JPH0288661A - Aromatic resin composition - Google Patents

Abstract

PURPOSE:To obtain an aromatic resin composition having excellent mechanical strength and impact resistance and high strength and elastic modulus by compounding an aromatic resin with a modified elastomer and optionally a polyamide resin. CONSTITUTION:The objective aromatic resin composition can be produced by melting and kneading (A) 50-99 pts.wt. of an aromatic resin (preferably polyester resin, polyphenylene oxide resin or ABS resin) with (B) 1-50 pts.wt. of a modified elastomer produced by modifying (B1) 100 pts.wt. of an elastomer (e.g., hydrogenated styrene-butadiene block copolymer) with (B2) 0.01-10 pts.wt., preferably 0.1-5 pts.wt. of a modifying agent (e.g., 1-acryloylbenzotriazole). As an alternative, the resin is produced by melting and kneading 1-50 pts.wt. of the component B to 100 pts.wt. of a composition composed of 5-95 pts.wt. of the component A and 5-95 pts.wt. of a polyamide (preferably nylon 6 or nylon 66 having a number-average molecular weight of 10,000-50,000).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a high-strength, high-modulus aromatic resin composition that is composed of an aromatic resin and a modified elastomer and has high mechanical strength and impact resistance. Regarding. The present invention also relates to a high-strength and high-modulus aromatic resin composition comprising an aromatic resin, a polyamide resin, and a modified elastomer.

[Prior art and problems to be solved by the invention] Aromatic resins such as aromatic polyamide and aromatic polyester have excellent heat resistance and mechanical strength and are used in engineering, plastic snacks, electrical and electronic parts, mechanical parts, and automobile parts. It is widely used in fields such as However, the impact strength is low,
It was restricted in its field of application.

Conventionally, it has been known that impact resistance can be increased by blending polyamide, polyester, etc. with ionomer, elastomer such as ethylene propylene rubber, etc. had not yet achieved sufficient impact strength.

In addition, many proposals have been made to blend aromatic resins and polyamide resins to obtain products with higher mechanical strength. It was difficult to obtain.

An object of the present invention is to provide an aromatic resin composition having excellent impact resistance without impairing the mechanical strength of the aromatic resin.

[Means to solve the problem]

In order to achieve the above object, the present invention provides the use of a modified elastomer modified with an unsaturated compound in place of the elastomer conventionally used to improve impact strength.

That is, the present invention provides an aromatic resin composition comprising 50-99 parts by weight of an aromatic resin and 1-50 parts by weight of a modified extramer, or an aromatic resin composition comprising 5-95 parts by weight of an aromatic resin and a polyamide resin. 5 to 95 parts by weight, and 100 parts by weight of the total amount of the aromatic resin and the polyamide resin,
An aromatic resin composition comprising 1-50 parts by weight of a modified elastomer is provided.

The aromatic resin used in the present invention is a polymer containing at least a plurality of aromatic groups in the polymer or polyacecool; for example, polystyrene resin, polyester resin including polyarylate and polycarbonate, polyester resin) These include aromatic polyether resins such as polyether ether ketone, polyether sulfone, and polysulfone, polyarylate resins, polyphenylene oxide resins, polyphenylene sulfide resins, and ABS resins. Furthermore, the polymer does not contain aromatic groups, but is a polyacetal resin.

Among these aromatic resins, polyester resins, polyphenylene oxide resins and ABS resins are preferably used.

A polyester resin is a resin obtained by a polycondensation reaction between a dicarboxylic acid or its derivative and a glycol or its derivative, and either the dicarboxylic acid or the glycol has an aromatic group.

Examples of dicarboxylic acids include terephthalic acid, isophthalic acid,
2-chlorothyrefucuric acid, 2,5-cyclothyrefucuric acid, 2-methylterephthalic acid, 44-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, bisbenzoic acid, Bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 44-diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dodecandioic acid, 1.
3-cyclohexanedicarboxylic acid, 4-cyclohexanedicarboxylic acid, etc. can be used alone or in combination of two or more. Among these compounds, terephthalic acid, isophthalic acid, and 4,4-stilbenedicarboxylic acid alone or a mixture thereof are particularly preferred.

