JPH02261858A - Impact-resistant resin composition - Google Patents

Abstract

PURPOSE:To prepare a resin composn. with excellent impact, chemical and heat resistances and moldability by compounding a resin mixture of a polyarylate with a polyamide with specified amts. of a plurality of specific polyolefin copolymers. CONSTITUTION:A resin mixture comprising 10 to 70wt.% polyarylate obtd. from terephthalic acid and bisphenols and 90 to 30wt.% polyamide (e.g. polycaprolactam) is compounded with an epoxy-olefin copolymer (e.g. an ethylene-glycidyl mechacrylate-vinyl acetate copolymer) obtd. by the copolymn. of at least one unsatd. glycidyl monomer with at least one unsatd. olefin monomer and an acid anhydride-olefin copolymer (e.g. an ethylene-maleic anhydride- acrylate copolymer) obtd. by the copolymn. or graft polymn. of an unsatd. dicarboxylic acid anhydride with a polyolefin or olefin copolymer, the sum of said epoxy-olefin copolymer and said acid anhydride-olefin copolymer being 3 to 30wt.%.

Description

[Detailed description of the invention] (Industrial application field) The present invention has excellent impact strength and chemical resistance.

It relates to a new resin composition with excellent thermal properties and moldability, and more specifically, it relates to a resin composition consisting of a polyarylate obtained from terephthalic acid and bisphenols and a polyamide, and an olefin-based resin composition containing an epoxy group. The present invention relates to a resin composition formed by blending a copolymer and an acid anhydride-containing olefin copolymer.

The resin composition of the present invention has excellent impact resistance.

Due to its chemical resistance, heat resistance, and moldability, it is expected to be applied to automobile parts, especially outer panels or exterior parts, as well as general mechanical parts.

(Prior art) Composed of polyarylate and polyamide. Alternatively, resin compositions made of polyarylate, polyamide, and polyester are known. For example, Tokuko Sho 58-50260
The publication discloses the properties of a ternary resin composition of polyarylate, polyamide, and polyester or polyester ether.

Also, JP-A-52-100552 and JP-A-52
Publication No. 100553 discloses its manufacturing method.

JP-A-53-94366 discloses a flame retardant method.

Resin compositions made of polyarylate and polyamide (containing polyester or polyester ether if necessary) not only have excellent chemical resistance and heat resistance, but also excellent moldability, and are already being used mainly in the electrical and electronic fields. ing.

Although polyarylate has excellent heat resistance, as is well known, it does not have sufficient chemical resistance and is susceptible to environmental stress cranking. Furthermore, it cannot be said that the moldability is excellent. However, for example, 30% by weight of this polyarylate, 650% by weight of nylon, and 20% by weight of polyethylene terephthalate.
The resin composition consisting of 1% by weight exhibits excellent chemical resistance and has a high heat distortion temperature of 160°C. According to evaluation of moldability by spiral flow length, it is about 10 times better than polyarylate alone. Due to these characteristics, the resin composition has already been widely applied in the electrical and electronic fields.

However, the impact strength of resin compositions made of polyarylate and polyamide (containing polyester or polyester ether if necessary) is not necessarily a satisfactory value. For example, in the case of a resin composition comprising 50% by weight of polyarylate and 650% by weight of nylon, the impact strength of the resin composition is 7 kg·cm/cm. This value is relatively low for engineering plastics.

Therefore, their uses were also different. For example, when used as an outer panel or exterior part for an automobile, the Izot impact strength must be at least 20 kg-cm/cm.

Due to these circumstances, although the resin composition has excellent chemical resistance, heat resistance, and moldability, its insufficient impact resistance prevents its application to automobile outer panels or exterior parts. I've been exposed to it.

Therefore, it was expected that if the impact resistance of the resin composition could be improved, its uses would increase dramatically not only in automobile outer panels and exterior parts but also in other fields.

Nevertheless, the reality is that almost no attempts have been made to improve the impact resistance of resin compositions made of polyarylates and polyamides obtained from terephthalic acid and bisphenols.

