JPH0578566A - Production of thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having the effect of markedly improving the compatibility of a polyamide resin with a polyester resin. CONSTITUTION:The objective process comprises adding 0.01-10 pts.wt. catalyst prepared by homogeneously dispersing zinc oxide in silica and/or alumina to 100 pts.wt. total of 80-20 pts.wt. aromatic polycarbonate resin and 20-80 pts.wt. polyamide resin and reacting them by melting at 220-280 deg.C for 10-240min.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an aromatic polycarbonate resin, a polyamide resin, zinc oxide, or a predetermined amount of a catalyst obtained by uniformly dispersing zinc oxide in silica and / or alumina, and melting the catalyst under predetermined conditions. The present invention relates to a thermoplastic resin composition useful for compatibilizing a polymer alloy obtained by reacting.

[0002]

2. Description of the Related Art A crystalline thermoplastic resin has advantages such as being hard and rigid, excellent in abrasion and wear resistance, solvent resistance, and having good fluidity, but it is brittle and easily cracked, opaque, and has a large molding shrinkage. It has drawbacks such as On the other hand, an amorphous thermoplastic resin has advantages such as transparency and flexibility, which are opposite to those of a crystalline resin, a small molding shrinkage ratio and a high Tg, but it has poor chemical resistance, poor abrasion resistance, and fluidity. It has drawbacks such as poor property.

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. Therefore, in the case of a crystalline resin, In order to make up for the drawback, a polymer alloy with an amorphous resin is performed. However, the compatibility between the crystalline resin and the amorphous resin is usually poor, and the incompatibility micro phase separation type sea-island structure cannot be taken simply by mixing the two resins, so that the advantages of the two resins are It is difficult to obtain a thermoplastic resin composition that can be held together. As a method for improving the compatibility, a method of adding a compatibilizing agent having an affinity for both the crystalline resin and the amorphous resin is generally performed, and a polyamide resin and PET, PBT, PC, polyarylate, In the case of polyester-based polymers such as liquid crystal polymers, there is no suitable compatibilizing agent, and polymer alloying is difficult.

[0004]

The object of the present invention is to blend a predetermined amount of an aromatic polycarbonate resin, a polyamide resin, zinc oxide or a catalyst in which zinc oxide is uniformly dispersed in silica and / or alumina. Another object of the present invention is to provide a thermoplastic resin composition useful for compatibilizing a polyamide resin and a polyester resin, which is obtained by melting and reacting it under a predetermined condition.

[0005]

Means for Solving the Problems As a result of various studies aimed at improving the compatibility of polyamide resin and polyester resin, the present inventors have found that aromatic polycarbonate resin, polyamide resin, zinc oxide or silica and / or alumina A thermoplastic resin composition obtained by blending a predetermined amount of a catalyst in which zinc oxide is uniformly dispersed in the above, and further subjecting them to a melt reaction under predetermined conditions is remarkable for improving the compatibility between the polyamide resin and the polyester resin. The inventors have found that they have an effect and have completed the present invention.

That is, the present invention provides (a) 80 to 20 parts by weight of an aromatic polycarbonate resin, (b) 20 to 80 parts by weight of a polyamide resin, and (c) a total of 100 parts by weight of the aromatic polycarbonate resin and the polyamide resin. In contrast, 0.01 to 10 parts by weight of zinc oxide is added, or (a)
80 to 20 parts by weight of aromatic polycarbonate resin, (b)
20 to 80 parts by weight of polyamide resin and (c) a total of 10 of the aromatic polycarbonate resin and the polyamide resin.
0.01 to 10 parts by weight of a catalyst in which zinc oxide is uniformly dispersed in silica and / or alumina is added to 0 part by weight, and a melting reaction is performed at 220 to 280 ° C. for 10 to 240 minutes. The present invention relates to a method for producing a thermoplastic resin composition.

