JPH0459868A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition having excellent impact resistance, especially high speed punching impact resistance and surface property, and useful for moldings by adding an ionomer to a resin composition comprising an epoxy group-containing polyarylate and a polyamide. CONSTITUTION:(C) 1-40 pts.wt. of an ionomer consisting of the metal salt of an alpha-olefin-alpha,beta-unsaturated carboxylic acid copolymer is added to 100 pts.wt. of a resin composition comprising (A) 2-80wt.% 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 value (10<-6> equivalent of the epoxy groups contained in 1g of the resin) of 2-100 and an intrinsic viscosity (in a chloroform solution at 30 deg.C) of 0.2-1.5dl/g and (B) 80-20 of a polyamide (preferably nylon 6 or nylon 66) to provide the thermoplastic resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a molding resin composition characterized by excellent impact resistance, particularly high-speed punching impact resistance, and surface properties.

[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. For the purpose of improving such drawbacks, methods using various impact resistance imparting agents have been disclosed. No. 283,146 discloses a method using certain 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 #I impact resistance, which is more important in practical terms, remains low. Especially -30
The high-speed punching impact resistance at temperatures as low as 0.degree. C. remains extremely low, and this drawback is 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 silver marks, flow marks, etc. occur.

[Problem that the invention seeks to solve]

In view of the above circumstances, an object of the present invention is to improve high-speed punching impact strength and surface properties of molded articles in a resin composition comprising polyarylate and polyamide.

[Means for solving problems]

The present inventors have conducted intensive research for the purpose, and have found that the purpose of the present invention can be achieved to an extremely high level by using a polyarylate having an epoxy group as the polyarylate and using an ionomer as the impact resistance imparting agent. I found out.

That is, the present invention provides polyarylate 2 having an epoxy group.
Ionomer (
B) A thermoplastic resin composition containing 1 to 40 parts by weight.

The polyarylate used in the present invention is generally not particularly limited in its main chain structure as long as it is an aromatic polyester obtained from bisphenols or derivatives thereof and aromatic dicarboxylic acids or derivatives thereof, but it is essential that it has an epoxy group. It is. Although the epoxy group may be present either in the main chain or at the end, it is preferable that the epoxy group be present at the end because the effects of the present invention are more clearly expressed.

Bisphenols have the following general formula [However, in the formula, -X- is -o--s--s.

, --CO-, an alkylene group or an alkylidene group (the hydrogen atom of these alkylene groups or alkylidene groups may be substituted with one or more hydrocarbon groups, halogen groups, or halogenated hydrocarbon groups) selected from the group,
R1~R@ are hydrogen atoms, halogen atoms, and C1~CtO
selected from the group consisting of hydrocarbon groups. ] is preferable.

An example of such bisphenols is 2,2-bis(
4-Hydroxyphenyl)propane (bisphenol A
), bis(4-hydroxyphenyl)methane, bis(4
-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexylmethane, 1,1-bis(4-hydroxyphenyl) ) ethane, 1,1-bis(4-hydroxyphenyl)1
-Phenylethane, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone , 4,4'-dihydroxybenzophenone, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, etc., and these may be used alone or in combination of two or more.

If necessary, other divalent compounds, such as 4゜41-
Biphenol, hydroquinone, resorcinol, 2.6
-Sihydroxynaphthalene or the like can be used by adding a small amount to the above-mentioned bisphenols.

The derivatives of bisphenols include their alkali metal salts, diacetates, and the like. Among these bisphenols, bisphenol A, l.

(2) The use of -bis(4-hydroxyphenyl)1-phenylethane or a mixture thereof is preferred since it has an excellent balance between molding fluidity and heat resistance.

As the aromatic dicarboxylic acid in the above polyarylate,
For example, terephthalic acid, isophthalic acid, diphenyl ether-4,4'-dicarboxylic acid, benzophenone-4,4
'-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, etc., which may be used alone or in combination of two or more.

In view of the balance between molding fluidity and heat resistance, 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 1010 to 7/3. Examples of the aromatic dicarboxylic acid derivatives include dichlorides of these acids, and diesters of alkyl, aryl, and the like.

In the present invention, the content of epoxy groups is preferably in the range of 2 to 100 in terms of epoxy value (10-6 equivalents of epoxy groups contained in 1 g of resin), and more preferably in the range of 10 to 100.
The range is 50. Outside this range, high-speed punching impact strength and surface properties are reduced, and weld strength is reduced.

The above epoxy value is calculated by the following formula according to the 15O-3001 method (method for measuring the epoxy value of epoxy resin).

