JPH0459869A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition having excellent impact resistance, especially high speed punching impact resistance, surface property and thermal stability in storage in a melted state and suitable especially for moldings by compounding an epoxy group-containing polyarylate and a polyamide. CONSTITUTION:A thermoplastic resin composition comprises (A) 20-80wt.%, preferably 30-60wt.%, of an epoxy group-containing polyarylate, preferably an aromatic polyester prepared from bisphenol A and terephthalic acid and/or isophthalic acid and having an epoxy group content of 2X10<-6> equivalent/g, especially 5X10<-6> to 80X10<-6> equivalent/g, and an intrinsic viscosity (in a chloroform solution at 30 deg.C) of 0.2-1.5dl/g, especially 0.4-0.8dl/g, and (B) 80-20wt.%, preferably 70-40wt.%, of a polyamide preferably nylon 6 or nylon 66 having a relative viscosity of 2-5.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a thermoplastic material that has excellent impact resistance, particularly high-speed punching impact resistance, surface properties, and retention heat stability in a molten state, and is particularly suitable for molding. The present invention relates to a desirable resin composition.

[Conventional technology]

Polyarylate is an engineering plastic obtained from aromatic dicarboxylic acid or its derivative and bisphenol or its derivative, and is known to have a high heat distortion temperature and a high thermal decomposition temperature.

In addition, a resin composition composed of polyarylate and polyamide is expected to have an excellent balance of physical properties as a molding material that has the good moldability and chemical resistance of polyamide and the heat deformation resistance of polyarylate.

The usefulness of such resin compositions is disclosed in Japanese Patent Publication No. 56-14699,
It is disclosed in Japanese Patent Application Laid-Open No. 52-98765. However, resin compositions consisting only of polyarylate and polyamide have a drawback of low impact resistance. In order to improve these drawbacks, methods using various impact resistance imparting agents have been disclosed. For example, Japanese Patent Publications No. 62-944, No. 61183353, No. 62-277462, and No. 62-283146 disclose methods using specific modified polyolefins. As described above, when a specific modified polyolefin is used as an impact resistance imparting agent, the Izod impact strength is certainly improved, but the high-speed punching impact resistance, which is more important in practical terms, remains low. These drawbacks are a major hindrance in applications that require impact resistance at low temperatures, such as automobile exterior panels. Furthermore, when modified polyolefins are used, the surface properties of molded products are generally poor, and there is a problem in that silver marks, flow marks, etc. are present. Furthermore, molded articles made of polyamide undergo large dimensional changes due to moisture absorption, and resin compositions made of polyarylate and polyamide also have this problem. Furthermore, resin compositions made of polyarylate and polyamide generally have poor thermal stability when melted at high temperatures such as during injection molding. However, there is a problem in that the mechanical properties of the molded product deteriorate.

[Problem that the invention seeks to solve]

In view of these circumstances, the purpose of the present invention is to improve high-speed punching impact strength and surface properties of molded products in a resin composition made of polyarylate and polyamide, and further improve thermal stability during melt retention at high temperatures. It's about forcing.

[Means for Solving the Problems] As a result of intensive research aimed at this purpose, the present inventors have discovered that the purpose of the present invention can be achieved at an extremely high level by using polyarylate having an epoxy group. .

That is, the present invention provides polyarylate 2 having an epoxy group.
The thermoplastic resin composition contains 0 to 80% by weight of polyamide and 80 to 20% by weight of polyamide.

The polyarylate used in the present invention has the following general formula lydene group (the hydrogen atoms of these alkylene groups and alkylidene groups may be substituted with I or more hydrocarbon groups, halogen groups, and halogenated hydrocarbon groups) -0--50--
A divalent group selected from 502--CO-1 or a direct bond; each R1-Re independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group. ] There is no particular restriction on the main chain structure of the aromatic polyester obtained from the bisphenols or derivatives thereof represented by the following and aromatic dicarboxylic acids or derivatives thereof, but it is essential that the polyester has an epoxy group.

