JPH0718168A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a modified polyphenylene ether reactive with an ester, COOH or OH group, a saturated polyester and a phosphorous acid triester, good in impact and solvent resistances and heat- resistant rigidity and useful as industrial materials, etc. CONSTITUTION:This thermoplastic resin composition is obtained by blending (A) a modified polyphenylene ether, prepared by dissolving a polyphenylene ether such as poly(2,6-dimethyl-1,4-pheny1ene ether) in toluene, etc., adding sodium ethoxide and glycidol to the resultant solution, carrying out the reaction at 100 deg.C for 5hr, pouring the reactional mixture into methanol and then separating the product and having a functional group reactive with an ester, carboxyl or an alcoholic hydroxyl group with (B) a saturated polyester such as polybutylene terephthalate and (C) a phosphorous acid triester in an amount of 0.1-10 pts.wt. based on 100 pts.wt. total amount of the components (A) and (B). This composition is excellent in high rigidity and balance in mechanical strength.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition containing a modified polyphenylene ether and a saturated polyester. This composition is an engineering plastic useful as an industrial material such as an automobile member and an electric member having excellent solvent resistance and heat resistance rigidity as a connector, an ignition manifold, a coil sealing material, a gear, a crankshaft and the like.

[0002]

2. Description of the Related Art Polyphenylene ether (hereinafter referred to as "PP
"E") is used as an engineering plastic having excellent heat resistance, dimensional stability, non-hygroscopicity, and electrical characteristics. However, the melt fluidity is poor, molding processing such as injection molding or extrusion molding is difficult, and
The molded product has the drawback of poor solvent resistance and impact resistance.

On the other hand, saturated polyester represented by polybutylene terephthalate is widely used as an engineered plastic excellent in moldability, solvent resistance and mechanical strength in automobile parts, electric / electronic device parts and the like. However, the molded body of this resin has the drawbacks that the molding shrinkage rate and the linear expansion rate are large, and that the rigidity at high temperatures is greatly reduced.

Therefore, if a composition having good properties of PPE and saturated polyester and complementing undesired properties can be obtained, it becomes possible to provide an excellent resin material having a wide range of fields of use, and its industrial meaning. Can be said to be very large.

Here, a composition obtained by simply melt-mixing both resins is disclosed in, for example, Japanese Patent Publication No. 51-21664 and Japanese Patent Laid-Open No. 49-49.
-75662 and 59-159847. However, PPE and saturated polyester have poor compatibility with each other, and in such a simple blend system, the composition is unlikely to be in a uniform and fine mixed form. As a result, no satisfactory improvement of the impact resistance, heat resistance rigidity, dimensional accuracy and solvent resistance of the obtained molded product can be seen, and the appearance of the molded product is rather deteriorated.

JP-A-62-257958 and JP-A-4
No. 153259 discloses a composition of PPE modified with an alcoholic hydroxyl group and polybutylene terephthalate, but these compositions show improvement in mechanical properties as compared with the above compositions. However, it is still not sufficient and there is a gap in practical application.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a novel thermoplastic resin composition which has improved compatibility between PPE and saturated polyester, and is excellent in impact resistance, heat resistance and solvent resistance, and appearance of molded articles. The purpose is to provide.

[0008]

Means for Solving the Problems The present inventors have succeeded in adding a phosphite triester to a modified PPE having a functional group capable of reacting with an ester group, a carboxyl group or an alcoholic hydroxyl group, and a saturated polyester, and The present invention has been completed by finding that a composition having good compatibility and desirable physical properties can be obtained.

That is, the present invention provides the following component (A),
A thermoplastic resin composition containing (B) and (C). (A) Modified PPE having a functional group that reacts with an ester group, a carboxyl group or an alcoholic hydroxyl group (B) Saturated polyester (C) Phosphorous triester is a component (A) and a component (B).
0.1 to 10 parts by weight relative to 100 parts by weight in total, especially phosphite triester is represented by the general formula (I)

[0010]

[Chemical 2]

(In the formula, n represents 1 or 2, Ar represents an unsubstituted or substituted aryl group having 6 to 30 carbon atoms, and n is 2
At this time, Ar may be the same or different. R
Represents an alkylene group or an arylene group having 2 to 18 carbon atoms when n is 1, and represents an alkanetetrayl group having 4 to 18 carbon atoms when n is 2. Further, Ar and R are the above-mentioned thermoplastic resin compositions which are compounds represented by oxygen atom, nitrogen atom, sulfur atom and halogen atom)

Further, the modified PPE is an alcoholic hydroxyl group,
The above thermoplastic resin composition is a modified PPE having a functional group selected from an epoxy group and an acid anhydride group.