The aromatic polycarbonate resin used in the present invention is not particularly limited and is commercially available. It is a method of reacting a divalent phenol with phosgene in the presence of an acid binder or a solvent, or a divalent phenol. It can be produced by transesterifying a phenol and diphenyl carbonate in a molten state. Suitable dihydric phenols that can be used in the production of the aromatic polycarbonate resin include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), resorcinol, hydroquinone, 2,2′-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl)
There are ketones and bis (4-hydroxyphenyl) ether. In producing the aromatic polycarbonate resin, two or more dihydric phenols may be used, a homopolymer of dihydric phenols, a copolymer using two or more dihydric phenols, or a mixture thereof.

The polyamide resin used in the present invention is not particularly limited and is commercially available. Hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,3- or 1,4-bis (amino) Methyl) cyclohexane, diamines such as aliphatic, alicyclic and aromatic such as m- or p-xylylenediamine, and aliphatic and fats such as adipic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid and isophthalic acid Polyamide resins produced from dicarboxylic acids such as aromatics and aromatics, polyamide resins produced from lactams such as ε-caprolactam and ω-dodecaractam, and mixtures or copolymerized polyamide resins containing these components. Is exemplified.

Specific examples include polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 6).
6), polyhexamethylene sebacamide (nylon 6,1
0), polyhexamethylene dodecamide (nylon 6,1
2), polyundecane amide (nylon 11), polydodecane amide (nylon 12), polyxylylene adipamide, polyhexamethylene terephthalamide, polyphenylene phthalamide and the like. The degree of polymerization of the polyamide resin used here is not particularly limited, and one having a relative viscosity of 2.0 to 5.0 is usually preferable.

In the present invention, the aromatic polycarbonate resin (a) and the polyamide 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 (a):
(B) = 60: 40 to 40:60 parts by weight. If the blending amount of the aromatic polycarbonate 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 compatibility is reduced.

The catalyst used in the present invention, in which zinc oxide is uniformly dispersed in zinc oxide or silica and / or alumina, is an important component which acts as a reaction catalyst between the aromatic polycarbonate resin and the polyamide resin. The zinc oxide used in the present invention is not limited in its production method, for example, a method of burning metallic zinc in the air or zinc hydroxide is obtained from zinc nitrate and ammonia water or ammonia gas, and the zinc hydroxide is prepared at a low temperature. It can be obtained by a method of drying. Among the above-mentioned production methods, the method of obtaining zinc hydroxide from zinc nitrate and ammonia water or ammonia gas and drying it at a low temperature is preferable because the activity of zinc oxide is larger than that of other methods of treating at a high temperature.

The characteristic value of the zinc oxide used in the present invention is not particularly limited, but preferably the average particle diameter is 0.01 to 20 μm and the specific surface area is 5 to 100 m ² /.
g, more preferably having an average particle diameter of 0.01 to ² μm and a specific surface area of 10 to 100 m ² / g are suitably used.

The catalyst used in the present invention, in which zinc oxide is uniformly dispersed in silica and / or alumina, is a solution in which tetraethoxysilane and / or an inorganic salt of aluminum is added to an aqueous solution of zinc inorganic salt, and ammonia water is further added. Is added or ammonia gas is blown into the hydrogel lattice to form an intermediate in which zinc hydroxide is uniformly dispersed at a very micro level.
It can be obtained by drying at 200 ° C. and further baking at 300 ° C. to 500 ° C.

Inorganic salts are preferable because the activity of the catalyst from which nitrate is obtained is large. The compounding ratio of zinc inorganic salt, tetraethoxysilane and aluminum inorganic salt is as follows: mol number of Zn atom: (mol number of Si atom + Al
The number of atoms is preferably in the range of 1: 1 to 1: 0.1. When (the number of moles of Si atom + the number of moles of Al atom) exceeds 1, the content of zinc oxide in the catalyst becomes low and the catalytic activity decreases, and when it is less than 0.1, the dispersion of zinc oxide in the catalyst becomes low. It becomes insufficient, and the catalytic activity decreases.