JP-A-54-56 regarding a resin composition consisting of polyarylate and polyamide obtained from a slightly mixed phthalic acid of terephthalic acid and isophthalic acid and bisphenols
In No. 652, the formulation of the elastomer is
In 93043, the ionomer formulation is disclosed in Japanese Patent Application Laid-open No. 5
No. 9-105050 discloses the formulation of polyethylene terephthalate containing sulfonic acid groups, and JP-A-61-18
No. 3353 discloses the formulation of an olefinic copolymer of glycidyl ester of an α,β-unsaturated acid.

However, it has been found that resin compositions containing elastomers, ionomers, and sulfonic acid group-containing polyethylene terephthalates are extremely impractical due to the anisotropy in the mechanical properties of molded products. Also, α, β−
In a resin composition containing an olefin copolymer of glycidyl ester of an unsaturated acid, if a large amount of such olefin copolymer is blended in order to obtain a satisfactory impact strength, the resin composition may be Gelation, coloring, decomposition, etc. are likely to occur, which is also impractical.

'On the other hand, it is known that an olefin polymer containing an acid anhydride is blended with polyamide.

When a large amount of the resin composition is blended, phase separation occurs, which not only reduces the gloss of the molded article but also makes it impossible to obtain the desired impact strength.

In this way, in a practical sense, all attempts to improve the impact resistance of resin compositions made of polyarylate and polyamide obtained from mixed phthalic acids of terephthalic acid and isophthalic acid and bisphenols have all ended in failure. is the reality.

Furthermore, no attempt has been made to improve the impact resistance of a resin composition made of polyarylate and polyamide obtained from terephthalic acid and bisphenols.

(Problems to be Solved by the Invention) In view of the above circumstances, an object of the present invention is to provide a resin composition comprising a polyamide and a polyarylate obtained from terephthalic acid and bisphenols, which has excellent chemical resistance, heat resistance,
The objective is to significantly improve impact strength without impairing formability.

Another object of the present invention is to provide a new molding material that has excellent chemical resistance, heat resistance, moldability, impact resistance, and provides molded products with excellent gloss.

Still another object of the present invention is to provide a novel molding material that is highly productive and highly practical.

(Means for Solving the Problems) As a result of extensive research for this purpose, the present inventors have found that a resin composition containing epoxy groups and polyamides and polyarylates obtained from terephthalic acid and bisphenols has been developed. It has been surprisingly found that a resin composition formed by blending an olefin copolymer and an acid anhydride-containing olefin copolymer satisfies all of the objects of the present invention.

When an epoxy group-containing olefin copolymer and an acid anhydride-containing olefin copolymer are used alone, satisfactory impact strength may not be obtained, or gelation, coloring, decomposition, and phase separation may occur. Although there are various drawbacks, such as the occurrence of cracking or poor gloss of the molded product, when these are used together, all such problems are solved, and the impact strength is lower than when used individually. The improvement above is quite surprising.

That is, 1. the present invention provides a resin composition comprising 10 to 70% by weight of polyarylate obtained from terephthalic acid and bisphenols and 90 to 30% by weight of polyamide, (A) one or more unsaturated glycidyl monomers. and (B) an epoxy group-containing olefin copolymer obtained by copolymerizing one or more olefinic unsaturated monomers, and (B) a polyolefin or olefin copolymer copolymerizing an unsaturated dicarboxylic acid anhydride or The gist of the present invention is a resin composition containing 3 to 30% by weight of an acid anhydride-containing olefin copolymer obtained by graft addition.

The polyarylate used in the present invention is a general bisphenol represented by 2 (wherein -X-).

selected from the group consisting of o-, -s-, -so□-, -CO-, alkylene group or alkylidene group, RI+
RZ, R3, R4, R'l, R'2. R'i,
and R/.

It is obtained from functional derivatives of et al.

Examples of such bisphenols indicated above - at most include: 4,4'-dihydroxy-diphenyl ether, bis(4-hydroxy-2-methylphenyl) ether, bis(4-hydroxy-3-chlorophenyl) ether, bis( 4-hydroxyphenyl) sulfide,
Bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3
-methylphenyl)methane, bis(4-hydroxy-3
5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, bis(4-hydroxy-3,5-difluorophenyl)methane, 1.
1-bis(4-hydroxyphenyl)ethane, 2.2-
Bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydro,xy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5
-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5 dibromophenyl)propane, 1.1
-bis(4-hydroxyphenyl)butane, bis(4-
Hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-4°-methylphenylmethane, J, ■
-bis(4-hydroxyphenyl) -2,2,2,-
Trichloroethane, bis(4-hydroxyphenyl)-
(4”-chlorophenyl)methane.