Epoxy value (to-' equivalent/g) However, in the above formula, Ts: 0, 1 normal required for titration of the sample Amount of acetic acid solution of 1c304 (d) Tb: 0, 1 required for titration of blank test Normal HCl0. Amount of acetic acid solution (d) F: 0.1N HCl0. Factor W of acetic acid solution: weight of sample (g).

Polyarylate G having an epoxy group of the present invention is not limited to its production method, but for example, as described below, a polyarylate having a carboxylic acid chloride group,
It can be obtained by reacting a compound having a hydroxyl group and an epoxy group in the same molecule.

For polyarylates having acid chloride groups, for example, as disclosed in JP-A-1-22851, the dichloride of aromatic dicarboxylic acid is added to the functional group based on the total amount of bisphenols and phenolic compounds used as necessary. It can be obtained by carrying out polymerization using an amount in excess of the theoretical equivalent. The polyarylate having acid chloride groups obtained in this way must contain the amount of acid chloride groups necessary to obtain the desired epoxy value in the present invention. The chloride group content is determined by the acid chloride value (
10-h equivalent of acid chloride groups contained in 1 g of resin)
and must be between 2 and 100.

The hydroxyl group and epoxy group to be reacted with the polyarylate having such an acid chloride group are contained in the same molecule.
Specific examples of compounds include 2.3-epoxy-1-propatol, 3.4-epoxy-1-butanol, and 3.4-epoxy-1-propanol.
-Aliphatic and alicyclic compounds such as epoxycyclohexanol, ethylene glycol monoglycidyl ether, and tetramethylene glycol monoglycidyl ether, 4-
Examples include aromatic compounds such as (1'',2'-epoxyethyl)-phenol, glycidyl p-hydroxybenzoate, and 2,2-bis(4-hydroxyphenyl)-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, the polyarylate having an acid chloride group is dissolved in an organic solvent that is substantially incompatible with water. This is a method in which a compound having a hydroxyl group and an epoxy group in the same molecule is added and reacted in the presence of an acid acceptor. a! As a receptor,
An aqueous alkaline solution or tertiary amines are used.

The molecular weight of the polyarylate is preferably in the range of intrinsic viscosity (chloroform solution, 30 DEG C.) from 0.2 to 1.5 d1/g(1)N, more preferably from 0.4 to 0.8 d17H. Outside this range, high-speed punching impact resistance and moldability may deteriorate, which is not preferable.

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.

Polyamides particularly useful in the present invention include polycaproamide (
Nylon-6), polyhexamethylene adipamide (nylon-66), polytetramethylene adipamide (nylon-46), polydodecanamide (nylon-12), among which nylon-6 and nylon-66 are This is especially 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 sulfur NI solution.

The ionomer in the present invention refers to α-olefin and α-olefin.
, a metal salt of a carboxylic acid copolymer of β-unsaturated carboxylic acid. Copolymers of α-olefins and α,β-unsaturated carboxylic acids include ethylene/acrylic acid copolymers, ethylene/methacrylic acid copolymers, ethylene/ethyl acrylate/acrylic acid copolymers, and ethylene/acrylic acid copolymers.
Examples include propylene/acrylic acid copolymer. Metal salts include monovalent to trivalent metal ions (for example,
Na', K", L i", Cu", Mg"Zn", AI
”) is suitable.

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.
With respect to 100 parts by weight of the resin composition (A) consisting of % by weight,
Resin composition (A) 1 consisting of 1 to 40 parts by weight of ionomer (B), more preferably 30 to 60% by weight of polyarylate having epoxy groups and 70 to 40% by weight of polyamide
00 parts by weight, the ionomer (B) is 3 to 30]i
1 part is added. Outside this range, impact resistance, surface properties, 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, Brabender, Banbury mixer, etc. can be used.

The resin composition of the present invention may further contain lubricants such as wax, stabilizers such as phosphites and phenols, ultraviolet absorbers, pigments, flame retardants, plasticizers, inorganic fillers, fillers, and reinforcing agents. 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. These molded products are used in various automotive exterior parts, automotive exterior panels, mechanical parts, electrical and
Useful for applications such as electronic components.

〔Example〕

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

Reference examples (borea relays having epoxy groups) P-1 to P
-9 synthesis) P-1: 2.2-bis(4-hydroxyphenyl)-propane (
Bisphenol A) 674.6 g (2,955 mol), p-(t-butyl)phenol 13.52 (0,
09 mol), sodium hydrosulfide 5.28
g, 4N sodium hydroxide 1.920d and water 3,
After mixing 320 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, another 6i! In a flask, 124.25 g (0,612 mol) of terephthalic acid chloride and 496.99 g (2,448 mol) of isophthalic acid chloride were dissolved in 5,000 m of methylene chloride and cooled to 5°C.

Then another 15! In a separable flask, add 2
,000d and 0.94 g (0.03 mol) of benzyltributylammonium chloride as a catalyst were charged under a nitrogen atmosphere and 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.

