DE19607187A1 - Heat-stabilised polyphenylene ether crystalline thermoplastic resin blend - Google Patents

Abstract

Thermoplastic resin compsn. comprises 100 pts.wt. mixt. of (a) 1-99 wt.% polyphenylene ether resin (PPE) and (b) 99-1 wt.% crystalline thermoplastic resin (I) and (c) 0.001-15 pts. wt. 4-amino-2,2,6,6-tetramethylpiperidinyl cpd(s). (II) of formula (IIA) or (IIB). (Pip-N(R2)-)n-R3 (IIA) (Pip-N(R2)-(CH2)p-N(Pip))n-R3 (IIB) Pip=1-(R1)-2,2,6,6-tetramethyl-piperidin-4-yl; R1=H, O (oxy gp.), OH, (cyclo)alkyl, allyl, benzyl, aryl, alkanoyl, alkenoyl or (cyclo)alkoxy; R2=H, alkyl or -R4CO-(X)-R5; X=a direct bond, -O- or -NH-; R4=a direct bond, alkyl(id)ene or arylene; R5=H, alkyl, aryl, -CH=CCH-COOH or Pip; n=1-4; p=2-6; R3=an n-valent organic gp.

Description

The present invention relates to a thermoplastic resin composition which Polyphenylene ether and a crystalline thermoplastic resin comprises, with improved Properties in processing stability and heat stability in practical Use.

Polyphenylene ether resins are thermoplastic resins that have different properties properties such as mechanical properties, heat resistance and dimensional stability are outstanding. However, they tend to discolor and deteriorate, like Vernet when molded at high temperatures. Especially in the present from oxygen, they suffer severe deterioration from heat, causing gelling acts, which increases the molecular weight or sometimes gives black spots. Furthermore, polyphenylene ether resins change color easily in the light.

In order to compensate for these disadvantages, it has been proposed to use admit sentences. For example, Japanese Patent Kokoku No. 44-29751 Phosphorus additives and in Japanese Patent Kokoku No. 46-24782 phenolic additives suggested. In addition, many attempts have been made to use different ones Stabilizers, the hindered amines or hindered amines and phe contain nol additives, mainly to inhibit discoloration in the light below  as in Japanese Patent Kokai Nos. 60-149646 and 60-203150 U.S. Patent Nos. 4232131, 4233410, 4233412, 4234699, 4260689, 4260691 and 4299926, EP 094048 A2, EP 134523 A1, EP 146879 A2, EP 146878 A2, EP 151961 A1, EP 149454 A2, EP 233153 A2, EP 240723 A2, EP 229363 A2 and EP 313118 A1 are open beard. Many of these attempts can help improve evaporation resistance the stabilizers at the time of processing or when actually used be effective, and various compounds that hindered amines al contain lin or copolymers (oligomers) with other ingredients have been pre beat. However, none of these suggestions provided sufficient effects Inhibition of deterioration when heated.

An object of the present invention is to provide a thermo plastic resin composition comprising a polyphenylene ether resin and a crystalline thermo plastic resin which, before deterioration at the time of processing, ins special under heating, is protected.

This problem was solved on the basis of the finding that a striking Effect of inhibiting deterioration when heated by adding a verbin that contains a sterically hindered amine with a special structure into one thermoplastic resin composition comprising a polyphenylene ether resin and a crystalline ther plastic resin comprises, can be obtained.

The present invention relates to a thermoplastic resin composition comprising:

• (a) 1 to 99% by weight of a polyphenylene ether resin,
• (b) 99 to 1% by weight of a crystalline thermoplastic resin, and per 100% by weight Parts of the sum of (a) and (b)
• (c) 0.001 to 15 parts by weight of at least one 4-amino-2,2,6,6-tetramethylpiperidyl compound of the following formula (1) or (2): in which R₁ represents a hydrogen atom, an oxygen atom (an oxy group), a hydroxyl group, an alkyl, cycloalkyl, allyl, benzyl, aryl, alkanoyl, alkenoyl, alkyl oxy or cycloalkyloxy radical and R₂ represents a hydrogen atom, represents an alkyl radical or a radical of the following formula (3), in which X represents a direct bond, -O- or -NH-, R₄ represents a direct bond, a linear or branched alkylene, alkylidene or arylene radical and R₅ represents a hydrogen atom, an alkyl, aryl radical or a radical of the following formula ( 4) or (5), and in which n represents an integer from 1 to 4, p represents an integer from 2 to 6 and R₃ represents an n-valent organic radical.

The polyphenylene ether resin (a) of the present invention is a polymer obtained by oxidative polymerization of at least one phenol compound of the following formula  (11) with oxygen or an oxygen-containing gas using an oxidati ven clutch catalyst:

in which R₁₅, R₁₆, R₁₇, R₁₈ and R₁₉ each have a hydrogen or halogen atom or represent a substituted or unsubstituted hydrocarbon radical and min at least one of the residues is a hydrogen atom.

Examples of R₁₅, R₁₆, R₁₇, R₁₈ and R₁₉ are hydrogen, chlorine, bromine, Fluorine, iodine atoms, methyl, ethyl, n- or iso-propyl, primary, sec- or tert-butyl, Chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, Methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dime thylphenyl, ethylphenyl and allyl groups.

Examples of the compounds represented by formula (11) are phenol, o-, m- or p-cresol, 2,6-, 2,5-, 2,4- or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3,6- or 2,4,6-trimethylphenol, 3-methyl-6-tert-butylphenol, thymol and 2-methyl-6-allylphe nol.

The phenol compounds of the formula (11) can also be mixed with other Phe nol compounds, for example aromatic compounds containing several hydroxyl groups Compounds such as bisphenol A, tetrabromobisphenol A, resorcinol, hydroquinone and Novolak resins are copolymerized.

As preferred examples of the polyphenylene ether resin (a), homopoly mers of 2,6-dimethylphenol, homopolymers of 2,6-diphenylphenol, copolymers a larger amount of 2,6-dimethylphenol and a smaller amount of 3-methyl-6-tert- Mention butylphenol or 2,3,6-trimethylphenol.

Any oxidative coupling catalyst can be used for the oxidative polymerization of the Phenol compound can be used, provided it has polymerizability.

The crystalline thermoplastic resin (b) according to the invention is a thermoplastic resin with a crystallinity of 5% or more measured using a conventional molded article with a differential scanning calorimeter (DSC), and preferably at least one resin selected from polyethylene, polypropylene,  Polyamide, poly (alkylene dicarboxylate), polyacetal, polyarylene sulfide and Polyether ketone resins.

The polyethylene resin used in the present invention includes Ethylene homopolymer, an ethylene-α-olefin copolymer such as an ethylene-propylene co polymer, an ethylene-butene-1 copolymer, an ethylene-4-methylpentene-1 copolymer, an ethylene-hexene-1 copolymer, an ethylene-octene copolymer and an ethylene-decene 1-copolymer, a. These polyethylene resins can be made according to Japanese Industry standards JIS K6760 in a low density polyethylene (LDPE) with a Density from 0.914 to 0.925 g / cm³, a medium density polyethylene (MDPE) with a Density from 0.925 to 0.94 g / cm³ and a high density polyethylene (HDPE) with a density of 0.94 to 0.96 g / cm³ can be classified. In particular the ethylene-α- Olefin copolymer can be taken as linear low density polyethylene (LLDPE) called the LDPE.

Furthermore, the ethylene-α-olefin copolymer also includes one with a smaller one Density, such as very low density polyethylene with a density of 0.90 to 0.914 g / cm³ (VLDPE) and ultra low density polyethylene with a density of 0.88 up to 0.90 g / cm³ (ULDPE). Both VLDPE and ULDPE have a melt point of 80 ° C or more. At this point they are an ethylene-α-olefin co polymer rubber with the same density range different.

The polyethylene resin can be a modified polyethylene on which a mono mer with at least one functional group, such as an α, β-unsaturated carboxylic acid, aliphatic carboxylic acid and derivatives thereof, is grafted.

The polypropylene resin used according to the invention includes a crystalline poly propylene, such as a crystalline propylene homopolymer and a crystalline propylene-α- Olefin copolymer containing at most 30 mol% ethylene and / or at least one α-olefin other than propylene. This includes a crystalline one Propylene-α-olefin block copolymer obtained by polymerizing propylene or Copolymerize propylene with 6 mole% or less of ethylene and / or at least a kind of α-olefin, such as butene-1, in the first step and then in the second Step, copolymerizing propylene with 10 mol% or more ethylene and / or at least one kind of α-olefin, and a crystalline propylene-α-ol random fin copolymers obtained by copolymerizing propylene with 6 mol% or less ethylene and / or at least one kind of other α-olefin than butene-1 and Witches-1, a.