1.1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)cyclohexylmethane.

° ° etc., but the most commonly used and preferably preferred is 2,2-bis(4-hydroxyphenyl)propane, that is, bisphenol A. If necessary, mixtures of the above bisphenols or bisphenols and small amounts of other divalent compounds 1, such as dihydroxynaphthalenes such as 2,2' dihydroxydiphenyl, 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, 2,6- Mixtures of dihydroxychlorobenzene, 216-cyhydroxytoluene, 3,6-cyhydroxytoluene, etc. can be used.

Functional derivatives of terephthalic acid are halides or alkyl, aryl esters of these acids.

The phenylene group of terephthalic acid or a functional derivative thereof used in the present invention may be substituted with a halogen atom or an alkyl group. In addition to terephthalic acid or a functional derivative thereof, a small amount of other aromatic or aliphatic dicarboxylic acid or a functional derivative thereof may be used as a copolymerization component. Isophthalic acid or a functional derivative thereof is most preferred as such a copolymerization component.

The polyarylate used in the present invention can be synthesized by any method such as an interfacial polymerization method, a solution polymerization method, or a melt polymerization method. In order to obtain a resin composition having preferable physical properties, it is preferable to use a polyarylate having an average molecular weight of 5,000 to 100,000.

The polyamide used in the present invention is represented by the general formula [■] or the general formula (I[I]. Here, R, R, and R7 represent a phenylene group or an alkylene group.

The polyamide used in the present invention includes a polymer formed by a condensation reaction of a diamine and a dibasic acid, a self-condensation reaction of an amino acid, and a polymerization reaction of a lactam.

The polyamide used in the present invention may be any polyamide as long as it is represented by the above-mentioned maximum, but the preferred polyamide is nylon 46. nylon 6 nylon 66,
Nylon 610. Nylon 11. Examples include nylon 12 and the like.

Further, the polyamide used in the present invention may be a ternary or more copolymer, for example, terephthalic acid and/or isophthalic acid and 2.2.4-1-limethylhexamethylene diamine and/or 2. 4.4-
Even if it is a copolymer of 1-limethylhexamethylene diamine, a copolymer of terephthalic acid and/or isophthalic acid, bis(4-amino-3-methylcyclohexyl)methane, caprolactam and/or lavalyl lactum, etc., there are two types. It may be more than that.

In order to obtain a resin composition having preferable physical properties, it is preferable to use a polyamide having an average molecular weight of 5.000 to ioo or ooo.

The epoxy group-containing olefin copolymer used in the present invention is obtained by polymerizing one or more unsaturated glycidyl monomers and one or more olefin monomers. The copolymer may be a random copolymer, a block copolymer, or an alternating graft copolymer. The unsaturated glycidyl monomer is a monomer that has an unsaturated bond in one molecule that can be copolymerized with olefinic monomers and has one or more epoxy groups.

Specific examples of such unsaturated glycidyl monomers include glycidyl acrylate and glycidyl methacrylate.
itaconate monoglycidyl ester, itaconate diglycidyl ester, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester, p-
Styrene carboxylic acid glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether,
Styrene P-glycidyl ether, p-glycidylstyrene, 3,4-epoxy-1-butene.

3.4-Epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1=hexene and vinylcyclohexene mono Examples include oxides.

In the present invention, the olefinic monomer to be copolymerized with the unsaturated glycidyl monomer to form the olefinic copolymer may be any olefinic monomer as long as it can substantially introduce an epoxy group into the molecule, but preferably Olefins such as ethylene, propylene, butene-1, isobutylene, decene-1, octacene-1゜styrene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, or methyl acrylic acid and methacrylate, ethyl-propyl,
Esters with saturated alcohols such as butyl, 2-ethylhexylcyclohexyl, dodecyl, octadecyl, maleic acid diester, vinyl chloride, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, or N-vinyl N- such as pyrrolidone and N-vinylcaprolactam
Examples include vinyl lactams and acrylamide compounds, and one or more of these can be used.

Examples of the epoxy group-containing olefin copolymer used in the present invention include ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl acrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, and ethylene-glycidyl acrylate-vinyl acetate copolymer. Polymers are particularly advantageously used.