The present invention will be described in detail below. <Modified PPE (A) Having Functional Group Reactive with Ester Group, Carboxyl Group or Alcoholic Hydroxyl Group> Examples of the functional group reactive with ester group, carboxyl group or alcoholic hydroxyl group include alcoholic hydroxyl group, epoxy group and carboxyl group. Group, acid anhydride, ester, acid halide, amino group, amide group, oxazoline group, phosphoric acid group, phosphorous acid group and the like. Modified PPE used in the present invention
The base PPE of (A) has the general formula (II)

[0014]

[Chemical 3]

(Wherein R ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a halohydrocarbon group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and R 1 ² represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a halohydrocarbon group, a hydrocarbonoxy group or a halohydrocarbonoxy group)

It is a homopolymer or a copolymer having a structural unit represented by: Suitable examples of the primary alkyl group for R ¹ and R ² include methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, 2,
It is 3-dimethylbutyl, 2-, 3- or 4-methylpentyl or heptyl. Examples of secondary alkyl groups are
Isopropyl, sec-butyl or 1-ethylpropyl. In many cases, R ¹ is an alkyl group or a phenyl group,
Particularly, it is an alkyl group having 1 to 4 carbon atoms, and R ² is a hydrogen atom.

A specific example of PPE is poly (2,6-
Dimethyl-1,4-phenylene ether), poly (2,
6-diethyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether), poly (2-ethyl-6-methyl-1,4-phenylene ether), poly (2- Methyl-6-propyl-
1,4-phenylene ether), 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer,
2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol /
2,3,6-trimethylphenol copolymer, 2,6-
Dipropylphenol / 2,3,6-trimethylphenol copolymer, graft copolymer obtained by graft-polymerizing styrene to poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol / 2, 3,
Examples thereof include a graft copolymer obtained by graft-polymerizing styrene to a 6-trimethylphenol copolymer.

A preferred homopolymer of PPE is poly (2,6-dimethyl-1,4-phenylene ether). A preferable copolymer is a random copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. The molecular weight of PPE is usually preferably such that the intrinsic viscosity at 30 ° C. measured in chloroform is about 0.2 to 0.8 dl / g. The number average degree of polymerization is 25 to 400.

The PPE of the present invention is produced by oxidative coupling of phenolic compounds. Many catalyst systems are known for oxidative coupling of PPE, and any known catalyst can be used. For example, those containing an amino compound and at least one kind of a heavy metal compound such as copper, manganese, and cobalt, usually in combination with various other substances (eg, US Pat. No. 4,042,05).
No. 6, No. 3,306,874, No. 3,306,8
No. 75, No. 3,365,422, No. 3,639,
No. 656, No. 3,642, 699, No. 3,73
No. 3,299, No. 3,838,102, No. 3,6
61,848, 5,037,943, etc.).

Modified PP having a functional group which reacts with the ester group, carboxyl group or alcoholic hydroxyl group of the present invention
Preferable as E is P having an alcoholic hydroxyl group.
Examples thereof include PE, PPE having an epoxy group, and PPE having an acid anhydride group. P having these alcoholic hydroxyl groups
Known materials such as PE, PPE having an epoxy group, and PPE having an acid anhydride group can be used, and the structure and manufacturing method thereof are not particularly limited.

For example, PP having an alcoholic hydroxyl group
E is shown below, PPE having an epoxy group is shown below, and PPE having an acid anhydride group is shown in.

PPE modified with a compound having both an alcoholic hydroxyl group and an ethylenic double bond. This is a roll mill after mixing PPE with a compound having both an alcoholic hydroxyl group and an ethylenic double bond,
150-320 ° C using Banbury mixer, extruder, etc.
Or a compound having an alcoholic hydroxyl group and an ethylenic double bond in a solvent such as benzene, toluene, xylene, or chlorobenzene is heated and reacted with unmodified PPE in a solvent such as benzene, toluene, xylene, or chlorobenzene. .

Examples of the compound having both an alcoholic hydroxyl group and an ethylenic double bond include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,4-butanediol monoacrylate and 1,4.
-Butanediol monomethacrylate, bis (1,4-
Butanediol) malate, 1,6-hexanediol monoacrylate, 1,6-hexanediol monomethacrylate, trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, pentaerythritol monoacrylate, pentaerythritol monomethacrylate, allyl alcohol, etc. There is.
Of these, 2-hydroxyethyl methacrylate and the like are particularly preferable.

