JPH06240077A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a new well-balanced material markedly improved in the compatibility of the constituent polyester resin with the constituent polystyrenic rein, having the merits of both the constituents and excelling in heat and impact resistances, moldability and chemical resistance by using a specified thermoplastic polymer. CONSTITUTION:This resin composition is prepared by mixing 95-5 pts.wt. polyester resin (a) and 5-95 pts.wt. polystyrenic resin (b) with 0.1-10 pts.wt., per 100 pts.wt. total of components (a) and (b), thermoplastic polymer obtained by mixing 80-20 pts.wt. polyester resin (c) with 20-80 pts.wt. modified polystyrenic resin (d) having at least one kind of functional groups selected from among hydroxyl, carboxylic anhydride, carboxyl, epoxy and oxazoline groups with 0.001-5 pts.wt., per 100 pts.wt. total of components (c) and (d), ammonium salt (e) of an organic acid, particularly desirably ammonium oxalate or succinate, and reacting the obtained mixture by melting at 220-300 deg.C for 0.5-8hr.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention improves compatibility by adding a predetermined amount of a thermoplastic polymer having a polyester resin and a polystyrene 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 for films and molded products, but it has the drawback of poor moldability. On the other hand, amorphous polycarbonate (PC) and polyarylate (PAR) have excellent heat resistance, mechanical properties, and transparency, and impact resistance is considerably better than that of crystalline PET and PBT. , OA equipment, precision machinery, etc., but has the drawback of poor solvent resistance. On the other hand, polystyrene-based resins such as polystyrene (PS) and acrylonitrile-styrene copolymer (AS) have excellent moldability, cost and transparency, and are lightweight, so they are used in a wide range of applications such as sundries and plastic models. However, it has the drawback of poor impact resistance and solvent resistance. Generally, it is difficult to obtain a resin composition having good properties such as heat resistance, impact resistance, moldability, and chemical resistance from a single resin. A technique called polymer alloy is used in which two or more kinds of resins are combined. 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 polystyrene 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 compatibilizing agent having an affinity for both polyester resins and polystyrene resins, and as a result, ammonium salts of organic acids have been added to polyester resins. When added and melt-mixed, molecular chain scission occurs, and obtained by further reacting with a modified polystyrene resin having a functional group capable of reacting with an active intermediate having a hydroxyl group or a carboxylic acid group generated at that end It was found that the thermoplastic polymer to be obtained has an effect of remarkably improving the compatibility between the polyester resin and the polystyrene 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 a polyester resin, (b) 5 to 95 parts by weight of a polystyrene resin, and (c) the polyester resin and the polystyrene resin. Of 100 to 100 parts by weight of (a) polyester resin 80 to 20 parts by weight,
(B) Modified polystyrene resin 2 having at least one functional group selected from the group consisting of a hydroxyl group, a carboxylic acid anhydride group, a carboxylic acid group, an epoxy group and an oxazoline group 2.
0 to 80 parts by weight and (c) 0.001 to 5 parts by weight of ammonium salts of organic acids, particularly preferably oxalic acid and / or ammonium succinate, per 100 parts by weight of the polyester resin and the modified polystyrene resin. 0.1 to 10 parts by weight of the thermoplastic polymer obtained by melting reaction at 220 to 300 ° C. for 0.5 to 8 hours.
The present invention relates to a thermoplastic resin composition characterized by being added in parts by weight.

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, PE
Examples include T, PBT, aromatic PC, PAR, <Zider>, <Vectra>, <Rod Run>, and other liquid crystal polyesters that are commercially available. 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. Polystyrene resin used in the thermoplastic resin composition of the present invention is not particularly limited and is commercially available, for example, styrene monomer is heated, light,
Polystyrene resin obtained by polymerizing with a catalyst, or high impact polystyrene containing styrene-butadiene rubber (SBR), butadiene rubber (BR) or other synthetic rubber for improving the impact resistance of polystyrene resin, styrene and acrylonitrile Copolymerized A
Examples thereof include S resin, styrene, acrylonitrile, and ABS resin obtained by copolymerizing butadiene. These resins may be used alone or in combination of two or more.

In the present invention, the polyester resin (a) and the polystyrene resin (b) are (a): (b)
= 80: 20 to 20:80 parts by weight, preferably 70: 3
0 to 30:70 parts by weight, more preferably 60:40 to 4
It is blended in the range of 0:60. When the amount of the polystyrene-based resin is less than 20 parts by weight, the effect of improving the molding processability is insufficient, and when the amount of the polyester-based resin is less than 20 parts by weight, the impact resistance and the solvent resistance are improved. Is insufficient. The modified polystyrene resin used in the thermoplastic polymer of the present invention is a polyester resin in which ammonium salts of an organic acid are added and melt-mixed, molecular chain scission occurs, and a hydroxyl group or a carboxylic acid group generated at that time is terminated. A hydroxyl group capable of reacting with an active intermediate having, a carboxylic acid anhydride group, a carboxylic acid group, an epoxy group, a functional group having at least one selected from the group of oxazoline groups, for example, hydroxyl-modified polystyrene ( PS), maleic anhydride modified PS, ethylene-ethyl acrylate (EEA) PS grafted product, EEA AS grafted product, epoxy group modified PS polymethylmethacrylate (PMMA) or PS grafted product, oxazoline group modified PS, AS Etc.