The bisphenols in the above polyarylate are bisphenols or derivatives thereof represented by the following general formula (II) [However, in the formula, -X- can be an alkylene group or an alkyl group, and these can be used alone. It is also possible to use two or more kinds in combination. Specific examples of bisphenols include bis(4-hydroxyphenyl)-methane, 1,1-bis(
4-hydroxyphenyl)-ethane, 2,2-bis(4
-hydroxyphenyl)-propane (bisphenol A
), 11-bis(4-hydroxyphenyl)-1-phenylethane, 1.1-bis(4-hydroxyphenyl)
-cyclohexane, 2,2-bis(3゜5-dimethyl-
4-hydroxyphenyl)-propane, 2,2-bis(
3,5-di-5ec-butyl-4-hydroxyphenyl)-propane, 2゜2-bis(3,5-di-tert-
Butyl-4-hydroxyphenyl)-propane, bis(
3,5-dimethyl-4-hydroxyphenyl)-methane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-methane, l,1-bis(3,5-dimethyl-
4-hydroxyphenyl)-ethane, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenyl)-sulfide, bis(4-hydroxyphenyl)-sulfone, bis(3,5-dimethyl-4-hydroxyphenyl)- Examples include sulfone, bis(4-hydroxyphenyl-ketone, 4,4'-bishydroxybiphenyl, etc.).Other examples include fused polycyclic bisphenols such as dihydroxynaphthalene and dihydroxyanthracene, and bisphenolics such as phenolphthalein and ferorescein. Dyes, dinaphthyl compounds such as 2,2'-dihydroxy-1,1-dinaphthylmethane and 4,4'-dihydroxydinaphthyl can also be used as part of the bisphenol component. As the molecular weight modifier, monofunctional phenols such as phenol and p-(tert-butyl)phenol can be used.Derivatives of the bisphenols include their alkali metal salts, diacetates, and the like.

Examples of the aromatic dicarboxylic acid component in the polyarylate include terephthalic acid, isophthalic acid, diphenyl ether-4,4'-dicarboxylic acid, benzophenone-4
, 4'-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, and the like.

Preferred aromatic dicarboxylic acids are isophthalic acid and/or terephthalic acid, and more preferably the weight ratio of isophthalic acid and terephthalic acid in the polymer is 1 (I10A7/
It is 3. Examples of the aromatic dicarboxylic acid derivatives include dichlorides of these acids, and diesters of alkyl, aryl, and the like. These may be used alone,
Moreover, two or more types may be used in combination.

In order to effectively exhibit the effects of the present invention, the epoxy group is preferably a terminal epoxy group, and its content (hereinafter referred to as epoxy value) is 2 x 10-6 to 100 x
Desirably, the epoxy value is in the range of 10-'' equivalents/g, more preferably the epoxy value is in the range of 5 x 104 to 80 x 10-' equivalents/g.

Outside this range, high-speed punching impact resistance may decrease,
This is undesirable because moldability and surface properties of the molded product deteriorate.

In addition, the above epoxy value is according to the 15O-3001 method,
It can be calculated using the following formula.

However, in the above formula, Ts: Amount of 0, 1N HCl0n acetic acid solution required for titration of the sample (d) Tb: Amount of 0, 1N) 1cIL acetic acid solution required for titration of a blank test (relative) F: 0.1N HCl0. Factor W of acetic acid solution: weight of sample (g).

The effects of the present invention can be fully exhibited by using a polyarylate having an epoxy group, but the polyarylate may also have a carboxyl IM or an acid chloride group in addition to the epoxy group.

The molecular weight of the polyarylate is preferably in the range of 0.2 to 1.5 a/g, more preferably in the range of 0.4 to 0.8 a/g in terms of intrinsic viscosity (chloroform solution, 30°C).

Outside this range, high-speed punching impact resistance and moldability may deteriorate, which is not preferable.

The polyarylate used in the present invention is produced by interfacial polycondensation method, f
Although it can be produced by any method such as g-liquid polymerization or melt polymerization, it is essential that it has an epoxy group. Although the method for introducing epoxy groups into such polyarylate is arbitrary,
For example, as described below, an easy method is to synthesize a polyarylate having an acid chloride group and then react it with a compound having a hydroxyl group and an epoxy group in the same molecule in the presence of an acid acceptor. According to such a method, epoxy groups are introduced at the ends of the polymer.

