JPH0270748A - Production of thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in solvent resistance, impact resistance and heat resistance by melt-kneading a polyphenylene ether resin with a polyamide or a thermoplastic polyester in the presence of a peroxide or an azo compound. CONSTITUTION:The purpose resin composition is obtained by performing the following melt kneading in the presence of 0.001-10pts.wt. peroxide having a functional group selected from among a carboxyl and/or an amino acid/or azo compound per 100pts.wt. total of components (a), (b) and (c) in the production of a composition comprising 5-95wt.% polyphenylene ether resin (a), 5-95wt.% polyamide and/or thermoplastic polyester (b) and 0-50wt.% impact strength modifier (c). This resin composition can be obtained by kneading at a temperature in the range of 200-350 deg.C with an extruder, a Banbury mixer, a kneader, rolls or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a method for producing a thermoplastic resin composition having excellent solvent resistance, impact resistance and heat resistance.

b. Conventional technology Polyphenylene ether resin has excellent mechanical properties, electrical properties, and heat resistance, as well as good dimensional stability, so it is attracting attention as a resin suitable for a wide range of applications. However, solvent resistance, moldability,
A major drawback is poor impact resistance.

In order to improve the molding processability of polyphenylene ether resin, it was proposed in Japanese Patent Publication No. 45-99 to incorporate polyamide.
No. 7 was also blended with polyester in 1973.
-21664, but polyphenylene ether resin and polyester or polymide have very poor compatibility, and the resulting resin composition has poor mechanical properties (
In particular, when the polyester content exceeds 20%, the molded product obtained by injection molding of the resin composition is
It had very low impact resistance. Further, even when attempts were made to add various rubber components to improve the impact resistance of the resin composition, the impact resistance was hardly improved.

C1 Problems to be Solved by the Invention The present inventors have discovered
As a result of extensive research in order to obtain a resin composition that can be used in a wide range of applications, we found that polyphenylene ether, polyamide and/or polyester, an impact reinforcing agent, and a peroxide and/or chain transfer agent having a specific functional group were added. It has been discovered that a thermoplastic resin composition having unprecedented performance can be obtained by blending in a specific ratio and kneading with excitation, and based on this knowledge, the present invention has been achieved.

The means for solving the d0 problem, that is, the present invention, consists of (a) 5-95% by weight of polyphenylene ether resin (b) 5-95% by weight of polyamide and/or thermoplastic polyester <c> Impact-resistant reinforcing agent
In producing a composition consisting of 0 to 50% by weight,
For a total of 100 parts by weight of the above (a) + (b) + (c), add 0.001 to 10 parts by weight of a peroxide and/or azo compound having a functional group selected from a carboxyl group and/or an amino group. The present invention provides a method for producing a thermoplastic resin composition obtained by melt-kneading the thermoplastic resin composition.

The polyphenylene ether resin (a) used in the present invention is a polymer consisting of repeating structural units represented by the following general formula (I). 1,4-ether)°, poly(2°6-danitylphenylene-1,4-ether), poly(2,6-dipromophenylene-1,4-ether), poly(2-methyl-
6-ethylphenylene-1,4-ether), poly(2
-chloro-6-methylphenylene-1,4-ether)
, poly(2-methyl-6-itubropylphenylene-1
．． 4-ether), poly(2,6-di-n-propylphenylene-1,4-ether), poly(2-chloro-6
-bromphenylene-1,4-ether), poly(2-
chloro-6-nitylphenylene-1,4-ether),
Poly(2-methylphenylene-1,4-ether), poly(2-chlorophenylene-1,4-ether), poly(2-phenylphenylene-1,4-ether), poly-(2-methyl-6 -phenylphenylene-1゜4-ether), poly(2-bromo-6-phenylphenylene-1,4-ether), poly(2゜4'-methylphenylphenylene-1,4-ether), poly(2-bromo-6-phenylphenylene-1,4-ether), ,3,6
-drimethylphenylene-1,4-ether), copolymers thereof, and styrenic compound graft copolymers thereof.

The blending amount of the polyphenylene ether resin in the thermoplastic resin composition of the present invention is 5 to 95% by weight, preferably 10 to 60% by weight, and more preferably 10 to 50% by weight.

If the amount of polyphenylene ether resin is less than 5% by weight, no significant effect on improving heat resistance will be observed, and if it exceeds 95% by weight, solvent resistance will be poor.

The polyamide as the component (b) used in the present invention is generally expressed by the following formula % [wherein X is an integer between 4 and 12]. ] and a linear carboxylic acid represented by the following formula % (in the formula, y is an integer between 2 and 12), or a lactam. Those produced by ring-opening polymerization can be used.

