JPH0733467B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention comprises a polyarylate resin, a polyethylene terephthalate resin, a polyamide resin and an epoxy resin which have excellent impact strength, solvent resistance and moldability. It relates to a thermoplastic resin composition.

<Prior Art> A composition comprising a polyarylate resin, a polyethylene terephthalate resin and a polyamide resin has excellent heat resistance, solvent resistance and moldability, and is disclosed in, for example, Japanese Patent Publication No. 58-50260.

<Problems to be Solved by the Invention> However, although polyarylate and polyethylene terephthalate are easily compatible with each other, polyamide is incompatible with the former two, and thus a composition obtained by melt-kneading them shows a phase separation structure, Since the adhesive strength at the interface between the polyarylate or polyethylene terephthalate phase and the polyamide phase is weak, the impact strength is small, and there is a drawback that it is brittle.

In order to improve the impact strength of the resin composition, JP-A-52
No. -100552 has improved the manufacturing method, but has not yet reached sufficient mechanical strength.

The present invention has been made in view of the above-mentioned circumstances, and has excellent solvent resistance, heat resistance, moldability, and high rigidity, which are characteristics of a thermoplastic resin composition including a polyarylate resin, a polyethylene terephthalate resin, and a polyamide resin. An object of the present invention is to provide a thermoplastic resin composition having a significantly improved impact strength without impairing thermal stability.

<Means for Solving the Problems> The present inventors improve the impact strength of the composition by strengthening the bonding force between the interfaces of the polyester phase and the polyamide phase of polyarylate and polyethylene terephthalate, which are phase separated. In consideration of this, a diligent search was made for a compatibilizer having a functional group capable of interacting with both the amide bond of the polyamide phase and the ester bond of the polyester phase. As a result, the epoxy resin obtained from bisphenol and epichlorohydrin had a small impact strength. It was found that there was a remarkable effect on the improvement of.

That is, the present invention is a polyarylate resin 10 wt% or more,
To 100 parts by weight of a resin composed of 20% by weight or more of polyamide resin and 3 to 60% by weight of polyethylene terephthalate resin, (X is a direct bond, a methylene group having 1 carbon atom, a carbon number of 2 to 4
A lower alkylidene group, a lower alkylene group having 1 to 4 carbon atoms, _{-SO 2 -, - O -,} - and the S- either, may be part or all of the hydrogen atoms of X is substituted by a halogen atom, R represents a hydrogen atom, a halogen atom, 1 to carbon atoms Four
Of the lower alkyl groups, and n is an integer of 1 or more), the thermoplastic resin containing 0.1 to 15 parts by weight of the epoxy resin.

The present invention will be described in more detail below.

The polyarylate resin used in the present invention includes terephthalic acid, isophthalic acid (and their derivatives), and general formula And bisphenols and derivatives thereof (wherein Y is a methylene group having 1 carbon atom, a lower alkylidene group having 2 to 4 carbon atoms, a lower alkylene group having 1 to 4 carbon atoms, Or a hydrogen atom of Y may be partially or entirely replaced by a halogen atom, R is a hydrogen atom,
A halogen atom or a lower alkyl group having 1 to 4 carbon atoms, which may be the same or different from each other).

As the bisphenols represented by the above general formula, 2,
2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4- Hydroxyphenyl) ketone, bis (4-hydroxy-3-methylphenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane,
1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl)
Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5
-Dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl)
Examples thereof include diphenylmethane and bis (4-hydroxyphenyl) difluoromethane.

Of these, 2,2-bis (4-hydroxyphenyl)
Propane, that is, bisphenol A is preferable because of easy availability of raw materials. If necessary, a small amount of an aromatic dihydroxy compound such as 4,4'-biphenol, 2,6-naphthalenediol, hydroquinone, etc. may be added to the bisphenols.
It is also possible to use a mixture of chlorohydroquinone and the like. Derivatives of terephthalic acid and isophthalic acid include acid halogen compounds such as terephthalic acid dichloride and isophthalic acid dichloride, and diester acid compounds such as dimethyl terephthalate, dimethyl isophthalate, diphenyl terephthalate and diphenyl isophthalate.