The polyamide resin used in the present invention is one or more Other types of polyamide resins selected from a homopolyamide made by Polymerizing a lactam or an aminocarboxylic acid, and a copolyamide,  like an aliphatic polyamide made by copolymerizing equal moles a saturated dicarboxylic acid with 4 to 12 carbon atoms and an aliphatic Diamine with 2 to 12 carbon atoms. The content of the amine end group in the copolyamide may optionally be larger than that of the carboxyl end group if an excess Diamine is used. Conversely, the content of the carboxyl end group can be greater than that of the amine end group when an excess of dicarboxylic acid is used.

Similarly, these polyamide resins can be made using acid derivatives and the amine such as an ester, an acid chloride and an amine salt will.

The aliphatic dicarboxylic acid used to make the polyamide resin includes adipic acid, pimelic acid, azelaic acid, suberic acid, dodecanedioic acid, and on the other hand, the aliphatic diamine includes hexamethylene diamine and octamethy lendiamine one. In addition, the polyamide resin can be self-polycondensed Lactams are made.

Examples of the aliphatic polyamide include polyhexamethylene adipic acid amide (nylon 66), polyhexamethylene azelaic acid amide (nylon 69), polyhexamethylene sense bacic acid amide (nylon 610), polyhexamethylene dodecanoic acid amide (nylon 612), poly bis (p-aminocyclohexyl) methanedodecanoic acid amide, polytetramethylene adipic acid amide Copolymer (nylon 46, nylon 6, nylon 10, nylon 11, nylon 12, nylon 6/66), and two or more kinds of these nylon compounds can be used arbitrarily.

Preferably, nylon 46, nylon 6, nylon 66, nylon 11 and nylon 12 are used used by these crystalline polyamide resins. Nylon 6 is more preferred, Nylon 66 and a mixture of any ratio of nylon 6 and nylon 66 used.

From the functional end groups of these polyamide resins, a resin with egg ner excess amine end group, with an excess carboxyl end group and with both in equilibrium and a mixture of them in any ratio appropriately used.

An aromatic copolyamide with crystallinity is also included. To the For example, it includes a copolyamide that has an aromatic component such as poly contains hexamethylene isophthalamide (nylon 6I). So contains the aromatic copo lyamide mainly an aromatic amino acid and / or an aromatic dicarbon acid such as p-aminomethylbenzoic acid, p-aminoethylbenzoic acid, terephthalic acid and Isophthalic acid. It can be obtained by melt polymerization. That in the aromati The diamine used in copolyamide includes hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4- / 2,4,4-trimethylhexamethylene diamine, meta-Xy lylenediamine, para-xylylenediamine, bis (p-aminocyclohexyl) methane, bis (p-aminocyclo  hexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, 1,3-bis (aminomethyl) cyclo hexane and 1,4-bis (aminomethyl) cyclohexane. In addition, isocyanates instead of Di amines can be used. For example, they include 4,4'-diphenylmethane diisocyanate and tolylene diisocyanate.

The copolymerization stock optionally used in the polyamide resin part is not particularly restricted and is a derivative of lactam, | -amino acid with 4 to 12 carbon atoms, an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and an aliphatic diamine having 2 to 12 carbon atoms, such as Caprolac tam, | -laurolactam, lactams of 11-aminoundecanoic acid and 12-aminododecanoic acid, Amino acid and an equimolar salt of the diamines mentioned above with adipine Acid, azelaic acid or sebacic acid can be used.

Optionally, a mixture of an amorphous polyamide with an arbitrary ratio of the crystalline polyamide resin can be used.

The poly (alkylene dicarboxylate) resin used in the present invention is a resin hold by polycondensation of a dicarboxylic acid or its functional derivative and an alkylenedioxy compound or its functional derivative.

Examples of the dicarboxylic acid include an aromatic dicarboxylic acid such as Te rephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, a nucleus-substituted aromatic dicarboxylic acid in which a hydrogen atom of the aromatic nucleus passes through a methyl, ethyl or phenyl group has been replaced, an aliphatic dicarboxylic acid with 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarbon acid, and an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid. The functional derivative of dicarboxylic acid includes an acid chloride mentioned above compound and an ester such as carboxylic acid methyl ester and carboxylic acid phenyl ester, a.

Examples of the alkylenedioxy compound include an aliphatic diol and alicyclic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol and 1,4-cyclohexanediol.

An example of the functional derivative of the alkylenedioxy compound is a di acetate.

Two or more kinds of the above-mentioned compounds can be used can be used, and further a copolymer, the p-oxybenzoic acid or polyethylene Containing lenglycol can also be used.

Examples of the poly (alkylene dicarboxylate) resin preferably include ther plastic polyester resin such as polyethylene terephthalate, polybutylene terephthalate and a modified copolymer thereof, which further comprises a polyether such as polyethylene glycol and polypropylene glycol.  

The polyarylene sulfide resin used in the present invention is a polymer composed of consists of a repeating unit of the following chemical formula (12) (in which Ar represents a divalent aromatic radical).

Examples of Ar include a divalent aromatic residue and the nucleus substituted radicals of the following formulas (13) to (22).

Ar also includes a small amount of trifunctional groups of the following form mel (23).

Examples of the polyarylene sulfide resin in formula (12) include polyphenylene sulfide fid, poly (1,4-phenylene carbonyl-1,4-phenylene sulfide), poly (1,4-phenylene sulfonyl-1,4-phe nylene sulfide) and poly (biphenylene sulfide).

Among them, the polyarylene sulfide resin is preferably a polyarylene sulfide with 50 mol% or more of a repeating unit represented by the following formula (24), more preferably polyphenylene sulfide and most preferably polyphenylene sulfide with a crystallization temperature below decreasing temperature of 225 ° C or we Here, the crystallization temperature is one under decreasing temperature Temperature of the crystallization, measured under decreasing temperature after Schmel zen, and their value is measured with DSC at a rate of decreasing temp rature of 10 ° C / minute measured.

In general, there are two types of Har among these polyarylene sulfide resins zen, such as a linear type and a networked type, including partially networked. Both can be used in the present invention, and a linear type is prefers.

The 4-amino-2,2,6,6-tetramethylpiperidyl compound (c) with a steric ge hindered amino group as the basic structure is represented by the following formula (1) or (2) reproduced:

in which R₁ is a hydrogen atom, an oxygen atom (an oxy group), a hydroxyl group, an alkyl, cycloalkyl, allyl, benzyl, aryl, alkanoyl, alkenoyl, alkyl represents oxy or cycloalkyloxy. R₂ represents a hydrogen atom, an alkyl radical or a radical of the following formula (3),

in which X represents a direct bond, -O- or -NH-, R₄ represents a direct bond, one represents linear or branched alkylene, alkylidene or arylene and R₅ Hydrogen atom, an alkyl, aryl radical or a radical of the following formula (4) or (5) represents

and in which n represents an integer from 1 to 4, p represents an integer from 2 to 6 and R₃ represents an n-valent organic radical.

Preferred examples of the 4-amino-2,2,6,6-tetramethylpiperidyl compound of the Formula (1) or (2) are described in [I] to [VII] below.  

[I] n is 1 and R₃ is a hydrogen atom, an alkyl, cycloalkyl, alkenyl, Benzyl, aryl or a radical of the following formula (6):

in which Y represents a direct bond, -O- or -NR₈-, R₆ represents a direct bond, one represents linear or branched alkylene, alkylidene or arylene and R₇ and R₈ each represent a hydrogen atom, a hydroxyl group, an alkyl or aryl radical len.

More preferably, n is 1, R₁ and R₂ each represent a hydrogen atom or a Alkyl radical having 1-18 carbon atoms and R₃ represents a hydrogen atom, one Alkyl, cycloalkyl, alkenyl radical or the radical of the formula (6) in which Y is a direct Binding, -O- or -NR₈- represents, R₆ a direct bond, a linear or ver branched alkylene radical with 1-10 carbon atoms, an alkylidene or arylene radical represents and R₇ and R₈ are each a hydrogen atom, an alkyl radical with 1-18 Koh lenstoffatomen, an aryl radical with 6-21 carbon atoms or a radical of formula (4) or (5).

