JPH0292954A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition of high rigidity, outstanding in resistance to heat, impact and solvent, thus suitable for baking-coatable automobile outer ply plastics, etc., by blending each specific polyarylate resin, polyamide resin and epoxy resin at each specified amount. CONSTITUTION:The objective composition can be obtained by blending a total of 100 pts.wt. of (A) 10-90 (pref. 30-60) wt.% of a polyarylate resin containing >=70wt.% of a polyarylate resin component and (B) 90-10 (pref. 70-40) wt.% of a polyamide resin containing >=70wt.% of a polyamide resin component, with (C) 0.1-15 (pref. 2-10) pts.wt. of an epoxy resin of formula I (X is direct bond, 1-4C lower alkylene, of formula II, etc., part or the whole of the H atoms in X may by substituted by halogen atoms; R is H, halogen, etc.; n is >=1).

Description

Detailed Description of the Invention] (X is a direct bond, a lower alkylene group having 1 to 4 carbon atoms, <Industrial Application Field> The present invention has excellent impact strength, heat resistance, solvent resistance,
The present invention relates to a thermoplastic resin composition comprising a polyarylate resin, a polyamide resin, and an epoxy resin that also has excellent moldability.

<Prior Art> A composition made of a polyarylate resin and a polyamide resin has excellent heat resistance, solvent resistance, and moldability. For example, Japanese Patent Publication No. 56-14699 discloses a resin composition consisting of polyarylate and polyamide, and Japanese Patent Publication No. 52-10055 discloses a resin composition consisting of polyarylate and polyamide.
No. 2 discloses a resin composition comprising a polyarylate resin, which is a mixture of polyarylate and polyethylene terephthalate, and polyamide.

However, since polyarylate and polyamide are incompatible with each other, a composition obtained by melting and kneading them exhibits a phase-separated structure, and the adhesive strength at the interface between the polyarylate phase and polyamide phase is weak, resulting in low impact strength and brittleness. There were drawbacks.

In order to improve the impact strength of resin compositions made of polyarylate and polyamide, attempts have been made to add a compatibilizer or an impact strength imparting agent as a third component. For example, JP-A No. 58-67749 uses an N-substituted amide-containing polymer as the third component, JP-A No. 59-105050 uses a polyalkylene phenylene ester containing a sulfonate salt group, and JP-A No. 61-183353 uses a polyalkylene phenylene ester containing a sulfonate salt group. A glycidyl group-containing olefin copolymer was prepared in JP-A No. 62-2774.
No. 62 and JP-A-62-283146 use a mixture of an epoxy group-containing ethylene copolymer and an acid anhydride-containing olefin copolymer. However, JP-A-58-67749 and JP-A-59-105050
In the case of No. 2, the improvement in impact strength is not sufficient. Furthermore, in JP-A No. 61-183353, JP-A No. 62-277462, and JP-A No. 62-283146, the impact strength improvement effect is achieved when the content of the third component exceeds approximately 5% by weight. It is necessary to add 10 to 30% by weight to obtain a satisfactory impact strength. For this reason, the resulting resin composition is prone to thermal decomposition in the cylinder of an extruder or injection molding machine, and has disadvantages such as gelation, coloring, reduced mechanical strength, and poor appearance of molded products such as flow marks and silver. be. Furthermore, although the impact strength of the resulting resin composition is improved due to the inclusion of a large amount of olefin polymer, there is a drawback that the tensile/flexural strength, elastic modulus, and heat resistance are significantly reduced.

<Problems to be Solved by the Invention> The present inventors have discovered that the excellent solvent resistance, heat resistance, moldability, high rigidity, and thermal stability that are characteristics of a thermoplastic resin composition composed of polyarylate and polyamide are impaired. An attempt was made to significantly improve impact strength without any impact.

As a result of an intensive search for a compatibilizer with a functional group that interacts with any of the ester bonds of .

That is, in the present invention, the polyarylate resin component is 70% by weight.
Resin mixture 1 comprising 10 to 90% by weight of a polyarylate resin containing the above and 90 to 10% by weight of a polyamide resin containing 70% by weight or more of a polyamide resin component
00 parts by weight, Means for Solving the Problem> The inventors have found that the impact strength of the composition can be improved by increasing the bonding force between the interface between the phase-separated polyarylate phase and polyamide phase. Considering that the amide bond in the polyamide phase and the polyarylate phase (X is either a direct bond, a lower alkylene group having 1 to 4 carbon atoms, -S O2--0--S-, and the hydrogen atom of Part or all may be replaced with a halogen atom, and R is a hydrogen atom, a halogen atom, and has 1 to 4 carbon atoms.
(n is an integer of 1 or more) containing 0.1 to 15 parts by weight of an epoxy resin.