In the terephthalic acid, isophthalic acid and their derivatives used in the present invention, some or all of the hydrogen atoms of the phenylene group may be substituted with a halogen atom or a lower alkyl group.

The polyarylate resin used in the present invention is an interfacial polymerization method,
It may be synthesized by either a solution polymerization method or a melt polymerization method.

Examples of the polyethylene terephthalate resin used in the present invention include those produced from terephthalic acid (and its derivative) and ethylene glycol by any method.

The polyamide resin used in the present invention has the general formula (R ₁ , R ₂ and R ₃ represent an alkylene group having 2 to 16 carbon atoms), which is synthesized by condensation reaction of diamine and dibasic acid, self-condensation of amino acid, or ring-opening polymerization of lactam. It is what is done. For example, nylon 6 synthesized from ε-caprolactam or ε-aminocaproic acid, nylon 6-6 synthesized from hexamethylenediamine and adipic acid, nylon 6-10 synthesized from hexamethylenediamine and sebacic acid, and hexamethylenediamine Nylon 6-1 synthesized from dodecanedioic acid
2. Nylon 1 synthesized from ω-aminoundecanoic acid
1, Nylon 12, which is synthesized from ω-laurolactam or ω-aminododecanoic acid, and nylon 4-6, which is synthesized from 1,4-diaminobutane and adipic acid.
Nylon 6 and nylon 6-6 due to easy availability of raw materials
Is preferably used.

The epoxy resin used in the present invention has the general formula (X is a direct bond, a methylene group having 1 carbon atom, a carbon number of 2 to 4
A lower alkylidene group, a lower alkylene group having 1 to 4 carbon atoms, _{-SO 2 -, - O -,} - and the S- either, may be part or all of the hydrogen atoms of X is substituted by a halogen atom, R represents a hydrogen atom, a halogen atom, 1 to carbon atoms Four
Is a lower alkyl group of n, and n is an integer of 1 or more), and is obtained from the reaction of bisphenol and epichlorohydrin.

Examples of bisphenols. Bis (4-hydroxyphenyl) sulfone, 4,4'-biphenol, bis (4-hydroxyphenyl) methane, 2,2-bis (4-
Hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl)
Diphenylmethane, 2,2-bis (4-hydroxy-3,5-
Examples thereof include dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, and 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane. 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A, is preferably used because the raw materials are easily available.

The number n of repeating units represented by the general formula of the epoxy resin must be 1 or more. When n is zero, the effect of the terminal epoxy group is likely to be exerted, and the resulting resin composition is likely to cause gelation, coloring, and decomposition. Especially the melting temperature
The viscosity increases remarkably, making molding difficult. In order to sufficiently bring out the effect of improving the impact strength of the present invention, it is preferable that the epoxy group at the terminal and the polyether polyol portion at the repeating portion are present in an appropriate ratio. That is, preferable n
The range is about 6-20. The preferred epoxy equivalent range is about 1000 to 3000 in the case of the bisphenol A type epoxy resin.

The epoxy resin used in the present invention is a small amount of diol other than bisphenol, that is, an aromatic diol such as 2,6-naphthalene diol and hydroquinone, and an aliphatic diol such as 1,4-butane diol, propylene glycol and ethylene glycol. You may let me.

The composition ratio of the polyarylate resin, polyethylene terephthalate resin and polyamide resin used in the present invention is 10% by weight or more and 3 to 60% by weight, respectively, based on the total amount of the three components.
It is 20% by weight or more. When the polyarylate resin is less than 10% by weight, the resulting resin composition has low heat resistance and impact strength, and when the polyamide resin is less than 20% by weight, moldability and solvent resistance are deteriorated. If the polyethylene terephthalate resin content is less than 3% by weight, the moldability and rigidity (elastic modulus) of the resin composition obtained will decrease, and if it exceeds 60% by weight, heat resistance and impact strength will decrease.