With respect to 100 parts by weight of a resin composition in which an aromatic polycarbonate resin and a polyamide resin are blended in a predetermined ratio, a catalyst in which zinc oxide is uniformly dispersed in zinc oxide or silica and / or alumina is used. 1 to 10 parts by weight, preferably 0.1 to 3 parts by weight and added 220 to 280
It is possible to obtain a thermoplastic resin composition having an effect of remarkably improving the compatibility between the polyamide resin and the polyester resin by carrying out a melt reaction at 10 ° C. for 10 to 240 minutes.

When the reaction temperature is lower than 220 ° C., the resin is difficult to melt and thermal decomposition higher than 280 ° C. starts. or,
If the time is less than 10 minutes, the reaction between the resins becomes insufficient,
After 240 minutes, the reaction no longer proceeds.

As described above, the thermoplastic resin composition of the present invention has an effect of remarkably improving the compatibility of the polyamide resin and the polyester resin. The reason is as follows.
When a catalyst in which zinc oxide is uniformly dispersed in zinc oxide or silica and / or alumina acts as a reaction catalyst, a reaction occurs between the aromatic polycarbonate resin and the polyamide resin, and the aromatic polycarbonate component and the aromatic polycarbonate component are contained in the same molecule. The reaction product having a polyamide component acts as a surfactant to improve the compatibility with the polyamide resin and the polyester resin, which makes it possible to form an incompatible micro phase separation type sea-island structure. Conceivable.

The addition amount of the thermoplastic resin composition of the present invention to the polyamide resin and the polyester resin is preferably 0.5 to 10 parts by weight based on 100 parts by weight of both resins.

[0019]

【Example】

Example 1 Ammonia gas was blown at room temperature into a mixed solution obtained by mixing equal amounts of an aqueous zinc nitrate solution (0.1 mol / l) and an aqueous aluminum nitrate solution (0.1 mol / l), and the obtained precipitate was washed with water. Then dry with a spray dryer,
Further, it was dried at 350 ° C. for 8 hours to obtain zinc oxide A.

Aromatic polycarbonate resin (Panlite
RL-1225, Teijin Chemicals Ltd. 60 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.)
40 parts by weight) and 1 part by weight of zinc oxide A are put in a heat kneader, and the resin temperature is set to 230 to 240 ° C. under the conditions of 3
The mixture was melt-kneaded for 0 minutes and then cooled and pulverized to obtain a thermoplastic resin composition A of the present invention.

Aromatic polycarbonate resin (Panlite
RL-1225, Teijin Chemicals Ltd. 60 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.)
40 parts by weight) and 1 part by weight of the thermoplastic resin composition A are put into a Henschel mixer and mixed for several minutes at 800 to 1200 rpm, and the resin temperature is 230 to 2 by a biaxial kneader.
Melt-kneading is performed under the condition of 50 ° C to make pellets, and then injection molding is performed. With the evaluation of moldability, the heat distortion temperature, Izod impact strength, chemical resistance, and melt viscosity of the obtained test piece are evaluated. went. The evaluation results are shown in Table 1.
Shown in.

Example 2 Aqueous zinc nitrate solution (0.1 mo
1 / l) and tetraethoxysilane (0.02 mol /
1) and an aqueous ammonia solution (0.28 mol / l) are mixed in equal amounts at room temperature, the obtained precipitate is washed with water, dried with a spray drier, and further dried at 350 ° C. for 8 hours to obtain zinc oxide B. It was

Aromatic polycarbonate resin (Panlite
RL-1225, Teijin Chemicals Ltd. 60 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.)
40 parts by weight and 1 part by weight of zinc oxide B are put into a heat kneader, and the resin temperature is set to 230 to 250 ° C.
The thermoplastic resin composition B of the present invention was obtained by melt-kneading for 0 minutes, then cooling and pulverizing.

