JPH0593119A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve the compatibility of a polyester resin with a polystyrene resin by compounding the two resins with a specific thermoplastic polymer having a high affinity with them. CONSTITUTION:100 pts.wt. resin component comprising 95-5wt.% polyester resin and 5-95wt.% polystyrene resin is compounded with 0.1-10 pts.wt. thermoplastic resin which is prepd. by reacting 80-20 pts.wt. polyester resin, 20-80 pts.wt. modified polystyrene resin having at least one kind of group selected from the group consisting of hydroxyl, carboxylic anhydride, epoxy, and oxazolidone groups, and an inorg. nitrate in an amt. of 0.001-5 pts.wt.(based on 100 pts.wt. the sum of the polyester resin and the modified polystyrene resin) at 220-300 deg.C for 0.5-8hr in a molten state.

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 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-based resins are generally rich in surface smoothness, although they may vary depending on their structure.
It has a glossy appearance. Crystalline PET, PBT
Has a high melting point and a high degree of crystallinity, and is widely used for films, molded products, etc., with excellent dimensional stability, transparency, toughness, electrical insulation and chemical resistance. It has the disadvantage of poor performance. On the other hand, amorphous PC,
PAR is excellent in heat resistance, mechanical properties, and transparency, and is considerably better in impact resistance than crystalline PET and PBT, and is used for electric and electronic parts, OA equipment, precision machinery, etc. However, it has the drawback of poor solvent resistance.

On the other hand, polystyrene-based resins such as PS and AS are excellent in moldability, cost and transparency and are lightweight, so they are used in a wide range of applications such as daily sundries and plastic models. It has the disadvantage of poor resistance and solvent resistance. Generally, it is difficult to obtain a resin composition having good properties such as heat resistance, impact resistance, moldability, chemical resistance, etc. 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 the resins 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. .

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 carried out, but in the case of the polyester resin and the polystyrene resin, a suitable compatibilizing agent is used. There was no agent and the improvement effect was insufficient.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive investigations by the present inventors to obtain a compatibilizer having an affinity for both polyester resins and polystyrene resins, as a result, inorganic nitrates were added to the polyester resin. When melt-mixed, molecular chain scission occurs, and a heat 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 time It was found that the plastic polymer has an effect of remarkably improving the compatibility between the polyester resin and the polystyrene resin, and has completed the present invention.

[0006]

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) 100 parts by weight of the total of the polyester resin and the modified polystyrene resin, inorganic nitrates, particularly preferably ammonium nitrate, of 0.
001 to 5 parts by weight is added, and at 220 to 300 ° C, 0.5 to
The present invention relates to a thermoplastic resin composition comprising 0.1 to 10 parts by weight of a thermoplastic polymer obtained by performing a melt reaction for 8 hours.

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, polyethylene terephthalate, polybutylene terephthalate,
Polybutylene terephthalate, aromatic polycarbonate, polyarylate, <Zider>, <Vectra>, <
Examples include liquid crystal polyester and the like, which are commercially available under the name of Rod Run> and the like. 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 polyolefin resin used in the thermoplastic resin composition of the present invention is not particularly limited and is commercially available. For example, low pressure method, medium pressure method, high pressure method polyethylene, polypropylene, ethylene-propylene copolymer Examples thereof include polymers and copolymers obtained by copolymerizing ethylene or propylene with other olefins. 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)
= 95: 5 to 5:95 parts by weight, preferably 80:20 to
20:80 parts by weight, more preferably 70:30 to 30:
It is mixed in the range of 70. When the amount of the polystyrene resin compounded is less than 5 parts by weight, the effect of improving the moldability becomes insufficient, and when the amount of the polyester resin compounded is less than 5 parts by weight, the impact resistance and solvent resistance are improved. Is insufficient.

The modified polystyrene resin used in the thermoplastic polymer of the present invention is such that when inorganic nitrates are added to polyester resin and melt-mixed, molecular chain scission occurs and the hydroxyl group or carboxylic acid group generated at that time is generated. Those 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 capable of reacting with an active intermediate at the end, for example, a hydroxyl group-modified PS , Maleic anhydride modified PS, EE
Examples thereof include PS grafted products of A, AS grafted products of EEA, PMMA or PS grafted products of epoxy group-modified PS, oxazoline group modified PS, AS and the like.

The inorganic nitrates used in the thermoplastic polymer of the present invention are important components which act as a reaction catalyst between the polyester resin and the modified polystyrene resin. The inorganic nitrates are not particularly limited and are commercially available, and examples thereof include aluminum nitrate, sodium nitrate, potassium nitrate and the like. Among them, ammonium nitrate is particularly preferable because it has the property of decomposing and disappearing at about 210 ° C.