When the polyarylate component increases, the impact strength and heat resistance of the obtained resin composition increase, when the polyamide component increases, the moldability and solvent resistance improve, and when the polyethylene terephthalate component increases, the moldability improves and the rigidity increases. Increase. Preferably, the composition ratio that balances heat resistance, impact resistance, moldability, rigidity, and solvent resistance is 15 to 45% by weight of polyarylate resin, 45 to 65% by weight of polyamide resin, and 7 to 35% by weight of polyethylene terephthalate resin. Is.

The amount of the epoxy resin used as the compatibilizer is preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the mixture of the polyarylate resin, the polyamide resin and the polyethylene terephthalate resin. If it is less than 0.1 part by weight, the effect of improving impact resistance is small, and if it exceeds 15 parts by weight, the heat resistance of the resulting composition is lowered and the melting temperature and viscosity are increased, which makes molding difficult. The preferred addition amount is 2 to 10 parts by weight.

The method for producing the composition of the present invention can be used as long as it can melt-knead a polyarylate resin, a polyamide resin, a polyethylene terephthalate resin and an epoxy resin. For example, there are a two-roll mill, a Banbury mixer, a single-screw extractor, a twin-screw extruder, and the like, and molding may be performed while kneading in an injection molding machine. A high kneading type single-screw or twin-screw extruder is preferable.

The kneading order for obtaining the composition of the present invention may be any order. Polyarylate, polyamide,
The four components of polyethylene terephthalate and the epoxy resin may be kneaded at the same time, or two or more of the four components may be kneaded in advance and then the other components may be kneaded. The optimum kneading order is a method in which the polyarylate and polyethylene terephthalate are melt-kneaded in advance, and this mixture and the polyamide and epoxy resin are melt-kneaded.

You may add an additive, a filler, etc. to the resin composition in this invention. As additives, antioxidants such as copper halides and hindered phenols, heat stabilizers, phosphorus-based processing stabilizers, benzotriazole- and hindered amine-based light stabilizers, paraffins, higher fatty acids and their esters , Plasticizers such as metal salts, lubricants such as silicone resins and fluororesins; decabromodiphenyl ether, tetrabromobisphenol A, tetrachlorobisphenol A, aluminum hydroxide, antimony trioxide, ammonium phosphate, tricresyl phosphate, triethyl Flame retardants such as phosphates; pigments;
Examples include dyes. As the filler, talc, calcium carbonate, mica, wollastonite, ferrite, rare earth magnet powder, glass fiber, carbon fiber, asbestos fiber,
Examples include metal fibers, aramid fibers, and potassium titanate whiskers.

<Examples> Hereinafter, the present invention will be specifically described based on Examples.

First, raw materials used in Examples and Comparative Examples will be described.

(Raw material 1) Polyarylate resin (PAR) obtained from a 1/1 mixture of terephthalic acid / isophthalic acid and bisphenol A (U-polymer U-100 manufactured by Unitika Ltd.). Log viscosity is
0.65dl / g (phenol / tetrachloroethane = 60/40 weight ratio as solvent, concentration of 0.25g / dl, measured at 23 ° C).

(Raw material 2) Polyethylene terephthalate resin (PET) (Teijin Ltd.)
PET resin TR-4550BH) Numerical viscosity resistance 0.70 (same as the measurement method for raw material 1) (Raw material 3) Nylon 6 (PA6) (Amylan CM1017 manufactured by Toray Industries, Inc.) (Raw material 4) Nylon 6-6 (PA6-6) ) (Toray Industries, Ltd. Alamin C
M3001) (Raw materials 5 to 10) Epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc.) (Raw material 11) Phenoxy resin (Phenoxy manufactured by Union Carbide
PKHH) (Raw material 12) The terminal epoxy group of Epicron 9055 is modified with diethanolamine.

Next, physical properties and evaluation methods performed in Examples and Comparative Examples of the present invention will be shown.

1) Tensile test: According to ASTM D-638, tensile speed 50mm
/ Minute, the tensile breaking strength, tensile modulus,
The tensile breaking energy (work required to break) was determined.