The copolymerization ratio of unsaturated glycidyl monomer in the epoxy group-containing olefin copolymer used in the present invention is 0.05 to 95 mol%, preferably 0.1 to 50 mol%.

The acid anhydride-containing olefin copolymer used in the present invention is obtained by copolymerizing a polyolefin or an olefin copolymer with an unsaturated dicarboxylic acid anhydride.

The polyolefin or olefin copolymer referred to in the present invention is a homopolymer of olefins such as polyethylene, polypropylene, polybutene-1, or methyl methacrylate or ethyl methacrylate.

Polymers of methacrylic esters such as butyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate, or acrylic esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate. Polymer or ethylene-propylene copolymer, ethylene-
Different olefins such as butene-1 copolymer, propylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene-diene copolymer, or olefins and other different monomers such as acrylate ester. Contains copolymers with polymers. The copolymer may be a random copolymer, a block copolymer, a graft copolymer, or an alternating copolymer.

The unsaturated dicarboxylic anhydride as used in the present invention includes αβ-unsaturated dicarboxylic anhydride and alicyclic carboxylic anhydride having a cis-type 2ff bond in the ring. Examples of α,β-unsaturated dicarboxylic acid anhydrides include maleic anhydride, chloromaleic anhydride, citraconic anhydride, and itaconic anhydride.

Examples of alicyclic carboxylic acid anhydrides having a cis-type double bond in the ring include cis-4-cyclohexene 1,2-dicarboxylic acid, endo-bicyclo-[22,1)-5-hebutene-2, 3-dicarboxylic acid, methyl-endo-cis-bicyclo-(2,2,1]-5-hebutene-2,3-dicarboxylic acid, endo-bicyclo-(2,2,1)-L2.
3,4,7.7-hexachloro-2-heptene-5,6
- anhydrides such as dicarboxylic acids and optionally functional derivatives thereof such as dicarboxylic acids, metal salts of dicarboxylic acids;

Esters, amides, and acid halides can also be used.

The acid anhydride-containing olefin copolymer used in the present invention includes ethylene-propylene copolymer, ethylene-propylene copolymer, and ethylene-propylene copolymer.
Butene-1 copolymer, ethylene-hinyl acetate! Union,
Maleic anhydride or endo-bicyclo-(2,2,13-5-heptene 2,3- Copolymers or graft adducts of anhydrides of dicarboxylic acids are advantageously used.

The copolymerization ratio of unsaturated dicarboxylic acid anhydride in the acid anhydride-containing olefin copolymer used in the present invention is 0.05 to 95 mol%, preferably 0.1 to 50 mol%.

As a method for producing such an epoxy group-containing olefin copolymer or an acid anhydride-containing olefin copolymer, a known so-called radical copolymerization method is used, as well as a method for producing an olefin homopolymer or an olefin copolymer. Examples include a method in which a radical generator is present and one or more unsaturated monomers containing an epoxy group or an acid anhydride are subjected to a radical graft reaction in the presence or absence of a solvent or dispersion medium. Among these, when grafting is carried out in a molten state, the desired product can be obtained in a very short time using a simple method by using a melt kneading machine such as an extruder, kneader, or panburi mixer.

The composition ratio of polyarylate and polyamide V in the resin composition of the present invention is 10 to 70% by weight of polyarylate and 90 to 30% by weight of polyamide. Most preferably the polyarylate is 30 to 60% by weight and the polyamide is 70 to 40% by weight.

The blending ratio of the epoxy group-containing olefin copolymer and the acid anhydride-containing olefin copolymer used in the resin composition of the present invention is such that the equivalent ratio of epoxy group to acid anhydride is 1:9.
Preferably, the ratio is in the range of 9 to 1. Further, the combined amount of the epoxy group-containing olefin copolymer and the acid anhydride-containing olefin copolymer is preferably 3 to 30% by weight.

If it is less than 3% by weight, the effect of improving impact strength is not significant.

If it exceeds 30% by weight, the heat resistance will be greatly reduced.

The resin composition of the present invention further includes a heat stabilizer,
Additives such as antioxidants, light stabilizers, lubricants, pigments, N-smoking agents, and plasticizers may be added. Also fiber reinforcements like glass fibers, metal fibers, potassium titanate whiskers, carbon fibers, and talc.