<Specific Structure of the Invention> The polyarylate resin used in the present invention includes terephthalic acid and isophthalic acid (and their derivatives), and bisphenols and their derivatives represented by the general formula (wherein Y is a carbon number of 1 to 4). lower alkylene group, -5O2, -0-1-S-1-〇-,
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 they may be the same or different from each other. ).

The bisphenols represented by the above general formula include 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,
Examples include bis(4-hydroxyphenyl)diphenylmethane and bis(4-hydroxyphenyl)difluoromethane.

Among these, 2,2-bis(4-hydroxyphenyl)propane, i.e., bisphenol A, is preferred because of its ease of raw material availability. If necessary, a small amount of an aromatic dihydroxy compound such as 4,4'-biphenol, 2,6-naphthalenediol, hydroquinone, chlorohydroquinone, etc. may be mixed with the bisphenols. Derivatives of terephthalic acid and isophthalic acid refer to 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 8-conductor 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.

A polyarylate resin is a mixture of a polyarylate resin of the general formula synthesized from the above bisphenols, terephthalic acid, and isophthalic acid (and their derivatives) and a polycarbonate resin represented by the general formula, or a mixture of a polyarylate resin and a polycarbonate resin of the general formula It refers to a product containing 70% by weight or more of a polyarylate resin component consisting of the three components shown below.

For example, a mixture of polyarylate resin and polybutylene terephthalate, a mixture of polyarylate resin and general formula unsulfide resin, a mixture of polyarylate resin and general formula oxide, a mixture of polyarylate resin and polysulfone resin represented by general formula , a mixture with polyether sulfone, a mixture of polyarylate resin and polyester polycarbonate resin, a mixture of polyarylate resin and aromatic liquid crystal polyester, a mixture of polyarylate resin and polyetherketone resin, and a mixture of polyarylate resin and polyester A mixture with ether ether ketone resin is also a polyarylate resin used in the present invention when it contains 70% by weight or more of the polyarylate resin component consisting of the three components.

Furthermore, in addition to the above-mentioned bisphenols, terephthalic acid, isophthalic acid, and derivatives thereof, polyethylene terephthalate, 2,6-naphthalene dicarboxylic acid, and 4.
Aromatic dicarboxylic acids and their derivatives such as 4'-diphenyldicarboxylic acid, paraacetoxybenzoic acid and
A resin copolymerized with an aromatic hydroxycarboxylic acid such as -hydroxy-6-naphthoic acid and its derivatives is also a polyarylate resin if it contains 70% by weight or more of the polyarylate resin component consisting of the three components.

The polyamide resin used in the present invention is represented by the general formula (RI R2 and R3 represent an alkylene group having 2 to 16 carbon atoms), and is a condensation reaction of diamine and dibasic acid, self-condensation of amino acid, Alternatively, it is synthesized by 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, and nylon 6-10 synthesized from hexamethylene diamine and dodecanoic acid. Nylon 6-12 is synthesized, Nylon 11 is synthesized from ω-aminoundecanoic acid, Nylon 12.1 is synthesized from ω-laurolactam or ω-aminododecanoic acid, and Nylon 12.1 is synthesized from 4-diaminobutane and adipic acid. Examples include nylon 4-6. Nylon 6 and nylon 6-6 are preferably used because of their ease of raw material availability.

Polyamide resin refers to the polyamide resin component containing 70% of the polyamide resin component.
Refers to those containing more than % by weight.

For example, the polyamide resin blended with a polyolefin and/or modified polyolefin, and the polyamide resin graft copolymerized with an ethylene-(meth)acrylic acid ester copolymer (Japanese Patent Publication No. 44-2
There are so-called high-impact nylons such as 9262), and polyamide elastomers made by block copolymerizing polyamide resin with polytetramethylene glycol or the like. The above-mentioned modified polyolefins are polyolefins modified by copolymerizing α,β-unsaturated carboxylic acids or their esters, glycidyl ethers, metal salt derivatives, and polyolefins modified by copolymerizing or grafting acid anhydrides. For example, ethylene-methacrylic acid (ester) copolymer is modified with Na, Z
Ionomer resin ionized with n, Mg, etc., modified EPDM made by grafting maleic anhydride onto ethylene-propylene-diene copolymer, polypropylene or polyethylene grafted with maleic anhydride, ethylene-glycidyl methacrylate-vinyl acetate copolymer ,
Examples include styrene-maleic anhydride-acrylic acid ester copolymer.

Furthermore, blends of polyamide and other resins, such as polyamide and ABS resin, polyamide and acrylic acid ester copolymer, polyamide and rubber-modified styrene-maleic anhydride copolymer, polyamide and polyphenylene ether, can also be used as the polyamide component. is 70% by weight
If it is contained above, it is a polyamide resin used in the present invention.