Preferred examples of these polyamides include nylon 6
・6, Nylon 6/9, Nylon 6Y10, Nylon 6
・There are 12, nylon 6, nylon 12, nylon 11, nylon 4 and 6, etc.

Also, nylon 6/6/6, nylon 6/6/10, nylon 6/12, nylon 6/6/12, nylon 6/
Copolyamides such as 6Φ6/6/10 and nylon 6/6/6/12 can also be used.

Furthermore, semi-aromatic polyamides obtained from nylon 6/6・T (T: terephthalic acid component), aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and meta-xylene diamine, or alicyclic diene, meta-xylene diamine and Mention may be made of polyamides, polyesteramides, polyetheramides and polyesteretheramides obtained from the above-mentioned linear carboxylic acids. Note that the polyamide may be used alone, or two or more types of polyamides may be used in combination.

As the thermoplastic polyester of component (b) used in the present invention, aliphatic polyester, aromatic polyester, wholly aromatic polyester, etc. are used.

Preferred polyesters are those produced by condensation polymerization using the following general formula.

The dicarboxylic acid and diol components are used alone or in combination of two or more.

Particularly preferred polyesters are polyethylene phthalate, polybutylene terephthalate and modified products thereof.

Note that polyester may be used alone, or two or more types of polyester may be used in combination.

The above-mentioned polyamide and thermoplastic polyester as component (b) may be used alone or in combination.

The amount of component (b) used is 5 to 95% by weight, preferably 90% by weight.
~40% by weight, more preferably 90-50% by weight. If the amount used is less than 5% by weight, solvent resistance will be poor;
If it exceeds % by weight, the heat resistance will be poor.

The impact reinforcing agent used as component (c) of the present invention includes styrene-butadiene copolymer, polyacrylate rubber, polybutadiene, hydrogenated diene polymer,
Conjugated diene (co)polymers such as acrylonitrile-butadiene copolymers, hydrogenated acrylonitrile-butadiene copolymers, butadiene-acrylic acid ester copolymers,
Aromatic vinyl-conjugated diene block copolymer of ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer There is such a thing as merging. Aromatic vinyl-conjugated diene block copolymers include AB type, ABA type, ABA tapered type, radial teleblock type, and hydrogenated products thereof.

Also included are rubber-reinforced styrenic copolymers, such as copolymers obtained by grafting an aromatic vinyl compound or an aromatic vinyl compound and another vinyl compound onto the above-mentioned rubber.

Examples of the conjugated diene monomer used in the conjugated diene (co)polymer include butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene. In addition, copolymerized aromatic vinyl compounds are also preferably used, such as styrene, vallastylstyrene, and α-methylstyrene.

The microstructure of the diene polymer is 1.2-3.4-
The content of the vinyl bonded metal is 10% or more, preferably 20 to 80%, particularly preferably 20 to 50%.

If it is less than 10%, the hydrogenated diene polymer will have resinous properties, which is not preferable.

The content of the aromatic vinyl compound in the diene polymer is preferably 50% by weight or less, more preferably 35 to 5% by weight. If it exceeds 50% by weight, the hydrogenated diene polymer may take on resinous properties, which is not desirable. When the amount of the aromatic vinyl compound exceeds 50% by weight, it is preferable that the aromatic vinyl compound is partially polymerized to form blocks. Further, the present polymer may be either a linear polymer or a branched polymer.

The molecular weight of the diene polymer is 5゜000 in number average molecular weight.
1,000.000, preferably 30°000-300
．． It is 000. If it is less than 5,000, the hydrogenated diene polymer of the present invention will not become rubbery but will become liquid;
If it exceeds 0,000, workability tends to decrease. Further, the molecular weight distribution M w /M n of the polymer is 10 or less.

The diene copolymer is obtained, for example, by anionic living polymerization in a hydrocarbon solvent using an organolithium initiator. Further, the branched polymer can be obtained by adding a required amount of a trifunctional or more functional coupling agent at the end of the polymerization to perform a coupling reaction. Ethers, tertiary amine compounds, alkoxides, phenoxides, and sulfonates of alkali metals such as sodium and potassium are used to control the amount of vinyl bonds such as 1.2-13,4-bonds.

As the organolithium initiator, n-butyllithium, 5
ec-butyllithium, tert-butyllithium, etc. are used.

Hydrocarbon solvents include hexane, heptane, methylcyclopentane, cyclohexane, benzene, toluene,
xylene, 2-methylbutene-1,2-methylbutene-
2 etc. are used.