Polyarylates having an acid chloride group are, for example, disclosed in Japanese Patent Application No. 1-228951, in which the dichloride of an aromatic dicarboxylic acid is mixed with bisphenols and a phenolic compound used as necessary in an interfacial polycondensation method. It can be obtained by carrying out polymerization using an excess of the theoretical equivalent based on the amount of functional groups with respect to the total amount. The polyarylate having acid chloride groups obtained in this manner must contain the amount of acid chloride groups necessary to obtain the desired epoxy value in the present invention. That is, the acid chloride group content of the polyarylate having acid chloride groups must be from 2 to 100 in terms of acid chloride value (10-6 equivalents of acid chloride groups contained in 1 g of resin). The molecular weight of polyarylate having chloride groups is determined by the intrinsic viscosity (chloroform solution, 30°C)
It is preferably in the range of 0.2 to 1.5 a/g, more preferably in the range of 0.4 to 0.8 d1/g.

Specific examples of compounds having the same molecular weight of hydroxyl groups and epoxy groups to be reacted with such polyarylates include 2,3-epoxy-1-propatol, 3,4-epoxy-1-butanol, 3゜4- Aliphatic and alicyclic compounds such as epoxy-cyclohexanol, ethylene glycol monoglycidyl ether, and tetramethylene glycol monoglycidyl ether, 4-(1'2'-epoxyethyl)-phenol, glycidyl p-hydroxybenzoate, 2, 2-bis(4-hydroxyphenyl)-
Examples include aromatic compounds such as propane monoglycidyl ether.

The reaction between the acid chloride group of polyarylate and a compound having a hydroxyl group and an epoxy group in the same molecule can be carried out in the same manner as the reaction between the acid chloride group and hydroxyl group of a low-molecular compound.

That is, the reaction is carried out in the presence of an acid acceptor that traps the hydrogen chloride released by the reaction between the two. Specifically, a polyarylate having an acid chloride group is dissolved in an organic solvent that is substantially incompatible with water, and a compound having a hydroxyl group and an epoxy group in the same molecule is added in the presence of an acid acceptor. This is a method of causing a reaction. As the acid acceptor, an alkaline aqueous solution or tertiary amines are used.

The polyamide used in the present invention includes aliphatic amino acids,
It is a polyamide whose main components are lactam or diamine and dicarboxylic acid. Typical examples of its main components are:
6-aminocaproic acid, 11-aminoundecanoic acid, 1
Amino acids such as 2-aminododecanoic acid, lactams such as ε-caprolactam and ω-laurolactam, diamines such as tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, adipic acid, azelaic acid, sebacic acid, These include dicarboxylic acids such as dodecanoic acid and diglycolic acid, and it is also possible to use copolyamides into which small amounts of aromatic components and alicyclic components are introduced in addition to these aliphatic components.

Particularly useful polyamides in the present invention include polycaproamide (
Nylon-6), polyhexamethylene adipamide (Nylon-66), polytetramethylene adipamide (Nylon-46), and polydodecanamide (Nylon-12). Among them, nylon-6, nylon-66, and nylon-46 are particularly important. These may be used alone or in combination of two or more.

It is preferable that the relative viscosity of the polyamide resin is within the range of 2.0 to 5.0, as measured at 25° C. using a 1% concentrated sulfuric acid solution.

The thermoplastic resin composition of the present invention contains 20 to 80% by weight of polyarylate having epoxy groups and 80 to 20% by weight of polyamide.
% by weight, preferably 30-60% by weight of the polyarylate
and 70 to 40% by weight of polyamide. Outside this range, impact resistance, surface properties, dimensional stability upon moisture absorption, rigidity, moldability, chemical resistance, etc. deteriorate, making it undesirable.

The method for producing the resin composition of the present invention is not particularly limited, but a method using melt mixing is particularly preferred, and for example, an extruder, hot roll, Brahengu, Banbury mixer, etc. can be used.

The resin composition of the present invention may further include a lubricant such as a wax, a stabilizer such as a phosphite type or a phenol type, an ultraviolet absorber, a pigment, a flame retardant, a plasticizer, an inorganic filler, a filler, Reinforcing fibers etc. can be added.