[II] n is 2 and R₃ represents an alkylene radical or a radical of the following formula (7) represents:

in the R₉ a direct bond, a linear or branched alkylene radical, an Al represents kylidene or arylene radical. More preferably n 2, R₁ and R₂ each represent represents a hydrogen atom or an alkyl radical having 1-18 carbon atoms and R₃ represents an alkylene radical or a radical of the formula (7) in which R₉ is a direct bond, a linear or branched alkylene radical with 1-10 carbon atoms, an alky represents liden or arylene.

The compound of formula (1) in which, when n is 2, R₂ is a radical of formula (3) where X is a direct bond, -O- or -NH-, R₄ is a direct bond, represents a linear or branched alkylene, alkylidene or arylene radical, R₅ Represents hydrogen atom, an alkyl, aryl radical or a radical of the formula (4) or (5) represents and R₃ represents an alkylene radical, is also more preferred.

[III] n is 3 and R₃ is a group of the following formula (8):

[IV] n is 4 and R₃ is a group of the following formula (9) or (10):

[V] Further, a compound represented by the following formula (1) is also preferred.

In the formula (1) R₁ represents a hydrogen atom, an oxygen atom (an oxy group), a hydroxyl group, an alkyl radical with 1-8 carbon atoms, a cycloalkyl, allyl, benzyl, aryl, alkanoyl, alkenoyl, Alkyloxy or cycloalkyloxy radical, and n is an integer of 1, 2 or 4, and when n is 1, R₂ represents a hydrogen atom, an alkyl radical having 1-8 carbon atoms or
represents, where P and Q represent a radical selected from an alkylene, alkylidene, vinyl and vinylidene group, and R₃ represents a hydrogen atom, an alkyl, cycloalkyl, alkenyl, benzyl, aryl radical or a radical of following formula (6):

in which Y represents a direct bond, -O- or -NR₈-, R₆ represents a direct bond, one represents linear or branched alkylene, alkylidene or arylene radical, and R₇ and R₈ each represents a hydroxyl group, an alkyl, aryl radical or a radical of the following Represent formula (4) or (5)

when n is 2, R₂ represents a hydrogen atom, an alkyl radical having 1-8 carbon atoms or

where P and Q are a residue selected from egg nem represent alkylene, alkylidene, a vinyl and a vinylidene group, and R₃ represents an alkylene radical or a radical of the following formula (7):

in which R₉ represents a direct bond, a linear or branched alkylene, alkylidene or arylene radical,
and when n is 4, R₂ represents a hydrogen atom or an alkyl radical having 1-8 carbon atoms and R₃ represents a group of the following formula (9) or (10):

More preferably in formula (1), R₁ and R₂ each represent a hydrogen atom or an alkyl radical having 1-8 carbon atoms, and

• (i) when n is 1, R₃ is a hydrogen atom, an alkyl, cycloalkyl, alkenyl radical or a radical of formula (6) in which Y represents a direct bond, -O- or -NR₈-, R₆ a direct bond, a linear or branched alkylene radical with 1-10 carbons represents atomic atoms, an alkylidene or arylene radical and R₇ and R₈ are each a Hy droxyl group, an alkyl group with 1-18 carbon atoms, an aryl group with 6-21 Represent carbon atoms or a radical of the formula (4) or (5), and
• (ii) when n is 2, R₃ represents an alkylene radical or a radical of the formula (7) in which R₉ is a direct bond, a linear or branched alkylene radical with 1-10 Koh lenstoffatomen represents an alkylidene or arylene radical.

Furthermore, at least one compound of the following formulas (i) - (iv) is also stronger prefers:

in which R₁₀ represents a hydrogen atom, an alkyl or alkyloxy radical, R₁₁ one Represents alkylene radical, R₁₂ represents an alkyl radical and R₁₃ and R₁₄ each represent water represent atomic atom or a methyl group.

In formula (i) preferably R₁₀ represents a hydrogen atom, a hydroxyl group, an alkyl radical with 1-10 carbon atoms or an alkyloxy radical with 1-10 Koh lenstoffatomen and R₁₁ represents an alkylene radical with 2-8 carbon atoms, and stronger preferably R₁₀ represents a hydrogen atom or a methyl group and R₁₁ represents a hexa methylene group.

In formula (ii) preferably R₁₀ represents a hydrogen atom, a hydroxyl group, an alkyl radical with 1-10 carbon atoms or an alkyloxy radical with 1-10 Koh lenstoffatomen, R₁₁ an alkylene radical with 2-8 carbon atoms and R₁₂ an Al represents kylrest with 1-18 carbon atoms and more preferably R₁₀ is water represents atom of atom or a methyl group.

In formula (iii) preferably R₁₀ represents a hydrogen atom, a hydroxyl group, an alkyl radical with 1-10 carbon atoms or an alkyloxy radical with 1-10 Koh lenstoffatomen and R₁₁ represents an alkylene radical with 2-8 carbon atoms, and stronger preferably R₁₀ represents a hydrogen atom or a methyl group.

In the formula (iv) preferably R₁₀ represents a hydrogen atom, a hydroxyl group, an alkyl radical with 1-10 carbon atoms or an alkyloxy radical with 1-10 Koh lenstoffatomen and R₁₁ represents an alkylene radical with 2-8 carbon atoms, and stronger preferably R₁₀ represents a hydrogen atom or a methyl group.  

[IV] The compound of the following formula (1):

in the R₁ a hydrogen atom, an oxygen atom (an oxy group), a hydroxyl group, an alkyl radical with 1-8 carbon atoms, a cycloalkyl, allyl, Ben represents cyl, aryl, alkanoyl, alkenoyl, alkyloxy or cycloalkyloxy, R₂ a Represents hydrogen atom or an alkyl radical, and

• (i) when n is 1, R₃ represents a hydrogen atom, an alkyl, cycloalkyl, alkenyl, benzyl, allyl radical or a radical of the following formula (6), in which Y represents a direct bond, -O- or -NR₈-, R₆ represents a direct bond, a linear or branched alkylene radical, an alkylidene or arylene radical and R₇ and R₈ each represent a hydroxyl group, an alkyl, aryl radical or a radical of represent the following formula (4) or (5):
• (ii) when n is 2, R₃ represents a radical of the following formula (7) in which R₉ represents a direct bond, a linear or branched alkylene radical, an alkylidene or arylene radical, and
• (iv) when n is 4, R₃ represents a group of the following formula (9) or (10).

More preferably in formula (1) R₁ represents a hydrogen atom or an alkyl radical with 1-8 carbon atoms, R₂ represents a hydrogen atom or an alkyl radical with 1-18 carbon atoms and, if n is 1, R₃ represents a hydrogen atom, an alkyl, cycloalkyl, Al kenyl radical or a radical of the formula (6) in which Y is a direct bond, -O- or -NR₈-, R₆ is a direct bond, a linear or branched alkylene radical having 1-10 carbon atoms, an alkylidene radical having 1-10 carbon atoms or represents an arylene radical and R₇ and R₈ each represent a hydrogen atom, an alkyl radical having 1-18 carbon atoms, an aryl radical having 6-21 carbon atoms or a radical of the formula (4) or (5), and
when n is 2, R₃ represents a radical of formula (7) in which R₉ represents a direct bond, a linear or branched alkylene radical having 1-10 carbon atoms, an alkylidene radical having 1-10 carbon atoms or an arylene radical.

[VII] The compound represented by the following formula (2)

in the R₁ a hydrogen atom, an oxygen atom (an oxy group), a hydroxyl group, an alkyl radical with 1-8 carbon atoms, a cycloalkyl, allyl, Ben represents cyl, aryl, alkanoyl, alkenoyl, alkyloxy or cycloalkyloxy, R₂ a Represents hydrogen atom or an alkyl radical having 1-8 carbon atoms, n is 3, p is an integer from 2 to 8 and R₃ represents a group of the following formula (8):

Examples of [n = 1] in [I], [V] and [VI] of the compound of the invention (c) Include 4-amino-2,2,6,6-tetramethylpiperidine, 4-methylamino-2,2,6,6-tetrame thyl-4-piperidine, 4-ethylamino-2,2,6,6-tetramethylpiperidine, 4-propylamino-2,2,6,6-th tramethylpiperidine, 4-butylamino-2,2,6,6-tetramethylpiperidine, 4-hexylamino-2,2,6,6- tetramethylpiperidine, 4-octylamino-2,2,6,6-tetramethylpiperidine, 4-dodecanylamino 2,2,6,6-tetramethylpiperidine, 4-diethylamino-2,2,6,6-tetramethylpiperidine, N- (2,2,6,6-  Tetramethyl-4-piperidyl) piperidine, N- (2,2,6,6-tetramethyl-4-piperidyl) acetamide and N- (2,2,6,6-tetramethyl-4-piperidyl) stearoylamide. In addition, the connections of the following formulas (25) to (43).