The amount of the compound having both the alcoholic hydroxyl group and the ethylenic double bond used is 0.01 to PPE.
It is 20% by weight, preferably 0.1 to 10% by weight. In addition, in order to promptly proceed with this modification reaction,
For example, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, m-toluyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxybenzoate, di- Organic peroxides such as -t-butyl peroxide; 2,2'-azobisisobutyronitrile, 2,2
The presence of a radical initiator represented by an azo compound such as'-azobisisovaleronitrile is an effective method.

A modified PPE obtained by converting a phenolic hydroxyl group at the molecular end into an alcoholic hydroxyl group with a functionalizing agent. The following a) to e) are shown. a) Alcoholic hydroxyl group-modified PPE using glycidol as a functionalizing agent (JP-A-3-250025) b) Alcoholic hydroxyl group-modified PPE obtained by hydrolyzing the obtained terminal glycidyl PPE by using epihalohydrin as a functionalizing agent (special (Kaihei 3-250025) c) Alcoholic hydroxyl group-modified PPE using halogenated alkyl alcohol as a functionalizing agent (JP-A-3-292)
No. 326) d) Alcoholic hydroxyl group-modified PPE using alkylene carbonate as a functionalizing agent (JP-A-3-250027).
E) Alcoholic hydroxyl group-modified PPE using 1,2-alkylene oxide as a functionalizing agent (JP-A-63-128)
No. 021)

Modified PPE having an alcoholic hydroxyl group in the molecular chain (Japanese Patent Application Laid-Open No. 4-202223, Japanese Patent Application 3)
-325045). This alcoholic hydroxyl group-modified PPE has carbon-carbon as a substituent.
Produced by a method of reacting PPE containing a unit having a carbon unsaturated bond with a compound having both a thiol group and a hydroxyl group (JP-A-4-103629) or a method of reacting a borane compound (JP-A-4-20524). It is also possible to carry out the process, and as shown in JP-A-2-107634, it is also possible to produce by reacting ethylene oxide with PPE metallized with an alkali metal. The alcoholic hydroxyl group-modified PPE may be a random copolymer or a block copolymer.

PPE modified with a compound having both an epoxy group and an ethylenic double bond. This is a method in which a compound having both an epoxy group and an ethylenic double bond is mixed with PPE, and then melt-kneaded at a temperature of 150 to 320 ° C. using a roll mill, Banbury mixer, extruder or the like, for example, benzene. It can be produced by a method of heating and reacting a compound having an epoxy group and an ethylenic double bond with PPE in a solvent such as toluene, xylene or chlorobenzene.

Examples of the compound having both an epoxy group and an ethylenic double bond include maleic acid, fumaric acid, chloromaleic acid, citraconic acid, itaconic acid, glycidyl of unsaturated dicarboxylic acids such as 3- or 4-vinylphthalic acid. Ester; glycidyl ester of unsaturated monocarboxylic acid such as acrylic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, o, m or p-vinylbenzoic acid, undecenoic acid; N- [4- (2,3- Epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, N- [4- (2,3-epoxypropoxy) -3
-Methylbenzyl] acrylamide, N- [4- (2,2
Acrylamide derivatives such as 3-epoxypropoxy) benzyl] acrylamide; 3,4-epoxycyclohexylmethyl methacrylate, N- [4- (2,3-epoxy) propoxy] phenylmaleimide and the like. Of these, preferred are glycidyl methacrylate and N- [4- (2,3-epoxypropoxy)-
3,5-dimethylbenzyl] acrylamide and the like,
More preferred is N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide.

The amount of the compound having both the epoxy group and the ethylenic double bond used is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on PPE. Further, in order to promptly carry out this modification reaction, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, m-toluyl peroxide, diisopropyl are added to the reaction system. Peroxydicarbonate, t-butyl peroxybenzoate, di-t-
Organic peroxides such as butyl peroxide; the presence of radical initiators represented by azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobisisovaleronitrile is effective. Is the way.

The terminal glycidyl PPE shown in b) above. An epoxy group-modified PPE obtained by reacting epihalohydrin with PPE metallized with an alkali metal. A PPE modified with a compound having an acid anhydride group and an ethylenic double bond at the same time. This is obtained by mixing the above PPE, a compound having an acid anhydride group and an ethylenic double bond at the same time, and then using a roll mill, Banbury mixer, extruder or the like at 150 to 320 ° C.
Manufactured by a method of performing a melt-kneading reaction at a temperature of, or a method of heating and reacting the above PPE with a compound having an acid anhydride group and an ethylenic double bond in a solvent exemplified by benzene, toluene, xylene, chlorobenzene, etc. it can.

