JPH02173063A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare a thermoplastic resin compsn. excellent in impact strength, solvent resistance and moldability by compounding a specific epoxy resin into a resin component comprising a polyarylate resin, a polyamide resin and a polyethylene terephthalate resin. CONSTITUTION:100 pts.wt. resin component comprising at least 10wt.% polyarylate resin, at least 20wt% polyamide resin and 3-60wt.% polyethylene terephthalate resin is compounded with 0.1-15 pts.wt. epoxy resin of formula I (wherein X is a direct bond, 1-4C alkylene, formula II-IV, -SO2-, -O- or -S-, and a part or all of H atoms in X may be substd. by halogen; R is H, halogen or 1-4C alkyl; and n>=1) to give a thermoplastic resin compsn. The amt. of said epoxy resin compounded of less than 0.1 pt.wt. gives little improvement in the impact strength; that of more than 15wt.% reduces the heat resistance and increases the m.p. and viscosity, thus making its molding difficult.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is made of polyarylate resin, polyethylene terephthalate resin, polyamide resin, and epoxy resin that have excellent impact strength, excellent solvent resistance, and moldability. The present invention relates to a thermoplastic resin composition.

<Prior Art> Compositions made of polyarylate resins, polyethylene terephthalate resins and polyamide resins have excellent heat resistance, solvent resistance and moldability, and are disclosed, for example, in Japanese Patent Publication No. 58-50260.

<Problems to be Solved by the Invention> However, although polyarylate and polyethylene terephthalate are easily compatible, polyamide is incompatible with the former two, so a composition obtained by melt-kneading them exhibits a phase-separated structure, The disadvantage is that the adhesive strength at the interface between the polyarylate or polyethylene terephthalate phase and the polyamide phase is weak, resulting in low impact strength and brittleness.

In order to improve the impact strength of the resin composition,
Although the manufacturing method was improved in No. 2-100552, it still does not have sufficient mechanical strength.

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

Means for Solving the Problems The present inventors have discovered that the impact strength of the composition can be improved by increasing the bonding force between the interface between the polyester phase and the polyamide phase of polyarylate and polyethylene terephthalate, which are phase separated. With this in mind, we earnestly searched for a compatibilizer with a functional group that interacts with both the amide bond in the polyamide phase and the ester bond in the polyester phase, and found that an epoxy resin obtained from bisphenol and epichlorohydrin has improved impact strength with the addition of a small amount. It was found that it had a remarkable effect on improving the results.

That is, the present invention comprises 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, and 10% by weight of such resin.
0 parts by weight, 15O2--0--3-, some or all of the hydrogen atoms in X may be replaced with halogen atoms, and R is a hydrogen atom, a halogen atom, or a carbon atom. Any of the lower alkyl groups of numbers 1 to 4, n
is an integer of 1 or more) epoxy resin 0.1
-15 parts by weight of a thermoplastic resin.

The present invention will be explained in more detail below.

The polyarylate resin used in the present invention includes terephthalic acid and isophthalic acid (and their derivatives), and bisphenols represented by the formula (X is a direct bond, a lower alkylene group having carbons a1 to 4) and their derivatives. (However, Y is either a lower alkylene group having 1 to 4 carbon atoms, 13O2-1-〇-1-S--C-,
Some or all of the hydrogen atoms in Y may be replaced with halogen atoms, and R is either a hydrogen atom, a halogen atom, or a lower alkyl group having 1 to 4 carbon atoms, and may be the same or different. good).

The above-mentioned bisphenols represented by the formula are 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)sulfide -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)diphenylmethane,
Examples include bis(4-hydroxyphenyl)difluoromethane.

Among these, 2,2-bis(4-hydroxyphenyl)propane, i.e., bisphenol A, is preferred because it is easy to use as a raw material. If necessary, a small amount of an aromatic dihydroxy compound, such as 4,4'-
A mixture of biphenol, 2,6-naphthalenediol, hydroquinone, chlorohydroquinone, etc. can also be used. Conductors of terephthalic acid and isophthalic acid include acid halogen compounds such as terephthalic acid dichloride and isophthalic acid dichloride, dimethyl terephthalate,
Indicates diester acid compounds such as dimethyl isophthalate, diphenyl terephthalate, and diphenyl isophthalate.

In the terephthalic acid, isophthalic acid, and their readers 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 produced by interfacial polymerization method,
It may be synthesized by either solution polymerization method or melt polymerization method.