Examples of [n = 2] in [II], [V] and [VI] of the compound of the invention (c) include the following compounds.  

In formula (1) or (2), R₁ includes, for example, a hydrogen atom, a hydro xyl group, an alkyl radical with 1-10 carbon atoms, such as a methyl, ethyl or Propyl group, or an alkyloxy group with 1-10 carbon atoms, and includes white ter cyclic radicals such as cyclohexylmethyl and cyclohexylethyl groups in addition the linear or branched radicals when the carbon number is 3 or more, on. R₁ is preferably a hydrogen atom or a methyl group.

R₂ is preferably an alkyl radical having 1-18 carbon atoms or an alkyloxy radical with 1-18 carbon atoms, such as a methyl, ethyl, propyl, isopropyl, n-butyl, Isobutyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, 1,1,3,3- Tetramethylbutyl, n-decyl, n-dodecyl, n-octadodecyl, cyclohexyl, 3,3,5-tri methylcyclohexyl, cyclooctyl and cyclodecyl group.

R₃ includes an alkylene radical with 2-8 carbon atoms and alkylene radicals represented by -C _n H _2n - such as an ethylene, 1,2- or 1,3-propylene-1,2-, 1,3- or 1,4 - Butylene, pentamethylene, 2,2-dimethyl-1,3-propylene, hexamethylene and octa methylene and cyclohexylene and cyclohexylene dimethylene group. R₃ is preferably a hexamethylene group with 6 carbon atoms.

In the formula (3), R₄ is a hydrogen atom or an alkyl radical with 1-18 carbon atoms, such as a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n- Decyl, n-dodecyl, n-octadodecyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, cyclo octyl and cyclodecyl group.

In the formula (7) R₉ represents a direct bond, a linear or branched alkyl len residue with 1-10 carbon atoms, an alkylidene residue or an arylene residue, such as an ethylene, 1,2-, 1,3- or 1,4-propylene, 1,2-, 1,3- or 1,4-Bu tylene, pentamethylene, 2,2-dimethyl-1,3-propylene, hexamethylene, octamethylene, Cyclohexylene and cyclohexylene dimethylene group. Specific examples of connections gene include N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanediamine, N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) ethylenediamine, N, N'-bis (2,2,6,6-tetramethyl-4-piperi dyl) -1,8-octanediamine and a compound of the following formulas (44) to (49).

Examples of [n = 3] in [III] and [VII] of the compound (c) according to the invention include the connections below.

In formula (2) R₃ is a radical of formula (8).

Specific examples of the compounds include a compound of the following formulas (50) and (51).

Examples of [n = 4] in [I] and [IV] to [VI] of the verbin according to the invention Exercise (c) include the following compounds. In formula (1) or (2) R₃ is the group represented by formula (9) or (10).

Specific examples of the compounds include a compound of the following formulas (52) to (54).

The quantitative ratio of components (a) and (b) is:

• (a) 1 to 99% by weight of polyphenylene ether resin and
• (b) 99 to 1% by weight of crystalline thermoplastic resin, preferably
• (a) 10 to 90% by weight of polyphenylene ether resin and
• (b) 90 to 10% by weight of crystalline thermoplastic resin, more preferred
• (a) 10 to 80% by weight of polyphenylene ether resin and
• (b) 90 to 20% by weight of crystalline thermoplastic resin and most preferred
• (a) 15 to 60% by weight polyphenylene ether resin
• (b) 85 to 40% by weight of crystalline thermoplastic resin.

The amount of the component (c) is 0.001-15 parts by weight, preferably 0.1-10 Parts by weight, based on 100 parts by weight of the sum (a) of the polyphenylene ether resin and (b) the crystalline thermoplastic resin. If it is less than 0.001 Parts by weight, no effect of inhibition of gelling is found, and if if it is larger than 15 parts by weight, problems arise due to volatile substances, such as Foam up at the time of actual processing.

In the present invention, the thermoplastic resin composition further contains one Amount of a tolerance improver (d) that is effective to improve the mutual To improve the compatibility of components (a) and (b).

The tolerance enhancer (d) for mutual tolerance improvement tion of the polyphenylene ether (a) and crystalline ther The plastic resin (b) is at least one compound selected from the following Compounds (d1) to (d10).

(d1): An epoxy compound without an ethylenically and acetylenically unsaturated bond gene.

(d2): A compound with both at least one kind of an unsaturated molecule group such as a carbon-carbon double bond and a carbon Carbon triple bond, and (ii) at least one type of polar group.

(d3): A silane compound with ver in the molecule both (i) with an oxygen atom networked carbon atoms and (ii) at least one functional group chooses from an ethylenic carbon-carbon double bond, a carbon carbon-carbon triple bond, an amino group and a mercapto group, and without direct bonding of the functional group to the silicon atom.

(d4): A compound with at least two identical or different molecules functional groups selected from (i) OR (where R is a hydrogen atom, an Al represents kyl, aryl, acyl or carbonyldioxyrest) and (ii) a carboxylic acid, one Acid halide, an acid anhydride, an acid halide anhydride, an acid esters, an acid amide, an imide, an amide and salts thereof.  

(d5): A compound having both (i) an acid halide group and (ii) at least one group selected from a carboxylic acid group, a carbon acid anhydride group, an acid ester group and an acid amide group.

(d6): A copolymer of a vinyl aromatic compound and an α, β-unsaturated Dicarboxylic acid or a dicarboxylic acid anhydride or a copolymer of a vinylaro matic compound and an imide compound of an α, β-unsaturated dicarboxylic acid.

(d7): An organic compound without ethylenically and acetylenically unsaturated Bonds in the molecule with two or more isocyanate and / or isothiocyanate groups.

(d8): A compound without ethylenically and acetylenically unsaturated bonds in the Molecule and (OR) (where R is a hydrogen atom, an alkyl, aryl, acyl or carbo is nyldioxyrest) and with 2 or more amino groups.

(d9): one with at least one tolerance improver selected from (d1), (d2), (d3), (d4) and (d5) functionalized polyphenylene ether.

(d10): A copolymer of an alkenyl aromatic compound with a compound having mutual compatibility with the crystalline thermoplastic resin (b).

The compatibility improver (d1) used in the present invention includes condensation products of a phenol containing several hydroxyl groups, such as bisphenol A, tetrabromobisphenol A and resorcinol, with epichlorohydrin and such a glycol such as propylene glycol and polyethylene glycol with epichlorohydrin.

The compatibility enhancer (d2) used in the present invention includes compounds with both (i) at least one type of unsaturated in the molecule Group, such as a carbon-carbon double bond and carbon-Koh triple bond, and (ii) at least one type of polar group, more specifically a functional group, the affinity and chemical reactivity with an amidbin tion, a carboxyl end group and an amino end group which ent in the polyamide resin are showing.

These functional groups include both a carboxylic acid group, one of a carboxylic acid derived group in which a hydrogen atom of a carboxyl group or a hydroxyl group is replaced, such as a salt, an ester, an acid amide Acid anhydride, an imide, an acid azide and an acid halide, a nitrile group, a Oxazoline group, an epoxy group, an amino group, a hydroxyl group and iso cyanate group, a.

The tolerance improver (d2) includes unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, unsaturated epoxy compounds, unsaturated Alcohols, unsaturated amines and unsaturated isocyanates.  

Examples of the compatibility improver (d2) include maleic acid, maleic acid anhydride, fumaric acid, maleimide, maleic hydrazide and reaction products of maleic anhydride with diamines of the following formulas (55) and (56) on.

(where R represents an aliphatic radical or an aromatic radical).