The ammonium salt of an organic acid used in the thermoplastic polymer of the present invention is an important component which acts as a reaction catalyst for the polyester resin and the modified polystyrene resin. Ammonium organic acids are not particularly limited and are commercially available, for example, ammonium oxalate, ammonium succinate, ammonium tartrate,
Examples include ammonium oxalate, ammonium benzoate, ammonium citrate, etc. Among them, ammonium oxalate and ammonium succinate hardly decompose or sublime in the temperature range just before kneading the materials (around 200 ° C at most). , Temperature range for melting and kneading materials (250
It is particularly preferable because it has the property of rapidly decomposing or sublimating at temperatures of up to 300 ° C. Polyester resin (a) 80-
20 to 80 parts by weight of a modified polystyrene resin (b) having at least one functional group selected from the group consisting of 20 parts by weight, a hydroxyl group, a carboxylic acid anhydride group, a carboxylic acid group, an epoxy group and an oxazoline group, and the above. 0.001 to 5 parts by weight of an ammonium salt of an organic acid, particularly preferably oxalic acid and / or ammonium succinate, is added to 100 parts by weight of the polyester resin (a) and the modified polystyrene resin (b). The thermoplastic polymer of the present invention can be obtained by melt reaction at 220 to 300 ° C for 0.5 to 8 hours.

Although the reaction is possible in air,
Since coloring occurs, it is preferable to carry out under a nitrogen stream.
In the present invention, the polyester resin (a) and the modified polystyrene resin (b) are (a) :( b) = 80: 20.
To 20:80 parts by weight, preferably 70:30 to 30: 7
The amount is 0 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 modified polystyrene resin is less than 20 parts by weight, the effect of improving the compatibility is lowered.
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. Reaction temperature is 22
If the temperature falls below 0 ° C, the resin becomes difficult to melt, and if it exceeds 300 ° C, thermal decomposition begins. 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 the thermoplastic polymer (c) is added to 100 parts by weight of the resin composition in which the polyester resin (a) and the polystyrene resin (ii) are mixed at a predetermined ratio, and the biaxial is prepared. By kneading with a kneader or the like, a thermoplastic resin composition having good compatibility and a good appearance can be obtained. If the blending amount of the thermoplastic resin composition is less than 0.1 parts by weight, the effect of improving compatibility is insufficient, and if the blending amount exceeds 10 parts by weight,
The compatibility becomes too good and the characteristics deteriorate.

Thus, the thermoplastic polymer (c) of the present invention
Has an effect of remarkably improving the compatibility between the polyester resin and the polyolefin resin, because the ammonium salt of the organic acid acts as a reaction catalyst A reaction occurs between them, and the reaction product having the polyester component and the polyolefin component in the same molecule acts as a surfactant, improving the compatibility of the polyester resin and the polyolefin resin, and This is probably because it became possible to have a phase-separated structure. The thermoplastic resin composition of the present invention further uses, other compounding agents depending on the purpose, for example, talc, mica, calcium carbonate, inorganic fillers such as wollastonite, or glass fiber,
Reinforcing agent such as carbon fiber, flame retardant, flame retardant aid,
An antistatic agent, a stabilizer, a pigment, a release agent 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.

[0010]