Modified polystyrene resin having at least one functional group selected from the group consisting of 80 to 20 parts by weight of polyester resin (a), hydroxyl group, carboxylic acid anhydride group, carboxylic acid group, epoxy group and oxazoline group. 20 to 80 parts by weight of the resin (b) and a total of 10 of the polyester resin (a) and the modified polystyrene resin (b).
Inorganic nitrates, particularly preferably ammonium nitrate in an amount of 0.001 to 5 parts by weight to 0 parts by weight, 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 coloring, it is preferably carried 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 7
0:30 to 30:70 parts by weight, more preferably 60: 4
It is mixed in the range of 0 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 compatibility is lowered. The amount of inorganic nitrates is 0.001
If it is less than 10 parts by weight, the effect of accelerating the reaction becomes insufficient, and if it exceeds 10 parts by weight, the characteristics are deteriorated. If the reaction temperature is lower than 220 ° C, the resin becomes difficult to melt,
Thermal decomposition begins when the temperature exceeds 0 ° C. Also, the reaction time is 0.5
If it is less than the time, the reaction between the resins becomes insufficient, and if it exceeds 8 hours, the reaction no longer proceeds.

A resin composition 10 in which a polyester resin (a) and a polystyrene resin (b) are mixed in a predetermined ratio.
To obtain a thermoplastic resin composition having good compatibility and good appearance by blending 0.1 to 10 parts by weight of a thermoplastic polymer with 0 parts by weight and kneading with a biaxial kneader or the like. You can 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 characteristics 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 polyolefin resin, because the inorganic nitrates are used as the reaction catalyst. A reaction occurs between the polyester resin and the polyolefin resin by working, and the reaction product having the polyester component and the polyolefin component in the same molecule acts as a surfactant,
It is considered that the compatibility between the polyester-based resin and the polyolefin-based resin was improved and it became possible to have an incompatible microphase-separated structure.

The thermoplastic resin composition of the present invention may further contain other compounding agents such as talc, mica, depending on the use and purpose.
Inorganic fillers such as calcium carbonate, wollastonite,
Alternatively, a reinforcing agent such as glass fiber or carbon fiber, a flame retardant, a flame retardant aid, an antistatic agent, a stabilizer, a pigment, a release agent, etc. 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 material of the thermoplastic resin composition of the present invention is batched or divided and is used in a Henschel mixer. It can be obtained by sufficiently mixing and further kneading with a biaxial kneader.

[0018]

【Example】

<< Example 1 >> Polyester resin (Dianite R MA
-523V, Mitsubishi Rayon Co., Ltd. 60 parts by weight, epoxy group-modified polystyrene resin (Reseda RGP-500)
40 parts by weight of Toagosei Co., Ltd. and 0.1 parts by weight of ammonium nitrate were put into a stainless beaker equipped with a stirrer, evacuated and then replaced with nitrogen, and the resin temperature was 270-2.
Melt react for 2 hours under the condition of 80 ° C., and then apply 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 (Dyanite 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 make pellets, and then injection molding was performed. The obtained test pieces were evaluated for tensile strength, bending strength, bending elastic modulus, 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.), AS resin modified with oxazoline group (RAS-1005)
60 parts by weight of Nippon Shokubai Kagaku Kogyo Co., Ltd. and 1 part by weight of aluminum nitrate were placed in a stainless beaker equipped with a stirrer, and after vacuuming, the atmosphere was replaced with nitrogen and the resin temperature was 270 to 270.
Melt reaction was carried out for 2 hours under the condition of 280 ° C., 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 Kasei Co., Ltd. 40 parts by weight, AS resin (Clearpet R 1000 manufactured by Sumitomo Nogatac Co., Ltd.) 60 parts by weight, and thermoplastic polymer B3 parts by weight were put into a Henschel mixer, and 800- Mix for several minutes at 1200 rpm, and use a twin-screw kneader to increase the resin temperature to 270-28.
Melt and knead under the condition of 0 ℃ to make pellets,
After that, injection molding was performed, and the obtained test piece was subjected to tensile strength, bending strength, bending elastic modulus, Izod impact strength,
The chemical resistance was 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,
After molding, its characteristics were evaluated. The evaluation results are also shown in Table 1.

<< Comparative Example 1 >> Polyester resin (Dianite R MA-523V, manufactured by Mitsubishi Rayon Co., Ltd.) 90
Parts by weight, epoxy group-modified polystyrene resin (Reseda R
GP-500 manufactured by Toagosei Kagaku Co., Ltd., 0.1 parts by weight of ammonium nitrate was placed in a stainless beaker equipped with a stirrer, and the vacuum was applied, followed by nitrogen substitution, and the resin temperature was 270.
After melt-reacting for 2 hours under the condition of 280 ° C., vacuum was applied to remove residual ammonium nitrate, the mixture 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, 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 make pellets, and then injection molding was performed. The obtained test pieces were evaluated for tensile strength, bending strength, bending elastic modulus, 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.), AS resin modified with oxazoline group (RAS-1005)
60 parts by weight of Nippon Shokubai Kagaku Kogyo Co., Ltd. and 14 parts by weight of aluminum nitrate were put into a stainless beaker equipped with a stirrer, evacuated and then replaced with nitrogen. The resin temperature was 270.
A thermoplastic polymer D was obtained by melting and reacting for 2 hours at a temperature of ˜280 ° C., cooling to room temperature under a nitrogen stream, and pulverizing.