Examples of the compatibilizer (d2) also include anhydride methyl Nadin acid dichloromaleic, maleic acid amide, itaconic Itaconsäureanhy anhydride, natural fats and oils such as soybean oil, tung oil, castor oil, linseed oil, hemp oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil and Sardine oil, epoxidized natural fats and oils, an unsaturated carboxylic acid such as acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, tiglinic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethyl acrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octene acid, 4-decenoic acid, 9-undecenoic acid , 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, Dococenoic acid, erucic acid, tetracocenoic acid, mycolipenic acid, 2,4-pentadienoic acid, 2,4-hexadienoic acid, diallyl acetic acid, geranic acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linoleic acid, octadecatrienoic acid, eicosadiene acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, docosatrienic acid, docosapentaenoic acid, tetracosenoic acid, Hexaco sensäure, hexacodienoic acid, octacosenoic acid and Tetraaconitinsäure, an ester, an amide and an anhydride of these unsaturated carboxylic acids, an unsaturated alcohol such as allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methylpro penyl carbinol, 4-penten-1-ol, 10-undecen-1-ol, propargyl alcohol, 1,3-pentadien-3-ol, 1,4-hexadiene -3-ol, 3,5-hexadien-2-ol, 2,4-hexadien-1-ol, by the formulas C _n H _2n-5 OH, C _n H _2n-7 OH, or C _n H _{2n- 9} OH alcohols (n is an integer), 3-butene-1,2-diol, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-3,4-diol and 2,6-octadiene-4 , 5-diol, unsaturated amines in which the OH group of the unsaturated Al alcohol is replaced by an -NH₂ group, a (meth) glycidyl acrylate and allyl gly cidyl ether.

Furthermore, oligomers of butadiene or isoprene (for example at least one average molecular weight of about 500 to 10,000) or polymers with high Molecular weight (for example with an average molecular weight of 10,000 or more), in the maleic anhydride, phenol, an amino group, a car bonic acid group, a hydroxyl group or an epoxy group is introduced, and Allyl isocyanurate also used as a tolerance improver (d2) according to the invention closed.

In addition, the compatibility improver used according to the invention closes (d2) also compounds which have two or more unsaturated groups and two or contain multiple polar groups (same or different species), and two or several types of the specified compounds can also be used.

Among these compounds are maleic anhydride, maleic acid, fumaric acid, Itaconic anhydride, itaconic acid and (meth) acrylic acid glycidyl ester preferred, and starch Maleic anhydride and fumaric acid are preferably used.

The compatibility enhancer (d3) used in the present invention closes silane compounds with both (i) in the molecule through an oxygen atom networked carbon atoms and (ii) at least one functional group from an ethylenic carbon-carbon double bond, a carbon Koh triple bond, an amino group and a mercapto group, and without  direct bonding of the functional group to the silicon atom, and for example II- Aminopropyltriethoxysilane and 2- (3-cyclohexyl) ethyltrimethoxysilane are included sen.

The compatibility improver used in the present invention (d4) includes aliphatic polycarboxylic acids, their esters and their amides of the formula (R₁O) _m R (COOR₂) _n (CONR₃R₄) _l , in which R is a linear or branched saturated ge aliphatic hydrocarbon radical with 2 to 20, preferably 2 to 10, carbon atoms, R₁ represents a hydrogen atom, an alkyl, allyl, acyl or carbonyl radical and preferably represents a hydrogen atom, R₂ represents a hydrogen atom, an alkyl radical or an allyl radical having 1 to 20, preferably 1 represents 10 to carbon atoms, R₃ and R₄ represent a hydrogen atom, an alkyl or allyl radical having 1 to 10, preferably 1 to 6, more preferably 1 to 4, carbon atoms, m is 1, (n + 1) an integer of 2 or more, preferably 2 or 3, 1 is an integer of 0 or more, and (R₁O) is in the α- or β-position to the carbonyl group, where 2 to 6 carbon atoms, for between two carbonyl groups.

For example, they are saturated aliphatic carboxylic acid esters and their amides, Anhydrides, hydrates and salts. The saturated aliphatic polycarboxylic acid closes Citric acid, malic acid and agaricinic acid. The connections are in detail in Japanese Examined Patent Publication Sho No. 61-502195.

The compatibility improver (d5) used in the present invention includes compounds of the formula [(I) -Z- (II)] in which (I) is a radical of the formula (X- CO -) - (in which X represents a fluorine, chlorine, bromine, iodine atom, a hydroxyl group, represents a radical OR or -O-CO-R and R represents a hydrogen atom, an alkyl or Represents allyl radical), (II) a carboxylic acid group, anhydride group, acid amide group, Represents imide group, carboxylate group, amino group or hydroxyl group and the Residues (I) and (II) are covalently bound by a divalent hydrocarbon radical Z. are.

For example, chloroformyl succinic anhydride, chloroethanoyl amber acid anhydride, trimellitic anhydride acid chloride, trimellitic anhydride acetic acid anhydride and terephthalic acid chloride included.

The compatibility enhancer (d6) used in the present invention includes copolymers of a vinyl aromatic compound and an α, β-unsaturated Dicarboxylic acid or a dicarboxylic acid anhydride and copolymers of a vinyl flavor table compound and an imide compound of an α, ν-unsaturated dicarboxylic acid on. Examples are copolymers of an alkenyl aromatic compound such as styrene and α-methylstyrene, with maleic anhydride, maleic acid, fumaric acid, n-methylmalein acid imide or N-phenyl maleimide.  

The compatibility improver used in the present invention (d7) includes organic compounds without ethylenically or acetylenically unsaturated Bonds in the molecule, but with two or more isocyanate groups and / or Isothiocyanate groups. Examples are aromatic polyisocyanates, such as m- Phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'- Diphenylmethane diisocyanate, 4,4'-diphenylpropane diisocyanate, naphthylene-1,5- diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, Dimethyldiphenylmethane diisocyanate, diphenyl ether 4,4'-diisocyanate, diphenyl sulfone 4,4'-diisocyanate, triphenylmethane triisocyanate and xylylene diisocyanate, aliphatic Polyisocyanates, such as 4,4'-cyclohexane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, Isophorone diisocyanate, 1,12-dodecane diisocyanate, hexamethylene diisocyanate, 2,4,4- Trimethylhexamethylene diisocyanate and mixtures thereof, compounds with Isothiocyanate groups corresponding to these polyisocyanates, polymers such as dimers and trimers of these polyisocyanates and polyisothiocyanates, carbodiimide-modified Products of these polyisocyanates and polyisothiocyanates, and polyisocyanate-modified Products such as blocked products in which the isocyanate group contains phenols or Lactam is masked.

The compatibility enhancer (d8) used in the present invention includes compounds without ethylenically and acetylenically unsaturated bonds in the Molecule and (OR) (where R is a hydrogen atom, an alkyl, aryl, acyl or carbo nyldioxyrest), but with 2 or more amino groups. Examples are saturated aliphatic diamines and polyamines, such as ethylenediamine, propylenediamine, Diaminobutane, diaminopentane, 2-methylpentamethylene diamine, hexamethylene diamine, Octamethylene diamine, diaminodecane and diaminododecane, and aromatic polyamines, such as p-xylylenediamine, m-xylylenediamine, tris (3-aminopropyl) amine Carbon dioxide adduct of these amines, p-phenylenediamine, m-phenylenediamine, Tolylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide and 3,3'- Diaminodiphenyl sulfone.

The compatibility enhancer (d10) used in the present invention includes copolymers of an alkenyl aromatic compound with a compound mutual compatibility with the crystalline thermoplastic resin (b). Examples are copolymers of an alkenyl aromatic compound, such as styrene and α- Methylstyrene, with an α-olefin when a polyolefin such as polyethylene resin and poly propylene resin, is used as the crystalline thermoplastic resin (b).

However, the compatibility improver (d) used in the present invention is not limited to the compounds illustrated above. Any connection with  mutual compatibility with polyphenylene ether resin (a) and crystalline ther Plastic resin (b) can be used.

If the compatibility improver (d) in the present invention ver is used is the effective amount to improve the mutual contract of constituents (a) and (b) 0.01 to 30 parts by weight, preferably 0.05 to 25 Parts by weight, and more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the Sum of the components of (a) the polyphenylene ether resin and (b) the crystalline thermoplastic resin. An amount exceeding 30 parts by weight is not preferred. since the mechanical strength due to a deterioration in the stability of the thermi resistance and the decomposition that occurs. Besides, when the tolerance improver (d) is used, a radical initiator is used can be used together.