The polymerization may be carried out in a batch manner or in a continuous manner, and the polymerization temperature is usually in the range of 0 to 120°C and the polymerization time is in the range of 10 minutes to 3 hours. The coupling agent is a trifunctional or more functional coupling agent, and examples thereof include tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis(trichlorosilyl)ethane, divinylbenzene, adipic acid. Diester, epoxidized liquid polybutadiene, epoxidized soybean oil, epoxidized linseed oil, tolylene diisocyanate, diphenylmethane diisocyanate, 1.2.
Examples include 4-benzene triisocyanate.

Hydrogenated diene polymers thus polymerized can also be suitably used. In the case of hydrogenation, the hydrogenation rate of olefinic unsaturated bonds in the diene polymer is preferably 70% or more, more preferably 90% or more, particularly preferably 95% or more. By setting the hydrogenation rate to 70% or more, even better weather resistance and heat resistance can be obtained.

The hydrogenation reaction of the hydrogenated diene polymer before modification of the present invention is as follows:
Dissolving the conjugated diene polymer in a hydrocarbon solvent,
The reaction is carried out at 20 to 150° C. under pressurized hydrogen of 1 kg/eJ to 100 kg/cJ in the presence of a hydrogenation catalyst.

Hydrogenation catalysts include catalysts in which precious metals such as palladium, ruthenium, rhodium, and platinum are supported on silica, carbon, and diatom, complex catalysts such as rhodium, ruthenium, and platinum, and organic carboxylic acids and organic aluminum such as cobalt and nickel. or a catalyst consisting of organolithium,
Titanium compounds such as dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentajenyl titanium ditolyl, dicyclopentadienyl titanium dibenzyl, lithium, aluminum,
A hydrogenation catalyst consisting of an organometallic compound consisting of magnesium is used.

As the hydrogenated diene polymer, a hydrogenated product of a random copolymer of a conjugated diene and an aromatic vinyl compound is preferable from the viewpoint of impact resistance. The weight ratio of ethylene and α-olefin in the ethylene-α-olefin copolymer is 95:5.
~5:95, and the muniny viscosity (ML,
100°C) is 5 to 200, preferably 5 to 100 in terms of 1+4 impact resistance. Further, the amount of the cyclohexane-insoluble portion of the ethylene-α-olefin copolymer affects the impact resistance of the thermoplastic resin composition of the present invention, and is 50% by weight or less, preferably 5% by weight or less. The α-olefin used here is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and specific examples include propylene, butene-1, pentene-1
, hexene-1, heptene-1,4-methylbutene-1
, 4-methylpentene-1, and the like.

The aromatic vinyl compound of the styrene-butadiene block copolymer used in the present invention is preferably 5 to 60% by weight, and the weight average molecular weight of the entire block copolymer is preferably 10,000 to 50°, ooo, More preferably, it is 20,000 to 30o, ooo.

The amount of component (c) used in the thermoplastic resin composition of the present invention is 0 to 50% by weight, and in order to obtain an excellent Izot impact strength, 1 to 30% by weight, preferably 5 to 50% by weight.
It is 25% by weight. If it exceeds 50% by weight, heat resistance decreases, which is not preferable.

To obtain the thermoplastic resin composition of the present invention, it is necessary to melt-knead the composition in the presence of a peroxide and/or azo compound having at least one functional group selected from a carboxyl group and an amino group. Carboxyl group-containing peroxides have at least one 10-0-bond and at least one 10-OH bond in the molecule, and are used in hydroperoxide (R-C- 0-
0-H [wherein R is a hydrocarbon group] or hydrogen peroxide and an acid anhydride, hydroperoxide or hydrogen peroxide and (
XOC) -R-(cOOH) n.

The acid anhydrides used here include, for example, benzoic anhydride, succinic anhydride, acetic anhydride, naphthalic anhydride, lactic anhydride, phthalic anhydride, mylenic anhydride, mellitic anhydride, pyromellitic anhydride, isovaleric anhydride. Anhydride, cyclohexanedicarboxylic anhydride, cyclohexanedicarboxylic anhydride, citraconic anhydride, oxalic anhydride, camphoric anhydride, fluoroacetic anhydride, propionic anhydride, methylsuccinic anhydride, diphenylmaleic anhydride , palmitic anhydride, phenylacetic anhydride, caproic anhydride, etc., and these may be used alone or in combination of two or more. The above acid halide contains at least 1 acid halide in 1 molecule.
It has at least one acid halogen group and at least one carboxyl group.

The acid halide can be produced by a known method, for example, by reacting thionyl chloride with a carboxyl group.