Filler reinforcing agents such as calcium carbonate, mica, glass flakes, and metal flakes may also be added. In particular, the amount of glass fiber in the resin composition of the present invention is from 10 to 50%.
By adding % by weight, not only the mechanical strength and heat resistance temperature are significantly improved, but also the water resistance is improved, which is preferable in achieving the object of the present invention.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Examples 1 to 8 A reaction device (vacuum type twin-screw kneader) was charged with bisphenol A and acetic anhydride in a molar ratio of 1=2 and terephthalic acid in an equimolar amount with bisphenol A, and dimethyltin maleate was used as a catalyst to react with polyarylate. 4 per mole of structural unit
Add 10-' mol of
The reaction was allowed to take place while mixing for a period of time. The reaction mixture was further heated under reduced pressure at 250°C for 2 hours and further reduced to 50 torr to 260°C.
The reaction was allowed to proceed for 4 hours at °C.

The reactant was heated and depressurized sequentially for 1 hour to carry out the reaction.Finally, the temperature was raised to 340°C, the degree of vacuum was adjusted to 0.02 Torr, and melt polymerization was carried out for 3 hours. Polyarylate was obtained.

This polyarylate phenol/tetrachlorella 7
= 60/40 (weight ratio) at 25°C, 1g/df
The logarithmic viscosity at f is 0.5. Glass transition temperature is 240
It was °C. Melt index 2.0g/10 minutes/
190°C.

1000 parts by weight of an ethylene-propylene copolymer (hereinafter referred to as EPR) containing 1t72.0% of ethylene, 3 parts by weight of endobicyclo-(2,2,1)-5-hebutene-2,3-dicarboxylic anhydride, and dicarboxylic anhydride. - 1 part by weight of tertiary-butyl peroxide was mixed at room temperature using a Henschel mixer, then fed to a single-screw extruder and extruded at 200°C to create cylindrical pellets with a diameter of 2 mm and a length of 3 mm. An anhydride-containing olefin copolymer was obtained.

As a polyarylate, the above-mentioned polyarylate is made of polyamide and polycaprolactam (A 1030 manufactured by Unitika Co., Ltd.) is used.
BRL), ethylene-glycidyl methacrylate vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bond First E) as the epoxy group-containing olefin copolymer, and the above modified EPR as the acid anhydride-containing olefin copolymer. After mixing the composition for one day, vacuum drying was performed at 80°C for one night.
A pellet was obtained using a twin-screw press at 0°C. Using the obtained pellets, test pieces were obtained by ordinary injection molding and subjected to measurement. The results obtained are listed in Table 1.

Examples 9 to 16 Polycaprolactam (manufactured by Unitika Co., Ltd. A 1030 B) was used as the polyarylate and polyamide used in Examples 1 to 8.
RL), ethylene-glycidyl methacrylate-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bond First E) as an olefin-based copolymer containing an epoxy group, and ethylene-maleic anhydride-acrylic acid as an olefin-based copolymer containing an acid anhydride. After mixing an ester copolymer (manufactured by Sumika CDF, Bondine LX4110) with the composition shown in Table 1, 8
Vacuum drying was carried out at 0°C overnight, and then dried at 270°C for 2 days.
A pellet was obtained using a shaft press ratio machine. Using the obtained pellets, test pieces were obtained by ordinary injection molding.
It was used for measurement. The results obtained are listed in Table 2.

(Effects of the Invention) The resin composition of the present invention has no disadvantages when the impact resistance imparting material is used alone, and surprisingly, the impact strength is significantly improved compared to when the impact resistance imparting material is used alone.

Patent applicant: Unitika Co., Ltd.

Claims (1)

[Claims] (1) 10 to 70% by weight of polyarylate obtained from terephthalic acid and bisphenols and 90% by weight of polyamide
to 30% by weight of (A)
An epoxy group-containing olefin copolymer obtained by copolymerizing one or more unsaturated glycidyl monomers and one or more olefinic unsaturated monomers, and (B) a polyolefin or olefin copolymer. A resin composition comprising 3 to 30% by weight of an acid anhydride-containing olefin copolymer obtained by copolymerizing or grafting an unsaturated dicarboxylic anhydride.