Polyarylate resin (U polymer R U-1
060, Unitika Ltd.) 60 parts by weight, polyamide resin (UBE nylon 1013FB, Ube Industries Ltd.) 40
Parts by weight and 1 part by weight of the thermoplastic resin composition B are put into a Henschel mixer and mixed at 800 to 1200 rpm for several minutes, and this is heated at a resin temperature of 250 to 270 ° C. in a biaxial kneader.
The pellets were melt-kneaded under the following conditions to prepare pellets, which were then injection-molded, and the obtained test pieces were evaluated for heat distortion temperature, Izod impact strength, chemical resistance, and melt viscosity. 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 90 parts by weight of an aromatic polycarbonate resin (Panlite RL-1225, Teijin Chemicals Ltd.), a polyamide resin (UBE nylon 1013FB,
10 parts by weight of Ube Industries, Ltd. and 1 part by weight of zinc oxide B are put into a heat kneader, and melt-kneaded for 40 minutes under conditions such that the resin temperature is 230 to 250 ° C., then cooled and pulverized to heat. A plastic resin composition C was obtained.

Aromatic polycarbonate resin (Panlite
RL-1225, Teijin Chemicals Ltd. 60 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.)
40 parts by weight) and 1 part by weight of the thermoplastic resin composition C are put into a Henschel mixer and mixed for several minutes at 800 to 1200 rpm, and the resin temperature is set to 230 to 2 by a biaxial kneader.
Melt-kneading is performed under the condition of 50 ° C to make pellets, and then injection molding is performed. With the evaluation of moldability, the heat distortion temperature, Izod impact strength, chemical resistance, and melt viscosity of the obtained test piece are evaluated. went. The evaluation results are shown in Table 2.
Shown in.

Comparative Example 2 60 parts by weight of an aromatic polycarbonate resin (Panlite RL-1225, manufactured by Teijin Chemicals Ltd.), a polyamide resin (UBE Nylon 1013FB,
40 parts by weight of Ube Industries, Ltd.) and 15 parts by weight of zinc oxide A are put into a heat kneader, and melt-kneaded for 40 minutes under conditions such that the resin temperature is 230 to 250 ° C., then cooled and pulverized to heat. A plastic resin composition D was obtained.

Polyarylate resin (U polymer R U-1
060, Unitika Ltd. 60 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.)
40 parts by weight and 1 part by weight of the thermoplastic resin composition D were put into a Henschel mixer and mixed at 800 to 1200 rpm for several minutes, and this was mixed with a twin-screw kneader to obtain a resin temperature of 250 to 27.
Melt and knead under the condition of 0 ℃ to make pellets,
After that, injection molding was performed, and the obtained test pieces were evaluated for heat distortion temperature, Izod impact strength, chemical resistance, and melt viscosity. 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, after molding, its characteristics were evaluated. The evaluation results are also shown in Table 2.

[0032]

[Table 1]

[0033]

[Table 2]

* 1 Panlite R L-1225, Teijin Kasei Co., Ltd. * 2 U Polymer R U-1060 Unitika Co., Ltd. * 3 TK-3 Kanebo Co., Ltd. * 4 UBE Nylon 1013FB, Ube Industries ( Co., Ltd. * 5 Heat distortion temperature: When the test piece receives a constant load (18.6 Kg / cm ² ) and is bent by a predetermined amount (0.25 mm) when heated at a constant rate (2 ° C./min) AS the temperature
Measured according to TM D486. * 6 Izod impact strength: Measured according to the method described in ASTM D256 for a 1/4 "width notched test piece. * 7 Chemical resistance: Solvent cracks were generated by immersing the bending test piece in gasoline at 25 ° C for one day. The minimum stress value (critical stress value) was measured: In the table, ◯ indicates a critical stress value of 140 Kgf / cm ² or more, Δ indicates 100 to less than 140 Kgf / cm ² , and × indicates less than 100 Kgf / cm ^2. * 8 Melting Viscosity: Toyo Seiki Co., Ltd. Capillograph 280 ° C., nozzle descending speed 100 mm / min
Measured at.