The epoxy resin used in the present invention has a general formula (X is either a direct bond, a lower alkylene group having 1 to 4 carbon atoms, -so, -o--s-, and some of the hydrogen atoms of or all may be replaced with halogen atoms, R is a hydrogen atom, a halogen atom, or a lower alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or more), and bisphenol and epichlorohydrin.

Examples of bisphenols include bis(4-hydroxyphenyl)sulfone, 4,4'biphenol, and bis(4-hydroxyphenyl)sulfone.
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, coloring, and decomposition, and in particular, the melting temperature and viscosity will 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, i.e., aromatic diols such as 2,6-naphthalene diol and hydroquinone, and aliphatic diols such as 1,4-butanediol, propylene glycol, and ethylene glycol. You may let them.

The polyarylate resin and polyamide resin used in the present invention must each contain 70% by weight or more of the polyarylate resin component and polyamide resin component. If the content is less than 70% by weight, the polyarylate resin component Either or both of the excellent impact resistance and heat resistance will be lost, and the excellent moldability and/or solvent resistance of the polyamide resin will be lost, and as a result, the resin composition of the present invention will lose either or both of the excellent moldability and solvent resistance of the polyamide resin. One or more of the characteristics of impact resistance, heat resistance, moldability, and solvent resistance deteriorate.

The ratio of the polyarylate resin and polyamide resin used in the present invention is 10 to 90% by weight for the former and 90 to 90% by weight for the latter.
It is 10% by weight. If heat resistance and impact resistance are important, the amount of polyarylate resin may be increased, and if moldability is important, the amount of polyamide resin may be increased. Preferably, the composition ratio is 30 to 60% by weight of polyarylate resin and 70 to 40% by weight of polyamide resin, which have well-balanced heat resistance, impact resistance, and moldability.

The amount of the epoxy resin used as a compatibilizer is preferably 0.1 to 15 parts by weight per 100 parts by weight of the mixture of polyarylate resin and polyamide resin.
When the 0.11i weight part is not grooved, the impact resistance improvement effect is small.
If the amount exceeds 15 parts by weight, it is not preferable because the heat resistance of the resulting composition decreases and the melting temperature and viscosity increase, making molding difficult. The preferred amount added 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 and knead polyarylate resins, polyamide resins, and epoxy resins. For example, a two-roll mill,
Banbury mixer - There are axle-shaft extruders, twin-screw extruders, etc., and it is also possible to mold while kneading in an injection molding machine.
Preferably, a high-kneading type axle or twin-screw extruder is used.

Additives, fillers, etc. may be added to the resin composition of the present invention. Examples of additives include antioxidants such as copper halides and hindered phenols, heat stabilizers, niline processing stabilizers; Triazole and hindered amine light stabilizers; paraffins, higher fatty acids and their esters, plasticizers such as metal salts, lubricants such as silicone resins and fluorine resins; decabromodiphenyl ether, tetrabromobisphenol A1, tetrachlorobisphenol A1, water Examples include flame retardants such as aluminum oxide, antimony trioxide, ammonium phosphate, tricresyl phosphate, and triethyl phosphate; pigments; and dyes. Fillers include 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.

<Example> The present invention will be specifically described below based on Examples.

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

1. Polyarylate resin (PAR-1 to PAR-12
) PAR-1: Polyarylate resin obtained from a 1/1 mixture of terephthalic acid/isophthalic acid and bisphenol A (Unitika U-Polymer 〇-100), logarithmic viscosity is 0.65 (phenol/tetrachloroethane W
60/40 weight ratio as solvent, 0. 25 g/dl
1 concentration, measured at 23°C).

PAR-2 to 6: 80 parts by weight of polyarylate resin of PAR-1 and 20 parts by weight of the following resins were heated to cylinder temperature 3.
The mixture was melt-kneaded using a twin-screw presser at 00 to 360°C.
PAR-2, PAR-3, PAR-4, PAR respectively
-5, PAR-6.

PAR-2: Mixture with polyphenylene sulfide resin (Rydon, manufactured by Phillips Chemical Co.) PAR-3: Mixture with polyether ether ketone (VICTREX450G, manufactured by Sumitomo Chemical Co., Ltd.) PAR-4
: Mixture with polyether sulfone (VICTREX4100G manufactured by Sumitomo Chemical Co., Ltd.) PAR-5: Polysulfone (UD manufactured by Amoco Chemicals Co., Ltd.)
Mixture with EL P-1700) PAR-6: 2-
PAR is a mixture of fully aromatic liquid crystalline polyester (Vectra A-950 manufactured by Polyplastics ■) obtained from hydroxy-6-naphthoic acid and 4-hydroxybenzoic acid.
-7: A polyarylate resin having the following structure was synthesized by melt polymerization of bisphenol A diacetate, terephthalic acid, isophthalic acid, and paraacetoxybenzoic acid according to the method disclosed in US Pat. No. 4,075,173.