The acid halide and the hydroperoxide react to obtain the target carboxyl group-containing peroxide. Furthermore, when an unreacted acid halide is present in the reaction product, the scope of the present invention also includes those in which the acid halide is hydrolyzed to form a carboxyl group. Succinic acid peroxide, t-butylperoxymaleic acid, etc. are readily available as commercial products.

Further, the carboxyl group-containing azo compound is represented by the following general formula, and preferable examples include azobizvaleric acid and azobispropionic acid.

Peroxides and azo compounds containing amino groups include α, α
′-azobis(γ-amino-α, γ-dimethylvaleronitrile), α,α′-azobis(γ-methylamino)-α
, γ-dimethylvaleronitrile), α, α′-azobiz (γ-ethyleramino-α, γ-dimethylvaleronitrile), α, α′-azobis (γ-propylamino-α,
γ-dimethylvaleronitrile), α,α′-azobis(
γ-dimethylamino-α, γ-dimethylvaleronitrile), α, α′-azobis (γ-diethylamino-α, γ
-dimethylvaleronitrile), α.

Azo compounds such as α'-azobis (γ-dipropylamino-α, γ-dimethylvaleronitrile) and P-aminobenzoyl peroxide, P.

Examples include peroxides of P'-diaminobenzoyl peroxide.

In order to achieve the object of the present invention, those having a peroxide bond are preferable, and those having a peroxide bond and a carboxyl group are more preferable.

The above compound is the component (a) + component (b) + (c
) is used in an amount of 0.001 to 10 parts by weight per 100 parts by weight of component. Preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, particularly preferably 0.01 to 5 parts by weight.
It is 1 to 2 parts by weight.

If the amount used is outside the range of the present invention, the impact resistance will be poor.

The thermoplastic resin composition of the present invention can be obtained by kneading in various extruders, Banbury mixers, kneaders, rolls, etc. at a temperature in the range of 200 to 350°C. A preferred kneading method is a method using an extruder, and a particularly preferred extruder is a twin-screw co-rotating extruder.

In obtaining the thermoplastic resin composition of the present invention by the above method, (a), (b), (c) of the present invention and a compound having a functional group may be mixed together and added. The components may be added in multiple stages. Examples of the multistage divisional addition method include the following method.

(2) After kneading components (a) and (c) and the functional group-containing compound, component (b) is added.

(2) After kneading component (a) and the functional group-containing compound, components (b) and (c) are added.

When using the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, asbestos, wollastonite, calcium carbonate, potassium titanate whiskers, talc, mica, barium sulfate, molybdenum disulfide, glass flakes Fillers such as , fluororesin, etc. can be used alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of ~10 μm and a fiber length of 30° C. or more.

Additionally, known additives such as flame retardants, antioxidants, plasticizers, and blowing agents may be added. Preferred flame retardants are halogen-based ones, and preferred antioxidants are phosphite-based ones. Further, other polymers added depending on the required performance, such as polystyrene, polyethylene, polypropylene, polycarbonate, polysulfone, polyimide, pps, polyetheretherketone, vinylidene fluoride polymer, etc., can be blended as appropriate.

e. Examples The invention will be explained in more detail by the following examples and manufacturing examples, but these are merely illustrative and do not limit the content of the present invention.

In addition, in each side below, parts and % indicate parts by weight and % by weight, respectively.

Production Example 1 Polyphenylene ether used in Examples and Comparative Examples was obtained by the following method.

1) Production of polymer A (polyphenylene ether) 2.6
-xylenol, cupric bromide and di-n-butylamine as catalysts, and a polymerization reaction was carried out in a toluene solution at 30° C. while blowing oxygen. After the polymerization reaction was completed, an aqueous solution of disodium ethylenediaminetetraacetate was added to remove the catalyst.

The polymer solution phase was removed from the resulting product mixture by centrifugation. While stirring the polymer solution vigorously, methanol was gradually added to form a slurry. After separating the solid content, it was thoroughly washed with methanol and dried to obtain Polymer A.

[η] of Polymer A measured at 30° C. using chloroform solvent was 0.40.

2) The following was used as component (b) of the present invention.

Nylon 6 Amilan CM1017 made by Polymer B-2 Nitoshi ■ Nylon 6 Amiran CM1007 made by Polymer B-2 Nitoshi ■ Nylon 66 Amilan CM3 made by Polymer B-3 Nitoshi ■
006 Polymer B-4 CDSM Nylon 46 Polymer B-5
= PBT DURANEX XD6 manufactured by Polyplastics■
28 Polymer B-6 PET RY523 manufactured by Nippon Unipet ■ 3) The following was used as component (c) of the present invention.