Glycols include ethylene glycol, 1゜2-propylene glycol, 1,3-propanediol, 2,
2-dimethyl-1,3-propanediol, trans-
or cis-2,2,4,4-tetramethyl 1,3-cyclobutanediol, ■, 4-butanediol, neopentyl glycol, 1,5-bentanediol, 1,6
-hexanediol, 1,4-cyclohexane dimetatool, 1,3-cyclohexane dimetatool, decamethylene glycol, cyclobutanediol, P-xylene diol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis(2 -hydroxyethyl ether) can be used alone or in combination of two or more. Among these, ethylene glycol, 1,4-butanediol, and (1),4-cyclohexane dimetatool are preferred.

Specific examples of the polyacetal resin used in the present invention include:
Polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, poly(ethylene terephthalate/cyclohexane dimethylene terephthalate) copolymer, poly(ethylene terephthalate/
These include emolene isophthalate) copolymer, poly(butylene terephthalate/butylene dodecadiate) polyester ether copolymer, polyacrylate, polycarbonate, and the like. The number average molecular weight of these polyester resins may be at least 8,000, preferably 10,000.
~50,000. Further, these polyester resins may be used alone or in combination.

The polyphenylene oxide resin used in the present invention is 26
- It is a resin obtained by subjecting xylenol and orthocresol to an oxidative polymerization reaction in the presence of a catalyst. Alternatively, a modified polyphenylene oxide resin modified with styrene or the like may be used. Polyphenylene resin has an intrinsic viscosity of 0.3-0.8
It's fine to use one.

Further, the ABS resin used in the present invention may be a resin obtained by graft polymerizing an acrylonitrile-styrene copolymer to polybutadiene, as long as it can be injection molded or extruded.

The aromatic resins of the present invention can be used alone or in combination on two sides.

The polyamide resin used in the present invention is a known injection moldable resin, and is polymerized from an amino acid, a lactam, or a diamine, and a dicarboxylic acid.

Specific examples of monomers include 6-aminocaproic acid, 1
1-aminoundecanoic acid, 12-aminoundecanoic acid,
Amino acids such as para-aminomethylbenzoic acid, lactams such as ε-cabrolactum and ω-laurolactam, Te1-
Ramethylenediamine, hexamethylenediamine, undecamethylenediamine, F decamethylenecyamine, 2,2
．． 4-/2,4.4 trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, baraxylylenecyamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl) ) cyclohexane, ■-amino-3-aminomethyl-3.5.5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-
Diamines such as aminocyclohexyl)methane, 212-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, and aminoethylpiperazine, and adipic acid, sheric acid, azelaic acid, sebacic acid, dodecaniic acid, terephthalic acid, and isophthalic acid. , 2chloroterephthalic acid, 2-methylterephthalic acid, 5-methylterephthalic acid, 5-sodium sulfoisophthalic acid, hexahydroisophthalic acid, hexahydroisophthalic acid,
Some are in combination with dicarboxylic acids such as diglycolic acid.

Specific examples of polyamide resins obtained from these monomers include nylon 6, nylon 66, nylon 6/10, nylon 6/11, nylon 6/12, nylon 11, nylon 12, nylon MxD/6, and copolymer polyamides thereof. There is. These polyamide resins can be used alone or in combination of two or more. Among these polyamide resins used in the present invention, nylon 6 and nylon 66 are particularly preferred. The number average molecular weight of these may be at least 8,000, more preferably in the range of 10,000 to 50,000.

The modified elastomer used in the present invention is an elastomer that has a lower modulus of elasticity than the tensile modulus of the aromatic resin or polyamide resin used in the present invention, and is modified with an unsaturated compound.

Examples of elastomers include known styrene-based, olefin-based, urethane-based, polyester-based, polyamide-based, vinyl chloride-based, chlorinated polyethylene-based, 1,2-polybutadiene-based, fluorine-based, ionomer, ethylene/propylene rubber, butyl rubber, and styrene.・Rubbers such as butadiene rubber and acrylonitrile rubber are used.