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

The polyamide resin used in the present invention is represented by the formula % (R+ Rz and R3 represent an alkylene group having 2 to 16 carbon atoms), and is produced by the condensation reaction of a diamine and a dibasic acid, or the reaction of an amino acid. It is synthesized by self-condensation or ring-opening polymerization of lactam. For example, ε−
Nylon 6 synthesized from caprolactam or ε-aminocaproic acid, nylon 6-6 synthesized from hexamethylene diamine and adipic acid, nylon 6-10 synthesized from hexamethylene diamine and sebacic acid. Nylon 6-12 synthesized from hexamethylene diamine and dodecanoic acid, Nylon 11 synthesized from ω-aminoundecanoic acid, Nylon 12.1° 4-diaminobutane synthesized from ω-laurolactam or ω-aminododecanoic acid. Examples include nylon 4-6 synthesized from adipic acid and adipic acid. Nylon 6 and nylon 6-6 are preferably used because of their ease of raw material availability.

The epoxy resin used in the present invention has the general formula (X is either a direct bond, a lower alkylene group having 1 to 4 carbon atoms, 15o2- -0- -3-, and some of the hydrogen atoms of X or All may be replaced with halogen atoms, and R is a hydrogen atom, a halogen atom, and a carbon number of 1 to
(n is an integer of 1 or more) and is obtained from the reaction of bisphenol and epichlorohydrin.

Examples of bisphenols include 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-hydroxyphenyl)
3,5-dimethylphenyl)propane, 2,2-bis(
Examples include 4-hydroxy-3,5-dichlorophenyl)propane and 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane.

2,2-bis(4-hydroxyphenyl)propane, i.e., bisphenol A, is preferably used because of its ease of raw material availability.

The number of repeating units, n, represented by the general formula of the epoxy resin must be 1 or more.

When n is zero, the effect of the epoxy group at the terminal group is likely to be evident, and the resulting resin composition is likely to undergo gelation, coloration, and decomposition. In particular, the melting temperature and viscosity increase significantly, making molding difficult. In order to fully bring out the effect of improving impact strength of the present invention, it is preferable that the terminal epoxy group and the repeating polyether polyol moiety be present in an appropriate ratio. That is, the preferred range of n is about 6-20. In addition, the preferred range of epoxy equivalent is about 1000 to 300 in the case of bisphenol A epoxy resin.
It is 0.

The epoxy resin used in the present invention can be copolymerized with diols other than bisphenol, such as aromatic diols such as 2゜6-naphthalene diol and hydroquinone, and aliphatic diols such as 1,4-butanediol, propylene glycol, and ethylene glycol, if small amounts are used. You may let them.

The composition ratio of the polyarylate resin, polyethylene terephthalate resin, and polyamide resin used in the present invention is 10% by weight or more, 3 to 60% by weight, and 20% by weight or more, respectively, based on the total amount of the three components. Polyarylate resin is 1
If the content of the polyamide resin is less than 0% by weight, the resulting resin composition will have low heat resistance and impact strength, and if the content of the polyamide resin is less than 201i% by weight, the moldability and solvent resistance will decrease.

Moreover, if the polyethylene terephthalate resin is less than 3% by weight, the moldability and rigidity (modulus of elasticity) of the resulting resin composition will be reduced, and if it exceeds 60% by weight, the heat resistance and impact strength will be reduced.

When the polyarylate component increases, the impact strength and heat resistance of the resulting resin composition increases, 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 polyarylate resin has a well-balanced composition ratio of 15 to 4 in heat resistance, impact resistance, moldability, rigidity, and solvent resistance.
5% by weight of melon, 45-65% by weight of polyamide resin, and 7-35% by weight of polyethylene terephthalate resin.

The amount of the epoxy resin used as a compatibilizer was 1 o of a mixture of polyarylate resin, polyamide resin, and polyethylene terephthalate resin.

It is preferable to add 0.1 to 15 parts by weight based on the weight part. If it is less than 0.1 parts by weight, the effect of improving impact resistance will be small, and if it exceeds 15 parts by weight, the heat resistance of the resulting composition will decrease, and the melting temperature and viscosity will increase, making molding difficult. do not have. The preferred addition amount is 2
~10 parts by weight.

The method for producing the composition of the present invention can be any method that can melt and knead Borearyl 1 to resin, polyamide resin, polyethylene terephthalate resin, and epoxy resin. For example, two roll mill, Banbury mixer 1
There are single-screw extruders, twin-screw extruders, etc., and molding may be carried out while kneading in an injection molding machine, preferably a high kneading type axle-shaft or twin-screw extruder.

The kneading order for obtaining the composition of the present invention may be any order. 4 of polyarylate, polyamide, polyethylene terephthalate and epoxy resin
The components may be kneaded simultaneously, 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 polyarylate and polyethylene terephthalate are melt-kneaded in advance, and this mixture is melt-kneaded with polyamide and epoxy resin.