In the present invention, fillers can be used to improve the mechani properties, such as strength, rigidity and hardness, to thermoplastic Resin mass are given.

The fillers include calcium carbonate, magnesium carbonate, aluminum hy hydroxide, magnesium hydroxide, zinc oxide, titanium oxide, magnesium oxide, magnesium sulfate, Aluminum silicate, magnesium silicate, calcium silicate, silica. hydrated calci umsilicate, hydrated aluminum silicate, mineral fibers, zonotrite, xonotlite, potassium titanate fiber whisker, magnesium oxysulfate, glass beads, glass fibers, glass beads, anor ganic fibers such as carbon fiber, stainless fiber, aluminum fiber and aramid fiber, carbon black, inorganic fillers, such as metal whiskers, silicon dioxide, aluminum oxide, talc, mica, clay, kaolinite, TiO₂, ZnO and Sb₂O₃, and one or more Other types of these fillers can be mixed. In addition, they are in front fillers used in the present invention are not limited by these.

The thermoplastic resin composition according to the invention is obtained by mixing and Melt kneading of the components (a), (b) and (c) obtained by conventional methods. The Components (b) and (c) can be used in the polymerization process of component (a) be added.

The thermoplastic resin composition according to the invention can with various Ver drive, such as injection molding, extrusion molding, blow molding, sheet molding and foils shape, be shaped, which are most suitable, the mass before deterioration highly protected by heat.

In addition, a molded article provided by the present invention in a wide range as packaging material, material for household appliances, Au Outer material for automotive parts and interior decoration material, such as trim parts from Motor vehicles are used.  

Examples

The present invention will be described in more detail according to the following examples and comparative examples, but these are simply exemplary explanations The present invention is not limited to them.

The masses of the examples and comparative examples were obtained by mixing the in the components shown in Tables 1 to 3. That is, these components were with a twin screw kneader (TEM-50A, manufactured by Toshiba Machine Co., Ltd.) extruded at a cylinder temperature of 260 ° C and with one strand cutter crushed to get the mass after cooling in a water container The resulting granulate was ge under vacuum drying at 130 ° C ge dries and with an injection molding machine (IS220EN, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 290 ° C, an injection pressure of 1200 kg / cm² and a mold temperature of 80 ° C to obtain a test piece.

The granules thus obtained and the test piece were made by the following procedure were examined and the results listed below were obtained.

[Molecular weight of polyphenylene ether]

The granules obtained were dissolved in chloroform and with a gel permeati Chromatograph (GPC) (HLC-8020, manufactured by Toso Co., Ltd .; columns K-806 K-805, K-804 and K-803; UV detector with a wavelength of 290 nm; temperature 40 ° C; Flow rate 1.0 ml / min.), And the molecular weight, vice versa based on that of the standard polystyrene, was determined.

[Yellowing index of resin composition after melt kneading]

The yellowness index (YI) of the injection molding mentioned above The test piece was made with CCM (Color Eye 2020 (Macbeth)) manufactured by Su mika Color Company, Ltd. measured.

[Stability of thermal resistance]

A test piece obtained with the above injection molding for the Izod Impact test with a thickness of 3.2 mm was carried out by standing for 100 and 500 hours at egg subjected to a thermal hysteresis at a constant temperature of 120 ° C and then Notched according to ASTM D256 and the Izod impact test at a temperature of 23 ° C carried out.

The substances illustrated below were prepared to reduce the To obtain resin compositions of the examples and comparative examples.

(Polyphenylene ether, PPE)

The polyphenylene ether (PPE) was obtained by homopolymerizing 2,6-dime thylphenol with a logarithmic viscosity of 0.46 in chloroform solution (0.5 g / dl)  obtained at 30 ° C. The molecular weight (Mw) of the PPE before melt kneading was 46 100.

(Crystalline thermoplastic resin)

PA-1: Nylon 6 with a number average molecular weight of 17,500.

PA-2: Nylon 66 with a number average molecular weight of 17,000.

PP: Sumitomo Noblen HD100, manufactured by Sumitomo Chemical Company, Ltd.

PBT: Tafpet N-1000 manufactured by Mitsubishi Rayon Company, Ltd.

PPS: M2880 manufactured by Toray / Phillips Corporation.

Impact resistance modifier: Cariflex TR1101, manufactured by Shell Che mical Company, Ltd.

(Tolerance enhancer)

Tolerability improver 1: maleic anhydride
Tolerance improver 2: diaminododecane
Compatibility Improver 3: Kraton G1701X manufactured by Shell Chemical Company, Ltd.
Compatibility improver 4: 4,4'-diphenylmethane diisocyanate.

(Additive)

Addition 1: Sanol LS-770, manufactured by Sankyo Co. Ltd., of the formula (57):

Addition 2: Tinuvin 622, manufactured by Ciba-Geigy Corp., of formula (58):

Addition 3: Chimasorb 944, manufactured by Ciba-Geigy Corp., of the formula (59):

Addition 4: Adekastab PEP-36, manufactured by Asahi Denka Kogyo K.K., of the formula (60):

The compounds used in the examples are according to the following Reference examples shown produced. In addition, unless otherwise stated in the reference examples all percentages wt .-%.

Reference Example 1 Preparation of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanediamine (compound manure 1)

981 g (6.32 mol) of 2,2,6,6-tetramethyl-4-piperi were placed in a 5 l autoclave din, 350 g (3.01 mol) hexamethylenediamine, 1500 g methanol and 5.0 g activated carbon 5% platinum was added while maintaining the temperature at 45-55 ° C. The inside of the Autoclaves were pressurized with hydrogen to 40 bar and to 70-80 ° C heated to perform hydrogenation. The hydrogenation was after 4 to 5 Hours completely. The catalyst was removed by filtering at 70 to 80 ° C below 2 to 3 bar away, and 1070 g of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanediamine (Compound 1) was obtained by distillation. Yield: 90%. Boiling point: 188 up to 190 ° C / 0.80 mbar.  

Reference example 2 Preparation of N, N'-bis (2-methoxycarbonylethyl) -N, N'-bis (2,2,6,6-tetramethyl-4-pi peridyl) -1,6-hexanediamine (compound 2)

In a 1 l four-necked flask, 80 g (0.20 mol) of the in Reference Example 1 were N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanediamine (compound 1) and 200 g of methanol and completely dissolved. This was done by solving 35 g (0.41 mol) of methyl acrylate in 100 g of methanol at room temperature put solution dripped. The reaction was then allowed to reflux for 12 hours fen. After the reaction was complete, the solvent was distilled off and the residue was recrystallized from hexane, 98 g (0.17 mol) of compound 2 being white Solid were obtained. Yield: 85%. Melting point: 50-52 ° C.

Reference example 3 Preparation of N, N'-bis (2-octadecyloxycarbonylethyl) -N, N'-bis (2,2,6,6-tetramethyl-4-- piperidyl) -1,6-hexanediamine (compound 3)

In a four-necked flask equipped with a stirrer and a reflux condenser ben 20 g (35 mmol) of N'N'-bis (2-methoxycarbo obtained in Reference Example 2 nylethyl) -N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanediamine (compound 2), 21 g (77 mmol) of stearyl alcohol and 200 ml of toluene were added, followed by stirring Reflux. A solution of 0.1 g (4 mmol) of lithium amide in 3 g of methanol was added dripped. The solvent was then distilled off with the addition of toluene and the Reaction completed. After 4 hours of reaction, toluene was added, followed from cooling to room temperature. The organic layer was washed three times with water washed and then concentrated to give 23 g (22 mmol) of Compound 3 were. Yield: 63%. Melting point: 45-46 ° C.

Reference example 4 Preparation of N, N-bis (ethoxycarbonyl) -N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) - 1,6-hexanediamine (compound 4)

At a temperature of 0 ° C or less, 22.8 g (0.21 mol) of chlorine get carbonic acid ethyl ester to a solution of 39.4 g (0.1 mol) in reference example 1 Nem N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanediamine (compound 1) in 200 ml of 1,2-dichloroethane was added, which was cooled to -10 ° C. Then slowly 8.4 g of sodium hydroxide dissolved in 50 ml of water were added while adjusting the tempera kept at 0 ° C. Then the temperature was raised to 20 ° C and the reaction was mix into a water layer and an organic layer separated and the organic Washed layer with water and dried over anhydrous sodium sulfate to obtain the  Remove solvent. Then the residue was crystallized from octane, where 44.1 g of compound 4 were obtained. Yield: 82%. Melting point: 125 ° C.

