpm, and the resin temperature is 270 to 280 ° C. in a biaxial kneader.
The pellets were melt-kneaded under the following conditions to produce pellets, and then injection molding was performed. The obtained test pieces were evaluated for tensile strength, tensile elongation, Izod impact strength, chemical resistance, and water absorption. The evaluation results are shown in Table 2. << Comparative Example 2 >> 40 parts by weight of aromatic polycarbonate resin (Panlite RL-1225, Teijin Chemicals Ltd.), polyamide resin (UBE Nylon R 1013FB, Ube Industries Ltd.)
60 parts by weight Ammonium succinate 8 parts by weight is put into a stainless beaker equipped with a stirrer, and after vacuuming, the atmosphere is replaced with nitrogen, and the mixture is melted and reacted for 2 hours under the condition that the resin temperature is 270 to 280 ° C. Cool down to room temperature under airflow,
It was pulverized to obtain a thermoplastic polymer D. Aromatic polycarbonate resin (Panlite RL-1225 Teijin Kasei Co., Ltd.)
40 parts by weight, polyamide resin (UBE nylon R 10
13FB, 60 parts by weight of Ube Industries, Ltd., and 3 parts by weight of the thermoplastic polymer D were charged into a Henschel mixer, and 800-1
Mix for several minutes at 200 rpm, melt-knead the mixture with a twin-screw kneader under conditions such that the resin temperature is 270 to 280 ° C. to make pellets, then perform injection molding, and obtain tensile strength of the obtained test piece. The tensile elongation, Izod impact strength, chemical resistance and water absorption were evaluated. The evaluation results are shown in Table 2. << Comparative Examples 3 to 4 >> The mixture preblended with the composition shown in Table 2 was melt-kneaded in the same manner as in Example 1, and the characteristics of the mixture were evaluated after molding. The evaluation results are also shown in Table 2. << Comparative Examples 5 to 8 >> The mixture preblended with the composition shown in Table 3 was melt-kneaded in the same manner as in Example 1, and the characteristics thereof were evaluated after molding. The evaluation results are also shown in Table 3.

[0009]

[0010]

[0011]

* 1 Diamondite R MA-523V Mitsubishi Rayon Co., Ltd. * 2 Panlite RL-1225 Teijin Chemicals Co., Ltd. * 3 UBE Nylon R 1013FB Ube Industries Co., Ltd. * 4 Tensile strength: ASTM D It measured according to -638. * 5 Tensile elongation: Measured according to ASTM D-638. * 6 Izod impact strength: Measured according to the method described in ASTM D256 for a 1/4 "width notched test piece. * 7 Chemical resistance: The bending test piece was immersed in chloroform at 23 ° C for 3 months, and the appearance change was observed. In the table, ◯ indicates that it can be used, Δ indicates that it is slightly corroded or swollen, and x indicates that it cannot be used. * 8 Water absorption rate: Measured according to ASTM D570.

[0013]

As is apparent from Tables 1 to 3, in the thermoplastic resin composition of the present invention, the compatibility of the polyester resin and the polyamide resin becomes remarkable by adding the specific thermoplastic polymer. It is a new and well-balanced material with improved heat resistance, impact resistance, molding processability, and chemical resistance that have both advantages.

Claims (2)

[Claims] 1. (a) 95 to 5 parts by weight of a polyester resin, (b) 5 to 95 parts by weight of a polyamide resin, and (c)
For 100 parts by weight of the total of the polyester resin and the polyamide resin, (a) polyester resin 80
To 20 parts by weight, (b) 20 to 80 parts by weight of polyamide resin, and (c) 0.001 to 5 parts by weight of ammonium salt of organic acid with respect to 100 parts by weight of the total of the polyester resin and the polyamide resin. Added, 220-300
A thermoplastic resin composition comprising 0.1 to 10 parts by weight of a thermoplastic polymer obtained by melt reaction at 0.5 ° C. for 0.5 to 8 hours. 2. The thermoplastic resin composition according to claim 1, wherein the ammonium salt of an organic acid is an ammonium salt of oxalic acid and / or succinic acid.