【Example】

<< Example 1 >> Polyester resin (Dianite R MA
-523V Mitsubishi Rayon Co., Ltd.) 60 parts by weight, epoxy group-modified polystyrene resin (Reseda R GP-500 Toa Gosei Kagaku Co., Ltd.) 40 parts by weight, ammonium oxalate 0.1 parts by weight Stainless steel beaker with stirring device It was put into the inside, and after it was evacuated, it was replaced with nitrogen.
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 A of the present invention. Polyester resin 60 parts by weight (Dianite R MA-523V manufactured by Mitsubishi Rayon Co., Ltd.), polystyrene resin (Esbright R 4 Sumitomo Chemical Co., Ltd.)
40 parts by weight and 5 parts by weight of the thermoplastic polymer A 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, and chemical resistance. The evaluation results are shown in Table 1. << Example 2 >> 40 parts by weight of aromatic polycarbonate resin (Panlite RL-1225 Teijin Chemicals Ltd.), 60 parts by weight of oxazoline group-modified AS resin (RAS-1005 manufactured by Nippon Shokubai Kagaku Kogyo KK), succinic acid Ammonium 0.5
Put parts by weight into a stainless beaker with a stirrer,
After the vacuum is drawn, the atmosphere is replaced with nitrogen, and the resin temperature is 270-280 ° C.
The resulting mixture was melted for 2 hours, cooled to room temperature under a nitrogen stream, and pulverized to obtain a thermoplastic polymer B of the present invention. Aromatic polycarbonate resin (Panlite R L-
1225 Teijin Kasei Co., Ltd. 40 parts by weight, AS resin (Clearpet R 1000 manufactured by Sumitomo Nogatak Co., Ltd.) 60 parts by weight, and thermoplastic polymer B 3 parts by weight are charged into a Henschel mixer and the mixture is supplied at 800 to 1200 rpm for several minutes. The mixture was mixed and melt-kneaded with a biaxial kneader under conditions such that the resin temperature was 270 to 280 ° C. to prepare pellets, which were then injection-molded. Tensile strength, tensile elongation of the obtained test pieces, , Izod impact strength and chemical resistance were evaluated.
The evaluation results are shown in Table 1. << Examples 3 to 5 >> 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 polyester resin (Dianite R MA-523V manufactured by Mitsubishi Rayon Co., Ltd.), epoxy group-modified polystyrene resin (Reseda R GP
-500 Toa Gosei Kagaku Co., Ltd.), 0.1 parts by weight of ammonium oxalate was placed in a stainless beaker equipped with a stirrer, evacuated and then replaced with nitrogen.
After melt-reacting for 2 hours under the condition of 280 ° C., vacuum was applied to remove the remaining ammonium nitrate, the mixture was cooled to room temperature under a nitrogen stream and pulverized to obtain a thermoplastic polymer C. Polyester resin (Dianite RM
A-523V Mitsubishi Rayon Co., Ltd. 60 parts by weight, polystyrene resin (Esbright R 4 Sumitomo Chemical Co., 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, and chemical resistance. 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.), 60 parts by weight of oxazoline group-modified AS resin (RAS-1005 manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.), succinic acid 7 parts by weight of ammonium was placed in a stainless beaker equipped with a stirrer, evacuated and then replaced with nitrogen, and melted and reacted for 2 hours under the conditions that the resin temperature was 270 to 280 ° C. and cooled to room temperature under a nitrogen stream. Then, it was pulverized to obtain a thermoplastic polymer D. Aromatic polycarbonate resin (Panlite RL-1225, Teijin Chemicals Ltd.) 40 parts by weight, AS resin (Clearpet R 1
000 Sumitomo Nogatac Co., Ltd.) 60 parts by weight and thermoplastic polymer D3 parts by weight were put into a Henschel mixer to obtain 80
The mixture was mixed at 0 to 1200 rpm for several minutes, melted and kneaded in a twin-screw kneader under conditions such that the resin temperature became 270 to 280 ° C. to make pellets, and then injection molding was performed. The tensile strength, tensile elongation, Izod impact strength and chemical resistance were evaluated. The evaluation results are shown in Table 2. << Comparative Examples 3 to 5 >> 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 6 to 10 >> The mixture preblended according to the formulation shown in Table 3 was melt-kneaded in the same manner as in Example 1 and, after molding, its characteristics were evaluated. The evaluation results are also shown in Table 3.

[0012]

[0013]

[0014]

* 1 Dianite R MA-523V Mitsubishi Rayon Co., Ltd. * 2 Panlite RL-1225 Teijin Kasei Co., Ltd. * 3 Esbright R 4 Sumitomo Chemical Co., Ltd. * 4 Clearpet R 1000 Sumitomo Nogatac Co., Ltd.
Product * 5 Tensile strength: Measured according to ASTM D-638. * 6 Tensile elongation: Measured according to ASTM D-638. * 7 Izod impact strength: Measured according to the method described in ASTM D256 for a 1/4 "width notched test piece. * 8 Chemical resistance: The bending test piece was immersed in butyl acetate at 23 ° C for 3 months to change the appearance. In the table, ◯ indicates that it was judged to be usable, Δ indicates that it was slightly corroded or swollen, and x indicates that it was judged to be unusable.

[0016]

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 polystyrene resin is remarkably improved 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 polyester resin of 95 to 5 parts by weight, (b) a polystyrene resin of 5 to 95 parts by weight, and (c) a total of 100 parts by weight of the polyester resin and the polystyrene resin, (A) 80 to 20 parts by weight of polyester resin, (b) modified polystyrene resin having at least one functional group selected from the group consisting of hydroxyl group, carboxylic acid anhydride group, carboxylic acid group, epoxy group and oxazoline group. The resin is added in an amount of 20 to 80 parts by weight and (c) 0.001 to 5 parts by weight of an ammonium salt of an organic acid is added to 100 parts by weight of the polyester-based resin and the modified polystyrene-based resin at 220 to 300 ° C. ．
A thermoplastic resin composition comprising 0.1 to 10 parts by weight of a thermoplastic polymer obtained by melt reaction for 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.