Reference Example 5 Preparation of Compound 5 [Chemical Formula (61)]

In a four-necked flask equipped with a thermometer and a stirrer 156 g of 4-amino-2,2,6,6-tetramethylpiperidine, 400 ml of toluene and 98 g of maleic acid added acid anhydride and replaced the atmosphere in the flask with nitrogen, followed heating for 6 hours to 60 ° C. with stirring. After full implementation the white crystals formed are filtered and washed with toluene, 243 g of the Compound 5 were obtained.

Reference example 6

2,2,6,6-tetramethyl-4-piperidylamine was used as Compound 6.

Examples 1 to 11 and Comparative Examples 1 to 10

The mixing ratios of the examples and comparative examples and the molecular weights of the polyphenylene ether in the resin compositions obtained (according to the melting point ten) are shown in Tables 1 and 2.

Examples 12 and 13 and Comparative Examples 11 and 12

The yellowing indices of the resin compositions are shown in Table 3.  

Examples 14 and 15 and Comparative Example 12

The stability of the thermal resistance of the resin compositions is shown in Table 4 shows.

A deterioration in the polyphenylene ether caused by heat at the time of processing can be effected by adding a special hindered pi peridine compound to the mass containing the polyphenylene ether and the crystalline thermo plastic resin includes, can be significantly improved.

Claims (33)

1. A thermoplastic resin composition comprising:

• (a) 1 to 99% by weight of a polyphenylene ether resin,
• (b) 99 to 1% by weight of a crystalline thermoplastic resin, and per 100 parts by weight of the sum of (a) and (b)
• (c) 0.001 to 15 parts by weight of at least one 4-amino-2,2,6,6-tetramethylpiperidyl compound of the following formula (1) or (2): in which R₁ represents a hydrogen atom, an oxygen atom (an oxy group), a hydroxyl group, an alkyl, cycloalkyl, allyl, benzyl, aryl, alkanoyl, alkenoyl, alkyloxy or cycloalkyloxy radical, R₂ represents a hydrogen atom, an alkyl radical or represents a radical of the following formula (3), in which X represents a direct bond, -O- or -NH-, R₄ represents a direct bond, a linear or branched alkylene, alkylidene or arylene radical and R₅ represents a hydrogen atom, an alkyl or aryl radical or a radical of the following formula ( 4) or (5), and in which n represents an integer from 1 to 4, p represents an integer from 2 to 6 and R₃ represents an n-valent organic radical.