The resin composition of the present invention can be molded by injection molding, extrusion molding, blow molding, compression molding, etc. to produce molded products with excellent high-speed punching impact resistance, surface properties, dimensional stability upon moisture absorption, and weld strength. Obtainable. Moreover, the molded product after being retained in a molten state in an extruder or the like has almost no change compared to the product without being retained, and satisfies the above physical properties. These molded products are useful for various applications such as automobile exterior parts, automobile outer panels, mechanical parts, and electrical/electronic parts.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Reference Example 1 (Production of polyarylate having epoxy group) 2.2-bis(4-hydroxyphenyl)-propane (
Bisphenol A) 674.6 g (2,955 mol Lp-(t-butyl)phenol 13.52 (0,0
9 mol), sodium hydrosulfide 5.28
g, 4N sodium hydroxide 1,920 paper and water 3.3
After mixing 20 m in a 61 flask in a nitrogen atmosphere, the mixture was cooled to 5°C to prepare an alkaline aqueous solution of bisphenol.

Meanwhile, in another 61 flask, terephthalic acid chloride 1
24.25 g (0.6'12 mol) and 496.99 g (2.44 B mol) of isofucric acid chloride were dissolved in 5,000 m of methylene chloride and cooled to 5°C.

Next, another 151! In a separable flask,
2,000 M1 of water and 0.94 g (0.03 mol) of benzyltributylammonium chloride as a catalyst were charged under a nitrogen atmosphere, and the mixture was cooled to 5°C. While stirring the cooling liquid vigorously, the above two liquids prepared in advance were simultaneously added continuously using a pump over a period of 15 minutes.

After 60 minutes had elapsed from the end of the addition, stirring was stopped and the aqueous phase was decanted, then the same amount of water was added and neutralized with a small amount of hydrochloric acid while stirring. Furthermore, after repeated desalting by washing with water, acetone was added to precipitate a polymer powder, and after filtration, the powder was washed with the same amount of acetone and water, and filtered again in the same manner. The acid chloride number of the dried polymer (10
-' equivalent/g) was measured and found to be 45. Further, the molecular weight was 0.62 dIl/g expressed in intrinsic viscosity (chloroform solution, 30''C).

1,000 g of the polymer obtained in this way was
Pour into a separable flask and add 5 methylene chloride.
．． 0OOO was added and the polymer was dissolved under stirring and reflux. After the polymer solution became completely transparent, it was cooled to 5°C. Thereafter, under stirring, a solution of 44.45 g (0°6 mol) of 23-epoxy-1-panol in methylene chloride (5
00ml) and triethylamine 6.68g (0,
066 mol) in methylene chloride (50 m) was added. After 60 minutes, the same amount of acetone as methylene chloride was gradually added to precipitate the polymer powder. After filtration, the powder was washed with the same amount of acetone and filtered again in the same manner.

The epoxy value of the obtained polymer powder was measured by the following method.

Precisely weigh about 0.2 g of polymer powder and add 20 J! 1
! of chloroform was added to dissolve. After dissolution, 10Ii of 25% acetic acid solution of tetraethylammonium bromide
A small amount of a 0.1% acetic acid solution of crystal violet and crystal violet was added as an indicator. Immediately remove this purple sample solution.
．． A solution of IN HClO4 in acetic acid was titrated, with the end point being the point at which the color of the indicator changed to blue-green. Additionally, a blank test was conducted separately.

When the epoxy value was calculated using the old method, the epoxy value (
10-' equivalents/g) was 30. In addition, the molecular weight is expressed as an intrinsic viscosity (chloroform solution, 30°C) of 0.62.
It was cU/g.

Reference Examples 2-9 As shown in Table 1, 2.2-
Polyarylates having various epoxy values were produced by changing the ratio of bis(4-hydroxyphenyl)-furopane and acid chloride components. In addition, polyarylate using a mixture of 2.2-bis(4-hydroxyphenyl)-propane and 1.1-bis(4-hydroxyphenyl)-1-phenylecne in a molar ratio of 50:50 is also available as a bisphenol component. Manufactured.