2) Izod impact test: Measured according to ASTM D-256 with a 1/8 inch thickness and notch.

3) Heat distortion temperature: After annealing at 150 ℃ for 3 hours, according to ASTM D-648, 1/8 inch thickness, load 18.6kg / c
Measured in m ² .

4) Temperature at which the melt viscosity reaches 10,000 poise: Shimadzu Corporation, high load type flow tester CFT-500 φ 0.5
The viscosity of the resin was successively measured with a nozzle of × 1.0 mm, a load of 10 kg, and a temperature rising rate of 6 ° C./min, and the temperature at which the melt viscosity reached 10,000 poise was determined. It serves as a guide for the moldability of the resin and the progress of the gelling reaction. That is, the lower this temperature is, the less gelation progresses and the easier the molding.

(Examples 1 to 6 and Comparative Examples 1 and 2) 60 parts by weight of polyarylate resin (raw material 1) and 40 parts by weight of polyethylene terephthalate resin (raw material 2) were mixed to obtain 110
After drying at 5 ° C for 5 hours, the mixture was melt-kneaded and pelletized by a twin-screw extruder having a cylinder temperature of 300 ° C. 50 parts by weight of a mixture of this polyarylate resin and polyethylene terephthalate resin and 50 parts by weight of nylon 6 (raw material 3) are mixed,
To 100 parts by weight of this mixture, the amount of the epoxy resin (raw material 9) shown in Table 1 was added, dried at 110 ° C. for 5 hours, melt-kneaded with a twin-screw extruder at a cylinder temperature of 270 ° C., and pelletized. 1/2 × 1/5 × 1/8 of these pellets with an injection molding machine
Inch strip-shaped test pieces and tensile test dumbbells were molded and the physical properties were evaluated. The results are shown in Table 1.

From Table 1, it can be seen that the addition of a small amount of epoxy resin markedly increases the Izod impact strength and the tensile breaking energy. However, when the amount of epoxy resin added exceeds 15 parts by weight, impact strength and heat distortion temperature are lowered, and moldability is deteriorated.

(Examples 7 to 11 and Comparative Examples 3 to 8) Polyarylate resins having the composition ratios shown in Table 2 (raw material 1),
Example 1 using polyethylene terephthalate resin (raw material 2), nylon 6 (raw material 3) and epoxy resin (raw material 9)
Pellets were formed by the same kneading order and kneading method, injection molding, and physical properties were evaluated. The results are shown in Table 2.

(Examples 12 to 18, Comparative Examples 9 to 13) With the raw materials and composition ratios shown in Table 3, the same method as in Example 1, that is, the polyarylate resin and the polyethylene terephthalate resin were melt-kneaded in advance, and other Pellets were formed by a method of adding two components and melt-kneading, and injection molding and physical property evaluation were performed. The results are shown in Table 3.

<Effects of the Invention> The present invention has excellent moldability, heat resistance, impact resistance, and solvent resistance,
In addition, it provides an excellent resin composition with high rigidity and well-balanced physical properties. Applications that take advantage of these features, that is, housings of electronic and electrical equipment exposed to high heat, slitches, knobs, solvent resistance Most suitable for various containers and daily necessities.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08L 77/00 LQU

Claims (1)

[Claims] 1. To 100 parts by weight of a resin composed of 10% by weight or more of polyarylate resin, 20% by weight or more of polyamide resin and 3 to 60% by weight of polyethylene terephthalate resin,
The following formula (X is a direct bond, a methylene group having 1 carbon atom, a carbon number of 2 to 4
A lower alkylidene group, a lower alkylene group having 1 to 4 carbon atoms, _{-SO 2 -, - O -,} - are either S- of some or all of the hydrogen atoms of X is may be replaced a halogen atom (s), R is a hydrogen atom, a halogen atom, 1 to carbon atoms Four
Any of the lower alkyl groups, and n is an integer of 1 or more) in an amount of 0.1 to 15 parts by weight, the thermoplastic resin composition.