Aromatic polycarbonate resin (Panlite
RL-1225, Teijin Kasei Co., Ltd. 40 parts by weight, AS resin (Clearpet R 1000 manufactured by Sumitomo Nogatac Co., Ltd.) 60 parts by weight, and thermoplastic polymer D3 parts by weight were charged into a Henschel mixer, and 800- Mix for several minutes at 1200 rpm, and use a twin-screw kneader to increase the resin temperature to 270-28.
Melt and knead under the condition of 0 ℃ to make pellets,
After that, injection molding was performed, and the obtained test piece was subjected to tensile strength, bending strength, bending elastic modulus, Izod impact strength,
The chemical resistance was 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,
After molding, its characteristics were evaluated. The evaluation results are also shown in Table 2.

Comparative Examples 6 to 10 The mixture preblended with the composition 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.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

* 1 Diamondite R MA-523V,
Mitsubishi Rayon Co., Ltd. * 2 Panlite R L-1225, Teijin Kasei Co., Ltd. * 3 Esbright R 4 Sumitomo Chemical Co., Ltd. * 4 Clearpet R 1000 Sumitomo Nogatak Co., Ltd. * 5 Tensile strength: It was measured according to ASTM D-638. * 6 Tensile elastic modulus: Measured according to ASTM D-638. * 7 Izod impact strength: Measured on a 1/4 "width notched test piece according to the method described in ASTM D256. * 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.

[0033]

As is clear 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 thermoplastic polymer. It is a new and well-balanced material with excellent heat resistance, impact resistance, moldability and chemical resistance, which have the advantages of both.

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[Procedure amendment]

[Submission date] August 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction content]

[0015] Thermoplastic polymers The invention thus has the effect of significantly improving the compatibility with the polyester resin and the polystyrene-based resin, because, inorganic nitrates reaction catalyst by act reaction product surfactant manner having a polyester component and a polystyrene component to the reaction occurs, in the same molecule between the polyester resin and polystyrene resin by acting as a polyester resin to improve the compatibility of the polystyrene-based resin,
It is considered that it became possible to have an incompatible micro phase separation structure.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0019

[Correction method] Change

[Correction content]

Polyester resin 60 parts by weight (Dyanite 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.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

Aromatic polycarbonate resin (Panlite
RL-1225, Teijin Kasei Co., Ltd. 40 parts by weight, AS resin (Clearpet R 1000 manufactured by Sumitomo Nogatac Co., Ltd.) 60 parts by weight, and thermoplastic polymer B3 parts by weight were put into a Henschel mixer, and 800- Mix for several minutes at 1200 rpm, and use a twin-screw kneader to increase the resin temperature to 270-28.
Melt and knead under the condition of 0 ℃ to make pellets,
Thereafter, injection molding was performed, and 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.

[Procedure correction 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

Polyester resin (Dianite R MA
-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.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Aromatic polycarbonate resin (Panlite
RL-1225, Teijin Kasei Co., Ltd. 40 parts by weight, AS resin (Clearpet R 1000 manufactured by Sumitomo Nogatac Co., Ltd.) 60 parts by weight, and thermoplastic polymer D3 parts by weight were charged into a Henschel mixer, and 800- Mix for several minutes at 1200 rpm, and use a twin-screw kneader to increase the resin temperature to 270-28.
Melt and knead under the condition of 0 ℃ to make pellets,
Thereafter, injection molding was performed, and 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.

[Procedure Amendment 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

* 1 Diamondite R MA-523V,
Mitsubishi Rayon Co., Ltd. * 2 Panlite R L-1225, Teijin Kasei Co., Ltd. * 3 Esbright R 4 Sumitomo Chemical Co., Ltd. * 4 Clearpet R 1000 Sumitomo Nogatac Co., Ltd. * 5 Tensile strength: It was measured according to ASTM D-638. * 6 Tensile elongation : Measured according to ASTM D-638. * 7 Izod impact strength: Measured on a 1/4 "width notched test piece according to the method described in ASTM D256. * 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.

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Claims (2)

[Claims] 1. A total of 100 parts by weight of (a) polyester resin 95 to 5 parts by weight, (b) polystyrene resin 5 to 95 parts by weight, and (c) polyester resin and 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. 20 to 80 parts by weight of the resin and (c) 0.001 to 5 of the inorganic nitrate with respect to 100 parts by weight of the total of the polyester resin and the modified polystyrene resin.
0.1 parts by weight of a thermoplastic polymer obtained by adding a part by weight and performing a melt reaction at 220 to 300 ° C. for 0.5 to 8 hours.
A thermoplastic resin composition, which is added in an amount of from 10 to 10 parts by weight. 2. The thermoplastic resin composition according to claim 1, wherein the inorganic nitrate is ammonium nitrate.