Polymer C-1 = Ethylene-propylene copolymer rubber manufactured by Japan Synthetic Rubber ■ EP941P Polymer C - Ethylene-propylene copolymer rubber manufactured by Polymer Water Synthetic Rubber ■ EPOIP Polymer C
Styrene-butadiene-styrene block copolymer T made of polymer mortar synthetic rubber ■
R2900 Polymer C-4 Hydrogenated styrene-butadiene-styrene block copolymer manufactured by Nigel Co., Ltd. Kraton G1650 Polymer C-5 = Hydrogenated Random 5BR (Styrene content 30%, hydrogenation rate of butadiene portion is approximately 1
00%) 4) The following compounds were used as specific compounds having functional groups of the present invention.

D-1: Tertiary-butylperoxymaleic acid was used as a compound having both a peroxide bond and a carboxyl group.

D-2: Succinic acid peroxide was used as a compound having both a peroxide bond and a carboxyl group.

D-3=P-aminobenzoyl peroxide was used as a compound having both a peroxide bond and an amino group.

D-4: Azobisvaleric acid was used as a compound having both an azo bond and a carboxyl group.

D-5: Maleic anhydride D-6: 2.5 dimethyl-2,5-di(t-butylperoxy)hexane Examples, comparative examples The compositions of the various polymers and functional group-containing compounds shown in Table 1 mixed in proportion. In addition, the first stage component and second stage component shown in Table 1 refer to the first stage component (1st stage component) in the extrusion kneading process.
) Indicates that after the component (2) was added, the component (2) was further added in the middle of the second stage.

As an extruder, PCM-45 (twin screw extruder) manufactured by Ikegai Iron Works
The barrel temperature was set at 300° C. at the highest point, and the pellets were pelletized at a screw rotation speed of 30 rpm.

After sufficiently drying the obtained pellet-shaped thermoplastic resin composition in a dehumidifying dryer, test pieces were prepared using an injection molding machine, and impact resistance, heat resistance, and solvent resistance were evaluated.

Evaluation method Impact resistance: According to ASTM D256, thickness 1/4
"Measured at 23°C with a notch.

Heat resistance: 1/4' thickness according to ASTM D648
, measured at a load of 18.5 kg/c-.

Solvent resistance: A test piece (1/8' UL bar) was strained by 1%, immersed in kerosene and left for 48 hours, and then the state of breakage and cracking was observed, and the results were divided into four stages as shown below. evaluated.

◎: No breakage or cracking occurred.

O: A small rack has occurred.

Δ: A large rack has occurred.

×: Fracture Comparative Example 1 uses a large amount of component (a) outside the range of the present invention, and has poor impact resistance and solvent resistance.

Comparative Example 2 uses a large amount of component (b) outside the scope of the present invention, and has poor impact resistance and heat resistance.

Comparative Example 3 uses a small amount of a compound having a specific functional group, which is outside the scope of the present invention, and has poor impact resistance, heat resistance, and solvent resistance.

In Comparative Example 4, the amount of the compound having a specific functional group used was large beyond the scope of the present invention, and the impact resistance was poor.

In Comparative Example 5, the amount of component (c) used was small, outside the scope of the present invention, and the impact resistance was poor.

Comparative Example 6 uses a large amount of component (c) outside the scope of the present invention, and has poor heat resistance and solvent resistance.

Comparative Example 7 is an example in which maleic anhydride was used instead of the compound having a specific functional group of the present invention, and the impact resistance and heat resistance were poor. Furthermore, the molded product obtained by this method has peeling and poor compatibility.

Comparative Example 8 is an example in which the peroxide of the present invention having no functional group was used, and the compatibility was very poor, the molded product peeled off considerably, and the impact resistance and solvent resistance were poor.

Margin below F6 Effects of the Invention The thermoplastic resin composition obtained by the present invention has highly balanced solvent resistance, impact resistance and heat resistance,
It provides molded products such as automobile exterior and interior parts that require high quality, various electrical and electronic related parts, and nosings, and has extremely high industrial value.

Claims (1)

[Claims] (1) Produce a composition consisting of (a) 5-95% by weight of polyphenylene ether resin, (b) 5-95% by weight of polyamide and/or thermoplastic polyester, and (c) 0-50% by weight of impact reinforcing agent. Accordingly, the above (a) + (b)
0.001 to 10 parts by weight of a peroxide and/or azo compound having a functional group selected from a carboxyl group and/or an amino group are present in a total of 100 parts by weight of +(c), and the mixture is melt-kneaded. A method for producing the obtained thermoplastic resin composition.