Specific examples of styrene are styrene, butadiene,
Styrene block copolymer, styrene/isoprene/
There are styrene block copolymers, styrene/ethylene styrene block copolymers, etc. Specific examples of olefins include homopolymers and copolymers of ethylene olefins such as ethylene, propylene, butene-1, hexene-1, decene-1,4-methylbutene-1,4-methylpentene-1, These ethylene olefins and 1,
Copolymers with non-conjugated dienes such as 4-hexadiene, pentadiene, dicyclopentadiene, methyltetrahydroindene, methylenenorbornene, and ethylidene norbornene; specific examples of ethylene-acryurethane systems include polyurethane-caprolactone block copolymers and polyurethane adipine. There are acid block copolymers and the like, and a commercially available product is Elastran (manufactured by Nippon Elastran Co., Ltd.). Specific examples of polyester-based polymers include butylene terephthalate-tetramethylene ether glycol block copolymers, and commercially available products include Hytrel (manufactured by DuPont Toshi) and Pelprene (manufactured by Toyobo Co., Ltd.). Specific examples of polyamides include polyester amide, polyether amide, polyester ether amide, etc., and commercially available products include Glylux (manufactured by Dainippon Ink Co., Ltd.) and Tsubamitsu (manufactured by Mitsubishi Kasei Co., Ltd.). Specific examples of vinyl chloride-based products include Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.) and Sunbrene (manufactured by Mitsubishi Monsanto Kasei Co., Ltd.).
etc. Specific examples of chlorinated polyethylene include chlorosulfonated polyethylene and the like. Specific examples of the 1,2-polybutadiene type include hydrogenated products thereof, as well as copolymers with styrene and butadiene, and commercially available products include JSRRB (manufactured by Japan Synthetic Rubber Co., Ltd.). Specific examples of fluorine-based materials include vinylidene fluoride-propylene hexafluoride copolymer, ethylene trifluoride-ethylene fluoride copolymer, and the like. Specific examples of ionomers include:
There is DuPont's Surlyn (trade name), which is an ethylene-ethyl acrylate copolymer crosslinked with metals such as sulfur and zinc.

The modified elastomer used in the present invention is obtained by modifying the aforementioned elastomer using an unsaturated compound as a modifying agent.

Modifiers include (1) alkenylcarboxylic anhydrides and derivatives thereof, such as dodecenylsuccinic anhydride, octadecenylsuccinic anhydride, and 4-methacryloxyethyl trinolitic anhydride; and dicarboxylic acid corresponding to the above-mentioned anhydrides. Unsaturated compounds of acids and their monoesters, metal salts, etc., (2) 1-acryloylhencytriazole, 1-acryloylphthalimide, 1-acryloylsulfonehenshiimide, ■-acryloylnaphthalimide, methacryloylbenzotriazole, etc., and derivatives thereof unsaturated compounds represented by the following formula (i), and CR+=CR2Co R:+...(i) provided that R,, R2=H or an alkyl group, Rz=1,2.
Residues obtained by removing H from 3-benzotriazole, phthalimide, orthosulfobenzimide, 1,8-naphthalimide, succinimide, lactams, etc. and their derivatives (3) Acrylic acid, methacrylic acid, maleic acid, maleic acid α, β unsaturated carboxylic acids such as monomethyl ester, maleic anhydride, iconic acid, itaconic acid monomethyl ester, itaconic anhydride, fumaric anhydride, metal salts thereof, monoesters thereof, anhydrides thereof, etc., and derivatives thereof,
Endo-bicyclo(2゜21)-5-heptene-2,3
- Carboxylic acids, alicyclic carboxylic acids such as cis-4-cyclohexene-1,2-galponic acid, metal salts thereof, anhydrides thereof, and derivatives thereof, or methacroyl chloride, acryloyl-oxy-benzoic acid, oligomers, etc. Added oligomeric additional unsaturated compounds can be used.

The oligomer used in the oligomer addition unsaturated compound is the aromatic resin used in the present invention, such as polyester,
Oligomers such as polyetherketone, polyphenylene oxide, polysulfone, polyacetal, etc., oligomers of the polyamide resins, or silane compound oligomers containing part of the constituent components of the aromatic resins and polymers of the polyamide resins, such as aromatic These include silane compound oligomers containing bisphenol A for resin polycarbonate.

The degree of polymerization of the oligomer is 3-50, preferably 6-30.

The oligomer-added unsaturated compound can be obtained by adding the oligomer to the unsaturated compound by a known method.