<< Effects of the Invention >> As is clear from Tables 1 and 2, the thermoplastic resin composition of the present invention obtained by the melt reaction markedly improves the compatibility between the polyamide resin and the polyester resin. It has an effect and is useful for polymer alloying these resins.

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[Procedure amendment]

[Submission date] August 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

Polyarylate resin (U polymer R U-
100 , Unitika Ltd. 60 parts by weight, polyamide resin (UBE Nylon 1013FB, Ube Industries Ltd.) 40
Parts by weight and 1 part by weight of the thermoplastic resin composition B are put into a Henschel mixer and mixed at 800 to 1200 rpm for several minutes, and this is heated at a resin temperature of 250 to 270 ° C. in a biaxial kneader.
The pellets were melt-kneaded under the following conditions to prepare pellets, which were then injection-molded. The obtained test pieces were evaluated for heat distortion temperature, Izod impact strength, chemical resistance, and melt viscosity. The evaluation results are shown in Table 1.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

Polyarylate resin (U polymer R U-
100 , manufactured by Unitika Ltd., 60 parts by weight, polyamide resin (UBE nylon 1013FB, produced by Ube Industries, Ltd.)
40 parts by weight and 1 part by weight of the thermoplastic resin composition D were put into a Henschel mixer and mixed at 800 to 1200 rpm for several minutes, and this was mixed with a twin-screw kneader to obtain a resin temperature of 250 to 27.
Melt and knead under the condition of 0 ℃ to make pellets,
After that, injection molding was performed, and the obtained test pieces were evaluated for heat distortion temperature, Izod impact strength, chemical resistance, and melt viscosity. The evaluation results are shown in Table 2.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

* 1 Panlite RL-1225, Teijin Kasei Co., Ltd. * 2 U Polymer R U-100 Unitika Co., Ltd. * 3 TK-3 Kanebo Co., Ltd. * 4 UBE Nylon 1013FB, Ube Industries ( Co., Ltd. * 5 Heat distortion temperature: When the test piece receives a constant load (18.6 Kg / cm ² ) and is bent by a predetermined amount (0.25 mm) when heated at a constant rate (2 ° C./min) AS the temperature
Measured according to TM D486. * 6 Izod impact strength: Measured according to the method described in ASTM D256 for a 1/4 "width notched test piece. * 7 Chemical resistance: Solvent cracks were generated by immersing the bending test piece in gasoline at 25 ° C for one day. The minimum stress value (critical stress value) was measured: In the table, ◯ indicates a critical stress value of 140 Kgf / cm ² or more, Δ indicates 100 to less than 140 Kgf / cm ² , and × indicates less than 100 Kgf / cm ^2. * 8 Melting Viscosity: Toyo Seiki Co., Ltd. Capillograph 280 ° C., nozzle descending speed 100 mm / min
Measured at.

Claims (2)

[Claims] 1. (a) Aromatic polycarbonate resin 80
.About.20 parts by weight, (b) 20 to 80 parts by weight of polyamide resin, and (c) 100 parts by weight of the aromatic polycarbonate resin and the polyamide resin, 100 parts by weight of zinc oxide.
Add 01 to 10 parts by weight and add 10 to 2 at 220 to 280 ° C.
A method for producing a thermoplastic resin composition, which comprises performing a melting reaction for 40 minutes. 2. (a) Aromatic polycarbonate resin 80
To 20 parts by weight, (b) 20 to 80 parts by weight of polyamide resin, and (c) 100 parts by weight of the total amount of the aromatic polycarbonate resin and the polyamide resin, silica and /
Alternatively, 0.01 to 10 parts by weight of a catalyst in which zinc oxide is uniformly dispersed in alumina is added, and the catalyst is added at 220 to 280 ° C for 10
The method for producing a thermoplastic resin composition, characterized in that a melting reaction is carried out for min.-240 min.