Additives, fillers, etc. may be added to the resin composition in the present invention. Additives include antioxidants and heat stabilizers such as copper halides and hindered phenols; phosphorus processing stabilizers; benzotriazole and hindered amine light stabilizers; paraffins, higher fatty acids, and their Preservatives such as esters and metal salts, lubricants such as silicone resins and fluorine resins; decabromodiphenyl ether, tetrabromobisphenol A, tetrachlorobisphenol A, aluminum wood oxide, antimony trioxide, ammonium phosphate, tricresyl phosph Examples include flame retardants such as 8, triethyl phosphate, pigments, and dyes. Fillers include talc, calcium carbonate, mica, wollastonite, ferrite, rare earth magnet powder, glass fiber, carbon fiber, and asbestos! Examples include a fiber, metal m fiber, aramid fiber, and potassium titanate whiskers.

<Example> The present invention will be specifically described below 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-poly v-U-100) manufactured by Unitika ■. Logarithmic viscosity is 0.65 afl/g (0.25 g using phenol/tetrachloroethane = 60/40 weight ratio as solvent)
/dIl concentration, measured at 23°C).

(Raw material 2) Polyethylene terephthalate resin (PET) (PET resin manufactured by Teijin ■ TR-4550B) I) Logarithmic viscosity 047
0 (same measurement method as raw material 1) (raw material 3) Nylon 6 (PA6) (manufactured by Toshi ■ Amilan C old 01
7) (Raw material 4) Nylon 6-6 (PA6-6) (Alamine C manufactured by Toshi ■)
M3001) (Raw materials 5 to 10) Epoxy resin (manufactured by Dainippon Ink & Chemicals) CHo (Raw material 11) Phenoxy resin (Phenoxy PKHH manufactured by Union Carbide) rll.

n Medium 100 Melt.

(Raw material 12) A product obtained by modifying the terminal epoxy group of Epiclon 9055 with jetanolamine.

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

1) Bow H Length Test 2 According to ASTM D-638, measurements were carried out at a tensile speed of 50 mm for 7 minutes, and the tensile breaking strength, tensile modulus of elasticity, and tensile breaking energy (the amount of work required to break) were determined. Ta.

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

3) Heat deformation temperature: After annealing at 150° C. for 3 hours, measurements were made according to ASTM D-648 at a thickness of 1/8 inch and a load of 18.6 kg/cm.

4) Temperature at which the melt viscosity reaches 10,000 boids: φ0 by high load type flow tester CFT-500 manufactured by Oshi Seisakusho ■
．． 5X1. The viscosity of the resin was sequentially measured using a nozzle of 0.0 mm, a load of 10 kg, and a temperature increase rate of 6° C./min, and the temperature at which the melt viscosity reached 10,000 voids was determined. A guide to the moldability of resin,
This serves as a guide to the progress of the gelation reaction. That is, the lower the temperature, the more gelation progresses and the easier it is to mold.

(Examples 1 to 6, Comparative Examples 1 to 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,
After drying at 110℃ for 5 hours, cylinder temperature 3
The mixture was melted and kneaded in a 2@extruder at 00°C to form pellets.
50 parts by weight of this mixture of polyarylate resin and polyethylene terephthalate resin and 50 parts by weight of nylon 6 (raw material 3) are mixed, and the amount of epoxy resin (raw material 9) shown in Table 1 is added to 100 parts by weight of this mixture. 5 at 110℃
After drying for several hours, the mixture was melt-kneaded in a twin-screw extruder with a cylinder temperature of 270°C to form pellets. This pellet was made into an injection molding machine with 1/2 x 115 x 1/8 inch short shelf test pieces and dumbbells for tensile testing. It was molded and its physical properties were evaluated. The results are shown in Table 1.

Table 1 shows that adding a small amount of epoxy resin
It can be seen that the impact strength and tensile energy to break increase significantly. However, if the amount of epoxy resin added exceeds 15 parts by weight, impact strength and heat distortion temperature will decrease, and moldability will deteriorate.

(Examples 7 to 11, Comparative Examples 3 to 8) Polyarylate resin (raw material 1) having the composition ratio shown in Table 2,
Example 1 Polyethylene terephthalate resin (raw material 2), nylon 6 (raw material 3) and epoxy resin (raw material 9)
The pellets were made into pellets using the same kneading order and kneading method as above, and injection molding and physical property evaluation were performed. The results are shown in Table 2.

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

<Effects of the Invention> The present invention has excellent moldability, heat resistance, impact resistance, and solvent resistance.
Moreover, it provides an excellent resin composition with high rigidity and well-balanced physical properties, and it is suitable for applications that take advantage of these characteristics, such as housings for electronic and electrical appliances that are exposed to high heat, switches, knobs, and solvent-resistant. It is ideal for various types of containers and daily necessities that take advantage of its characteristics.

Claims (1)

[Claims] (1) For 100 parts by weight of a resin consisting 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, apply the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (X is a direct bond, a lower alkylene group with 1 to 4 carbon atoms, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, -SO_2-, -O-, -S-, some or all of the hydrogen atoms of X may be replaced with halogen atoms, and R is a hydrogen atom, a halogen atom, or has 1 carbon atom.
-4 lower alkyl groups, and n is an integer of 1 or more.