Examples 1 to 12 and Comparative Examples 1 to 4 The polyarylates obtained in Reference Examples 1 to 9 and the polyamide Amilan CM1026 (poly ε-caprolactam, relative viscosity 3.2) manufactured by Toshi ■ are shown in Table 2. After blending and tri-blending, vacuum drying was performed at 80°C for 15 hours, and then 270°C to 28°C was mixed using a twin-screw extruder.
Pellets were obtained by kneading at 0″C.
Vacuum drying was performed at ℃ for 15 hours, and test pieces were obtained by injection molding.

The properties of the test pieces were evaluated by the following method, and the results are shown in Table 2.

[High-speed punching impact strength] Using a high-speed punching impact tester model HRIT8000 manufactured by Rheometric Co., Ltd., a punch (5/8 inch diameter) was used to punch 5 m.
A test piece (100 x 100 x 3 mm) was punched out at a speed of /s, and the energy required for punching was measured.

[Surface properties of molded product]

A flat plate of 10100 x 100 x 3 was molded, and the presence or absence of defects such as flow marks and silver marks near the gate was visually observed and evaluated.

○: Almost no defect Δ: Slightly defective ×: Significantly defective [retention thermal stability in molten state] The above pellets were continuously injection molded at a resin temperature of 290°C to obtain test pieces. Obtained. Tensile elongation at break of this test piece (
Measured at 23° C., ASTM D63B). On the other hand, the pellets were kept in an injection molding machine at 290° C. for 20 minutes, then injection molded and the same measurements were made on the first shot test piece and compared with the above tensile elongation at break.

Further, the viscosity of the pellet was measured using a capillary rheometer immediately after melting at 290°C and after staying at 290°C for 20 minutes (shear rate 1216S-').

As is clear from the results in Table 2, the resin composition of the present invention has significantly improved melt viscosity and physical property deterioration after residence, and also has extremely excellent physical properties of molded articles.

[Action/Effect]

Although it is not clear why the use of polyarylate having an epoxy group at the end produces a remarkable effect,
It was observed by scanning electron microscopy that the dispersed particle size of the polyarylate dispersed phase in the polyamide was much smaller and more uniform than when polyarylate without epoxy groups was used. Furthermore, it was found that even after this resin composition was allowed to remain in a molten state, the dispersed particle size remained almost unchanged. From these facts, it can be assumed that in the composition of the present invention, the interface between the polyarylate particles and the polyamide is particularly stabilized. Such an effect exerted by the epoxy group of polyarylate was completely unknown in the past, and was discovered for the first time by the present inventors.

As with soft soil, the present invention provides a resin composition having a good balance of impact resistance, particularly high-speed punching impact resistance, surface properties, and retention stability in a molten state.

Patent applicant Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1. A thermoplastic resin composition comprising 20 to 80% by weight of polyarylate having an epoxy group and 80 to 20% by weight of polyamide. 2. The epoxy group content of the polyarylate having epoxy groups is 2 x 10^-^6 to 100 x 10^-^6 equivalent/
The thermoplastic resin composition according to claim 1, which is g. 3. The epoxy group content of the polyarylate having epoxy groups is 5 x 10^-^6 to 80 x 10^-^6 equivalent/g
The thermoplastic resin composition according to claim 1. 4. The thermoplastic resin composition according to claims 1 to 3, wherein the polyarylate is an aromatic polyester consisting of 2,2-bis(4-hydroxyphenyl)-propane (bisphenol A) and terephthalic acid and/or isophthalic acid. . 5. Polyarylate is 2,2-bis(4-hydroxyphenyl)-propane (bisphenol A) and/or 1
, 1-bis(4-hydroxyphenyl)-1-phenylethane, and terephthalic acid and/or isophthalic acid. 6. The thermoplastic resin composition according to claims 1 to 5, wherein the polyarylate has a molecular weight of 0.2 to 1.5 dl/g expressed in intrinsic viscosity (chloroform solution, 30°C). 7. The thermoplastic resin composition according to claims 1 to 5, wherein the polyarylate has a molecular weight of 0.4 to 0.8 dl/g expressed in intrinsic viscosity (chloroform solution, 30°C). 8. The thermoplastic resin composition according to claims 1 to 7, wherein the polyamide is nylon-6. 9. Claims 1 to 7 wherein the polyamide is nylon-6,6.
The thermoplastic resin composition described.