When stirring was stopped 60 minutes after the addition was completed, the mixture was separated into two phases: a methylene chloride phase and an aqueous phase. After decanting the aqueous phase, the same amount of water was added and neutralized with a small amount of hydrochloric acid while stirring. Furthermore, after repeated desalination by water washing, the same amount of acetone was added to the methylene chloride phase 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. . When the acid chloride value (10-” equivalent/g) of the dried polymer was measured,
It was 45. Further, the molecular weight was 0.62 d1/g expressed in terms of 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.
．． OOO++d was added and the polymer was dissolved under stirring and reflux. After the polymer solution became completely clear, it was cooled to 5°C. Thereafter, under stirring, a methylene chloride solution (500 ml) containing 44.45 g (0.6 mol) of 2°3-epoxy-1-propanol and 6.68 g of triethylamine was added.
(0,066 mol) in methylene chloride (50d) 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.

Approximately 0.2 g of polymer powder was accurately weighed, and 20 Id of chloroform was added thereto to dissolve it. After dissolution, a small amount of a 25% acetic acid solution of tetraethylammonium bromide and a 0.1% acetic acid solution of Crystal Hi-Olent were added as indicators. Immediately add this purple sample solution to 0. I
Titration was carried out using a solution of N HClO4 in acetic acid, 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 previous 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 0.6
It was 2 dl/g.

P-2 to 6 and P-8 = Various epoxy values were obtained by changing the ratio of 2,2-bis(4-hydroxyphenyl)-propane (bisphenol A) and acid chloride components in the same manner as in P-1 above. A polyarylate having the following was produced.

In addition, as a bisphenol component, the molar ratio of 2.2-bis(4-hydroxyphenyl)-propane (bisphenol A) and 1.1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol P) is 50: 5
A polyarylate was also produced using a mixture of 0 and 0 as the bisphenol component. Table 1 shows the epoxy value and intrinsic viscosity of the polyarylate measured in the same manner as P-1.

P-7 and P-9: In addition, for comparison, polyarylates having no epoxy groups were produced by a conventional interfacial polycondensation method. P-1
Table 1 shows the epoxy value and solid viscosity of the polyarylate, which were measured in the same manner as above.

Examples 1 to 1G and Comparative Examples I to 7 Polyarylates P-1 to P-9 obtained in Reference Examples and Amilan CM1026 (polyε
- caprolactam (relative viscosity 3°2) and Himilan 1652 (Zn salt of ethylene/methacrylic acid copolymer) manufactured by Mitsui Polychemical Co., Ltd. as an ionomer were blended in the proportions shown in Table 2 and triblended, then heated at 80°C. Vacuum dry for 15 hours, then use a two-wheel extruder to
Pellets were obtained by kneading at °C. This pellet at 120°
Vacuum drying was performed at C for 15 hours, and injection molding was performed at a resin temperature of 290°C to obtain a test piece.

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 HRJT8000 made by Rheometric, a punch (5/8 inch diameter) was used to punch 5 m/
A test piece (100×100×3+a+) was punched out at a speed of 100×100×3+a+, and the energy required for punching was measured.

Measurements were performed at 23°C and -30°C.

[Surface properties of molded product]

A 100×100×3on flat plate 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 △: Slightly defective ×: Significantly defective As is clear from the results in Table 2, the resin composition of the present invention shows no decrease in melt viscosity and physical properties after residence. This has been significantly improved, and the physical properties of the molded product are also excellent.

[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.

Furthermore, it is surprising that by using an ionomer as an impact resistance imparting agent, all of the above-mentioned problems of resin compositions made of polyarylate and polyamide can be solved.

As with soft soil, the present invention provides a resin composition that has excellent impact resistance, particularly high-speed punching impact resistance and surface properties.

Claims (1)

[Scope of Claims] 1. A resin composition consisting of 20 to 80% by weight of polyarylate having an epoxy group and 80 to 20% by weight of polyamide (
A) 1 to 40 parts by weight of ionomer (B) per 100 parts by weight
A thermoplastic resin composition prepared by adding parts by weight. 2. The thermoplastic resin composition according to claim 1, wherein the epoxy group content of the polyarylate having epoxy groups is 2 to 100 in terms of epoxy value (10^-^6 equivalents of epoxy groups contained in 1 g of resin). . 3. The thermoplastic resin composition according to claim 1, wherein the polyarylate having epoxy groups has an epoxy group content of 10 to 50 in terms of epoxy value (10^-^6 equivalents of epoxy groups contained in 1 g of resin). . 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 1,1-
4. The thermoplastic resin composition according to claim 1, which is an aromatic polyester consisting of 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.