Modification of the elastomer can be carried out by tri-blending the elastomer, the modifier, and a peroxide such as t-butyl hydroperoxide, and then melt-kneading the same, or by grafting the modifier onto the elastomer in a solvent or the like. This can be done by a known method. The modifier is 0.01 to 10 parts by weight per 100 parts by weight of the elastomer,
It is preferably used in a proportion of 0.1 to 5 parts by weight.

In the present invention, modified elastomers can be used alone or in combination. In this case, two or more of the modifiers may be used for one type of elastomer, two or more of the elastomers may be used and one modifier is used, or any one of the elastomer and modifier may be used. Two or more types may also be used. When using two or more modifiers, (1) or (3) is added to the modifier (1) or (3).
It is effective to use 2) in combination.

When using modified elastomers mixed on two sides, the modified elastomers may be blended, or a mixed modified elastomer may be obtained by mixing and using an elastomer and/or a modifier when modifying the elastomer. .

The resin composition of the present invention is a mixture of the aromatic resin and the modified elastomer, or the aromatic resin,
The polyamide resin and the modified elastomer are premixed simultaneously or individually and supplied to a conventional melt-kneading processing device such as a single-screw kneading extruder, a twin-screw kneading extruder, a Banbury mixer, or a kneader; It can be easily produced by melt-kneading at a temperature above the melting point of the resin used and below 350°C.

Furthermore, it can be processed into molded products for various uses by injection molding, compression molding, extrusion molding, etc.

Various reinforcing materials and fillers can be added to the resin composition of the present invention as long as their moldability and physical properties are not impaired. Specific examples of reinforcing materials and fillers include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica/alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, stainless steel, aluminum, and titanium. , metal fibers such as copper, brass, and magnesium; organic fibers such as polyamide, fluororesin, polyester, and acrylic resin; and metal powders such as copper, iron, nickel, zinc, soot, lead, stainless steel, aluminum, gold, and silver. , fumed silica, aluminum silicate, glass beads, carbon black, quartz powder, talc, titanium oxide, iron oxide, calcium carbonate, diatomaceous earth, etc.

The fibrous material has an average fiber diameter of 5 to 50 μm and a fiber length of 50 μm.
Those with a diameter of μm to 60 mm can be used. These reinforcements,
Fillers that have been surface-treated with known silane coupling agents or titanate camping agents can also be used. These reinforcing materials and fillers can be used alone or in combination of two or more. By mixing 5 to 100 parts by weight of these reinforcing materials and fillers with respect to 100 parts by weight of the resin composition of the present invention, they not only significantly improve mechanical strength and heat resistance temperature, but also improve water resistance. It is also preferable because it can be further improved.

The resin composition of the present invention may contain hindered phenol, hydroquinone, thioether, phosphites, substituted products thereof, etc., as long as the object of the present invention is not impaired.
Antioxidants and heat stabilizers such as copper compounds such as copper iodide, ultraviolet absorbers such as resorcinol, salicylate, henctriazole, and benzophenone, mold release agents such as stearic acid and its salts, stearyl alcohol, halogen-based,
It is also possible to add one or more additives such as melamine or cyanuric acid flame retardants, flame retardant aids, sodium dodecylhenzenesulfonate, antistatic agents such as polyalkylene glycol, crystallization accelerators, dyes, and pigments. It is.

In addition, thermoplastics such as polyethylene, polypropylene, ethylene/vinyl acetate copolymer, ethylene/propylene copolymer, thermoplastic polyurethane, polyacecool, polycarbonate, polysulfone, polyphenylene ether, ethylene propylene rubber, styrene butadiene block copolymer polyester, etc. Elastomers, thermoplastic resins, phenolic resins, melamine resins, silicone resins,
Thermosetting resins such as epoxy resins can also be added.

The present invention will be specifically explained below with reference to a method for producing a modified elastomer, Examples, and Comparative Examples.

The flexural modulus, impact strength, oil absorption, and compatibility of resin mixtures in Examples and Comparative Examples were measured by the following methods.

1) Flexural modulus: Measured according to ASTM D-790.