(Numbers are mol%) Logarithmic viscosity 0.68 (Measurement method similar to PAR-1) PAR-8: Polyethylene terephthalate (logarithmic viscosity 0.72) by the method disclosed in JP-A-48-88193.
A polyarylate resin with the following structure was synthesized by copolymerizing the following.

Logarithmic viscosity 0.70 (measured using the same method as PAR-1) 2. Polyamide resin (PA-1 to PA-3) PA-1
: Nylon 6 (Amiran CM1017 made by Toshi) PA-2: Nylon 6-6 Amiran CM300 made by Toshi
1) PA-3: 80 parts by weight of nylon 6 of PA-1 and ethylene-acrylic acid ester-maleic anhydride copolymer (
Sumika CDF Chemical Bondine LX4110)
Parts of 201i were melt-kneaded using a twin-screw presser with a cylinder temperature of 240°C.

(Numbers are mol%) 3. Third component (CP-1 to CP-8) cp-i to CP-6: Epoxy resin (manufactured by Dainippon Ink & Chemicals) 1': L *) By perchloric acid titration The epoxy groups in the epoxy resin are quantified to determine the weight (g) of the resin per equivalent of epoxy groups, that is, the epoxy equivalent.

CP-7: Phenoxy resin (Phenoxy PKHH manufactured by Union Carbide) I'll.

CP-8: Epiclon 9055 whose terminal epoxy group is modified with jetanolamine.

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, measurements were performed at a tensile speed of 50 mm for 7 minutes to determine tensile strength at break, tensile modulus, and tensile energy at break (work required to break).

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

3) After annealing at a heat distortion temperature of 2150° C. for 3 hours, measurements were made in accordance with ASTM D-648 at a thickness of 1/8 inch, a load of 18, and a load of 6 kg/cm2.

4) Temperature at which the melt viscosity reaches 10,000 poise:
, sxt, and Omm nozzles, a load of 10 kg, and a temperature increase rate of 6° C./min. The viscosity of the resin was sequentially measured, and the temperature at which the melt viscosity reached 10,000 poise 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 less gelation progresses and the easier it is to mold.

(Examples 1 to 6, Comparative Examples 1 to 2) PAR-1 as a polyarylate resin, PA-1 as a polyamide resin, and CP-5 as a third component were mixed at the blending ratio shown in Table 1, After drying at 110°C for 5 hours, the mixture was melt-kneaded in a twin-screw extruder with a cylinder temperature of 270°C to form pellets. This pellet was molded into a short shelf-shaped test piece of 1/2 x 5 x 1/8 inch and a dumbbell for ASTM tensile test using an injection molding machine.

The physical properties of this molded article were evaluated. The results are shown in Table 1.

(Examples 7 to 11, Comparative Examples 3 to 4) PAR-1 as a polyarylate resin, PA-1 as a polyamide resin, and CP-6 as a third component were mixed at the compounding ratio shown in Table 2, respectively. After drying at 110°C for 5 hours, the cylinder temperature was 240-360°C as appropriate.
The mixture was melted and kneaded using a shaft press ratio machine to form pellets. This was molded and the physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Examples 12 to 14, Comparative Examples 5 to 7) Using PAR-1 as the polyarylate resin, PA-1 as the polyamide resin, and the third component shown in Table 3, the blending ratio was PAR-1/PA- 1/3rd component=501501
5 (weight ratio), and kneaded, molded, and evaluated physical properties in the same manner as in Example 1. The results are shown in Table 3.

(Examples 15 to 23) Using the polyarylate resin, polyamide resin, and CP-5 as the third component shown in Table 5, the blending ratio was polyarylate resin/polyamide resin/CP-5=5
015015 (weight ratio), kneaded and molded in the same manner as in Example 1.

Physical properties were evaluated.

The results are shown in Table 4 <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 this feature can be used for applications such as plastics for automobile exterior panels that can be baked on, and housings for electronic and electrical equipment that are exposed to high heat. It is most suitable as

Claims (1)

[Claims] (1) To 100 parts by weight of a resin containing 10 to 90% by weight of a polyarylate resin containing 70% by weight or more of a polyarylate resin component and 90 to 10% by weight of a polyamide resin containing 70% by weight or more of a polyamide resin component. On the other hand, there are the following formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (X is a direct bond, lower alkylene group with 1 to 4 carbon atoms, ▲ Numerical formulas, chemical formulas, tables, etc.
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 a carbon number of 1
-4 lower alkyl groups, and n is an integer of 1 or more.