2. Thermoplastic resin composition according to claim 1, in which in the formula (1) or (2) n is 1 and R₃ is a hydrogen atom, an alkyl, cycloalkyl, alkenyl, benzyl, aryl radical or a radical of the following formula (6 ) is: in which Y represents a direct bond, -O- or -NR₈-, R₆ represents a direct bond, represents a linear or branched alkylene, alkylidene or arylene radical and R₇ and R₈ each represent a hydrogen atom, a hydroxyl group, an alkyl or Represent aryl radical. 3. Thermoplastic resin composition according to claim 1, in which in the formula (1) or (2) n is 2 and R₃ is an alkylene radical or a radical of the following formula (7): in which R₉ represents a direct bond, a linear or branched alkylene, alkylene or arylene radical. 4. Thermoplastic resin composition according to claim 1, in which in the formula (1) or (2) n is 3 and R₃ is a group of the following formula (8): 5. Thermoplastic resin composition according to claim 1, in which in the formula (1) or (2) n is 4 and R₃ is a group of the following formula (9) or (10): 6. Thermoplastic resin composition according to claim 1, in which in the formula (1) R₁ and R₂ each represent a hydrogen atom or an alkyl radical having 1-18 carbon atoms and n is 1 or 2, and
(I) when n is 1, R₃ is a hydrogen atom, an alkyl, cycloalkyl, alkenyl radical or the radical of the formula (6) in which Y is a direct bond, -O- or -NR₈-, R₆ is a direct bond represents a linear or branched alkylene radical with 1-10 carbon atoms, an alkylidene or arylene radical and R₇ and R₈ each represent a hydrogen atom, an alkyl radical with 1-18 carbon atoms, an aryl radical with 6-21 carbon atoms or a radical of the formula (4) or (5) and (II) when n is 2, R₃ is a radical of the following formula (7): in which R₉ represents a direct bond, a linear or branched alkylene radical having 1-10 carbon atoms, an alkylidene or arylene radical. 7. A thermoplastic resin composition according to claim 1, in which in the formula (1) n is 2 and R₃ is an alkylene radical. 8. Thermoplastic resin composition according to claim 1, in which in the formula (1) n is 2, R₂ is a hydrogen atom and R₃ is an alkylene radical. 9. Thermoplastic resin composition according to claim 1, in which in the formula (1) n is 2, R₁ is a hydrogen atom or a methyl group, R₂ is a hydrogen atom and R₃ is a hexamethylene group. 10. Thermoplastic resin composition according to claim 1, in which in the formula (1) n is 2, R₂ is an alkyl radical and R₃ is an alkylene radical. 11. Thermoplastic resin composition according to claim 1, in which in the formula (1) n is 2, R₂ is a radical represented by the formula (3) in which X is a direct bin  dung, -O- or -NH-, R₄ is a direct bond, a linear or ver represents branched alkylene, alkylidene or arylene radical, R₅ represents a hydrogen atom, represents an alkyl or aryl radical or a radical of the formula (4) or (5) and R₃ is an alkylene radical. 12. Thermoplastic resin composition according to claim 1, in which the crystalline thermopla Stische resin (b) at least one resin selected from polyethylene, polypro pylene, polyamide, poly (alkylene dicarboxylate), polyacetal, polyarylene sulfide and Polyether ketone resins. 13. Thermoplastic resin composition according to claim 1, in which the crystalline thermopla tical resin (b) is a polyamide resin. 14. The thermoplastic resin composition according to claim 1, wherein the resin composition further comprises Amount of a tolerance improver (d) contains that improve mutual compatibility of components (a) and (b) is effective. 15. Thermoplastic resin composition according to claim 14, in which the component (d) is at least one compound selected from the following compounds (d1) to (d10):
(d1): An epoxy compound without ethylenically and acetylenically unsaturated bonds.
(d2): A compound having (i) both at least one kind of an unsaturated group, such as a carbon-carbon double bond and a carbon-carbon triple bond, and (ii) at least one kind of a polar group in the molecule.
(d3): a silane compound having both (i) carbon atoms crosslinked with an oxygen atom and (ii) at least one functional group selected from an ethylenic carbon-carbon double bond, a carbon-carbon triple bond, an amino group and a mercapto group, and without direct binding of the functional group to the silicon atom in the molecule.
(d4): A compound with at least two identical or different functional groups in the molecule, selected from (i) OR (where R represents a hydrogen atom, an alkyl, aryl, acyl or carbonyl dioxide radical) and (ii) a carboxylic acid, one Acid halide, an acid anhydride, an acid halide anhydride, an acid ester, an acid amide, an imide, an amide and salts thereof.
(d5): A compound having both (i) an acid halide group and (ii) at least one group selected from a carboxylic acid group, a carboxylic acid anhydride group, an acid ester group and an acid amide group in the molecule.
(d6): A copolymer of a vinyl aromatic compound and an α, β-unsaturated dicarboxylic acid or a dicarboxylic acid anhydride or a copolymer of a vinyl aromatic compound and an imide compound of an α, β-unsaturated dicarboxylic acid.
(d7): An organic compound without ethylenically and acetylenically unsaturated bonds in the molecule, but with two or more isocyanate and / or isothiocyanate groups.
(d8): A compound without ethylenically and acetylenically unsaturated bonds in the molecule and (OR) (where R is a hydrogen atom, an alkyl, aryl, acyl or carbonyl dioxide radical), but with 2 or more amino groups.
(d9): A polyphenylene ether functionalized with at least one compatibility improver selected from (d1), (d2), (d3), (d4) and (d5).
(d10): A copolymer of an alkenyl aromatic compound having a mutually compatible compound with the crystalline thermoplastic resin (b). 16. The thermoplastic resin composition according to claim 1, in which the 4-amino-2,2,6,6-th tramethylpiperidyl compound (c) is a compound of the following formula (1): in which R₁ represents a hydrogen atom, an oxygen atom (an oxy group), a hydroxyl group, an alkyl radical having 1-8 carbon atoms, a cycloalkyl, allyl, benzyl, aryl, alkanoyl, alkenoyl, alkyloxy or cycloalkyloxy radical and n represents an integer of 1, 2 or 4, and when n is 1, R₂ is a hydrogen atom, an alkyl radical having 1-8 carbon atoms or represents, where P and Q represent a radical selected from an alkylene, an alkylidene radical, a vinyl and vinylidene group and R₃ represents a hydrogen atom, an alkyl, cycloalkyl, alkenyl, benzyl, aryl radical or a radical of the following formula ( 6) represents: in which Y represents a direct bond, -O- or -NR₈-, R₆ represents a direct bond, a linear or branched alkylene radical, an alkylidene or arylene radical, and R₇ and R₈ each represent a hydroxyl group, an alkyl or aryl radical or represent a radical of the following formula (4) or (5) when n is 2, R₂ is a hydrogen atom, an alkyl radical with 1-8 carbon atoms or represents, where P and Q represent a radical selected from an alkylene, an alkylidene radical, a vinyl and a vinylidene group, and R₃ represents an alkylene radical or a radical of the following formula (7): in which R₉ represents a direct bond, a linear or branched alkylene, alkylene or arylene radical,
and, when n is 4, R₂ represents a hydrogen atom or an alkyl radical having 1-8 carbon atoms and R₃ represents a group of the following formula (9) or (10): 17. Thermoplastic resin composition according to claim 16, in which in the formula (1) R₁ and R₂ each represent a hydrogen atom or an alkyl radical having 1-8 carbon atoms and n is 1 or 2, and
(i) when n is 1, R₃ is a hydrogen atom, an alkyl, cycloalkyl, alkenyl radical or a radical of the following formula (6) in which Y represents a direct bond, -O- or -NR₈-, R₆ represents a direct bond, a linear or branched alkylene radical having 1-10 carbon atoms, an alkylidene or arylene radical and R₇ and R₈ each represent a hydroxyl group, an alkyl radical with 1-18 carbon atoms, an aryl radical with 6-21 carbon atoms or a radical of the following formula (4) or (5) and (ii) when n is 2, R₃ represents a radical of the following formula (7) in which R₉ represents a direct bond, a linear or branched alkylene radical having 1-10 carbon atoms, an alkylidene or arylene radical. 18. Thermoplastic resin composition according to claim 16, in which in the formula (1) n is 2 and R₃ represents an alkylene radical. 19. The thermoplastic resin composition according to claim 16, in which in the formula (1) n is 2, R₂ represents a hydrogen atom and R₃ represents an alkylene radical. 20. Thermoplastic resin composition according to claim 16, in which in the formula (1) n is 2, R₁ represents a hydrogen atom or a methyl group, R₂ represents a hydrogen represents atom and R₃ represents a hexamethylene group. 21. Thermoplastic resin composition according to claim 16, in which in the formula (1) n is 2, R₂ represents an alkyl radical and R₃ represents an alkylene radical. 22. A thermoplastic resin composition according to claim 16, in which the compound (c) represented by the formula (1) is at least one compound of the following formulas (i) - (iv): in which R₁₀ represents a hydrogen atom, a hydroxyl group, an alkyl or alkyloxy radical, R₁₁ represents an alkylene radical, R₁₂ represents an alkyl radical and R₁₃ and R₁₄ each represent a hydrogen atom or a methyl group. 23. Thermoplastic resin composition according to claim 22, in which in the formula (i) R₁₀ Hydrogen atom, a hydroxyl group, an alkyl radical with 1-10 carbon represents atoms or an alkyloxy radical having 1-10 carbon atoms and R₁₁  represents an alkylene radical having 2-8 carbon atoms. 24. Thermoplastic resin composition according to claim 22, in which in the formula (i) R₁₀ Represents hydrogen atom or a methyl group and R₁₁ is a hexamethylene represents group. 25. Thermoplastic resin composition according to claim 22, in which in the formula (ii) R₁₀ Hydrogen atom, a hydroxyl group, an alkyl radical with 1-10 carbons represents atomic atoms or an alkyloxy radical having 1-10 carbon atoms, R₁₁ represents an alkylene radical having 2-8 carbon atoms and R₁₂ is an alkyl radical with 1-18 carbon atoms. 26. Thermoplastic resin composition according to claim 22, in which in the formula (ii), R₁₀ represents a hydrogen atom or a methyl group. 27. A thermoplastic resin composition according to claim 22, in which in formula (iii) R₁₀ a hydrogen atom, a hydroxyl group, an alkyl radical with 1-10 carbons  represents atomic atoms or an alkyloxy radical having 1-10 carbon atoms and R₁₁ represents an alkylene radical with 2-8 carbon atoms. 28. Thermoplastic resin composition according to claim 22, in which in the formula (iii) R₁₀ represents a hydrogen atom or a methyl group. 29. Thermoplastic resin composition according to claim 22, in which in the formula (iv) R₁₀ a hydrogen atom, a hydroxyl group, an alkyl radical with 1-10 carbons represents atomic atoms or an alkyloxy radical having 1-10 carbon atoms and R₁₁ represents an alkylene radical with 2-8 carbon atoms. 30. Thermoplastic resin composition according to claim 22, in which in the formula (iv) R₁₀ represents a hydrogen atom or a methyl group. 31. A thermoplastic resin composition according to claim 1, in which the 4-amino-2,2,6,6-th tramethylpiperidyl compound (c) is a compound of the following formula (1): in which R 1 represents a hydrogen atom, an oxygen atom (an oxy group), a hydroxyl group, an alkyl radical having 1-8 carbon atoms, a cycloalkyl, allyl, benzyl, aryl, alkanoyl, alkenoyl, alkyloxy or cycloalkyloxy radical, R₂ represents a hydrogen atom or an alkyl radical, and n is an integer of 1, 2 or 4, and

• (I) when n = 1, R₃ is a hydrogen atom, an alkyl, cycloalkyl, alkenyl, benzyl, allyl radical or a radical of the following formula (6): in which Y represents a direct bond, -O- or -NR₈-, R₆ represents a direct bond, a linear or branched alkylene radical, an alkylidene or arylene radical and R₇ and R₈ each represent a hydroxyl group, an alkyl, an aryl radical or represent a radical of the following formula (4) or (5):
• (II) when n = 2, R₃ represents a radical of the following formula (7), in which R₉ represents a direct bond, a linear or branched alkylene radical, an alkylidene or arylene radical, and
• (IV) when n is 4, R₃ represents a group of the following formula (9) or (10).

32. Thermoplastic resin composition according to claim 31, in which in the formula (1) R₁ represents a hydrogen atom or an alkyl radical having 1-8 carbon atoms, R₂ represents a hydrogen atom or an alkyl radical having 1-18 carbon atoms and n is an integer of 1 or 2 is
and, when n is 1, R₃ represents a hydrogen atom, an alkyl, cycloalkyl, alkenyl radical or a radical of the following formula (6) in which Y represents a direct bond, -O- or -NR₈-, R₆ represents a direct bond, a linear or branched alkylene radical having 1-10 carbon atoms, an alkylidene radical having 1-10 carbon atoms or an arylene radical and R₇ and R₈ are each one Hydrogen atom, an alkyl radical having 1-18 carbon atoms, an aryl radical having 6-21 carbon atoms or a radical of the following formula (4) or (5) and, when n is 2, R₃ represents a radical of the following formula (7) in which R₉ represents a direct bond, a linear or branched alkylene radical with 1-10 carbon atoms, an alkylidene radical with 1-10 carbon atoms or an arylene radical. 33. Thermoplastic resin composition according to claim 1, in which the 4-amino-2,2,6,6-th tramethylpiperidyl compound (c) is a compound of the following formula (2): in which R₁ represents a hydrogen atom, an oxygen atom (an oxy group), a hydroxyl group, an alkyl radical having 1-8 carbon atoms, a cycloalkyl, allyl, benzyl, aryl, alkanoyl, alkenoyl, alkyloxy or cycloalkyloxy radical and n is 3 and in which R₂ represents a hydrogen atom or an alkyl radical having 1-8 carbon atoms and p is an integer from 2 to 8 and R₃ represents a group of the following formula (8):