(Unit: kgf/c) 2) Notched Izot impact strength: ASTM D-2
It was measured according to No. 56. A 178 inch thick specimen was used for the measurements. (Unit: kg - cm/cm) 3)
Oil absorption rate: The change in weight of a test piece for measuring flexural modulus that was immersed in commercially available gasoline at room temperature for 24 hours before and after immersion was expressed as a ratio to ABS resin.

4) Compatibility: 8ST? A tensile test piece of ID-638 (178 inches thick) was bent an average of 100 times.
Phase separation was determined visually.

The modified elastomer used in the examples was manufactured by the following method.

"Modified elastomer production example 1 (modified hydrogenated styrene/butadiene block copolymer)" Hydrogenated styrene/butadiene block copolymer (Asahi Kasei ■
Manufactured by Toughtic H1041) Mixed evenly with a blender. This mixture was reacted with a screw extruder while kneading at a cylinder temperature of 250°C, and pelletized.
A modified elastomer ■ was obtained.

"Modified elastomer production example 2 (modified ethylene propylene rubber)" In modified elastomer production example 1, ethylene propylene rubber (Japan Synthetic Rubber product name: 1EP-02P) was used instead of the hydrogenated styrene-butadiene block copolymer.
A modified elastomer ■ was obtained in the same manner except that .

"Modified elastomer production example 3 (oligomer-modified hydrogenated styrene-butadiene block copolymer)" (Production method of oligomer addition modifier A) Polyethylene glycol terephthalate/polycyclohexane dimetatool terephthalate with a polymerization degree of 15 having a hydroxyl group at the end Oligomers were obtained by conventional methods. After neutralizing this oligomer with an aqueous solution of caustic soda, it was reacted with mecculoyl chloride to obtain oligomer addition modifier A, which is a Na salt of methacryloyl-oxy polyester.

(Production method of oligomer addition modifier B) Cupric bromide, di-n-butylamine, and 2,
Add and mix 6-dimethylphenol dissolved,
After homogeneous dissolution, polymerization was carried out while rapidly blowing oxygen into the solution to obtain an oligomer with a degree of polymerization of 18. This was carried out in the same manner as the method for producing the oligomer addition modifier A, to obtain an oligomer addition modifier B of methacryloyl-oxy-polyphenylene oxide.

(Production method of modified elastomer) In modified elastomer production example 1, 5 parts by weight of oligomer addition modifier A and 1 part of t-butyl hydroperoxide were used in place of 1-acryloylhensitriazole.
．． A modified elastomer (2) was obtained in the same manner except that 0 part by weight was added. Furthermore, a modified elastomer (2) was obtained in the same manner using oligomer addition and modification agent B instead of oligomer addition and modification agent A.

[Example 1] ABS resin (Ube Saikon Aji Co., Ltd. commercial name: EXIOI)
20 parts by weight of the modified elastomer (2) was added to 80 parts by weight, triblended, and then melt-kneaded at 270°C. Cylinder temperature: 270°C 1 mold temperature: 80°C
Various physical property test specimens were molded and their physical properties were measured. The results are shown in Table 1.

[Examples 2 to 6 and Comparative Examples 1 to 3] Test pieces were molded according to Example 1 at each blending ratio shown in Table 1. The polyamide resin used in this case was manufactured by Ube Industries, product name: 1013B, and the polyester resin used was manufactured by Eastman Kodasoku, product name: KODARPE.
T G10179, polyphenylene oxide resin (PP
O resin) used had an intrinsic viscosity of 0.50.

The results are shown in Table 1.

〔Effect of the invention〕

The resin composition of the present invention has good dispersibility of each component, and
Impact resistance is improved without impairing physical properties such as high mechanical strength of aromatic resins and polyamide resins. Furthermore, by selecting the blending ratio, various physical properties such as imparting oil resistance and moldability can be improved. Therefore, the resin composition according to the present invention can be provided with well-balanced physical properties in accordance with various uses.

(Hereafter, margin)

Claims (2)

[Claims] (1) (a) 50-99 parts by weight of aromatic resin, and (b) 1-50 parts by weight of modified elastomer An aromatic resin composition comprising: (2) (a) 5-95 parts by weight of aromatic resin, (b) 5-95 parts by weight of polyamide resin, and (c) 100 parts of the total amount of component (a) and component (b).
An aromatic resin composition comprising 1 to 50 parts by weight of modified elastomer.