The compound having an acid anhydride group and an ethylenic double bond at the same time is, for example, maleic acid, fumaric acid,
Unsaturated dicarboxylic acid anhydrides such as chloromaleic acid, citraconic acid, itaconic acid, 3 or 4-vinylphthalic acid, acrylic acid, crotonic acid, vinylacetic acid,
Examples thereof include acid anhydrides of monocarboxylic acids such as methacrylic acid, pentenoic acid, o-, m- or p-vinylbenzoic acid, and undecenoic acid. Of these, maleic anhydride, itaconic anhydride and the like are preferable, and maleic anhydride and the like are particularly preferable.

The amount of the compound having the acid anhydride group and the ethylenic double bond at the same time is 0.01 to 20 relative to PPE.
%, Preferably 0.1 to 10% by weight. Also,
In order to accelerate this modification reaction, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, m-toluyl peroxide, diisopropyl peroxide are added to the reaction system. Dicarbonate, t
-Butyl peroxybenzoate, organic peroxides exemplified by di-t-butyl peroxide, etc., 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, etc. The presence of a radical initiator represented by an azo compound or the like is an effective method.

A PPE modified by reacting a compound having an acid halide and an acid anhydride group at the same time with a phenolic hydroxyl group at the molecular end of PPE, or a compound having two or more acid anhydride groups. (JP-A-62-500456 and JP-A-63-199754)

<Saturated Polyester (B)> As the saturated polyester of the component (B), various polyesters can be used. For example, as one of them, there may be mentioned a thermoplastic polyester produced by condensing a dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative thereof and a dihydroxy compound according to a usual method.

Specific examples of the aromatic or aliphatic dicarboxylic acid suitable for producing this polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and terephthalic acid. acid,
Isophthalic acid, p, p'-dicarboxydiphenyl sulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, 2,6-naphthalenedicarboxylic acid or 2,7. -Naphthalenedicarboxylic acid and the like or a mixture of these carboxylic acids.

As the aliphatic diol suitable for producing the saturated polyester (B), a linear alkylene glycol having 2 to 12 carbon atoms, for example, ethylene glycol, 1,3
-Propanediol, 1,4-butanediol, 1,6
-Hexanediol, 1,12-dodecanediol and the like can be mentioned. As the aromatic diol, there are p-xylene glycol, pyrocatechol, resorcinol, hydroquinone, and alkyl-substituted derivatives of these compounds. Other suitable diols also include 1,4-cyclohexanedimethanol.

Other preferable saturated polyesters (B) include polyesters obtained by ring-opening polymerization of lactone. For example, polypivalolactone, poly (ε-caprolactone) and the like. In addition, as another preferable polyester, a polymer (Ther
There is polyester as motoropic Liquid Crystal Polymer: TLCP). Typical examples of polyesters that fall into these categories are Eastman Kodak's X7G, Dartco's Xydar, Sumitomo Chemical's Econor, and Celanese's Vectra.

Among the saturated polyesters (B) listed above, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PB).
N), poly (1,4-cyclohexanedimethyl terephthalate) (PCT), liquid crystalline polyester and the like are the saturated polyester (B) suitable for the thermoplastic resin composition of the present invention.

<Phosphorous Acid Triester (C)> As the phosphorous acid triester used in the present invention, all known phosphorous acid triesters can be used. As the phosphorous acid triester (C),
Examples thereof include compounds represented by the following general formulas (III) and (IV).

[0040]

[Chemical 4]

(In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms or an unsubstituted or substituted aryl group having 6 to 30 carbon atoms. R ³ represents an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. May be included)

[0042]

[Chemical 5]

(In the formula, the definitions of n, R and R ³ are the same as above.) Here, examples of R ³ include methyl, ethyl, propyl, octyl, isooctyl, isodecyl, decyl,
Stearyl, lauryl, phenyl, 2-, 3- or 4-methylphenyl, 2,4- or 2,6-dimethylphenyl, 2,3,6-trimethylphenyl, 2-,
3- or 4-ethylphenyl, 2,4- or 2,6-diethylphenyl, 2,3,6-triethylphenyl, 2-, 3- or 4-tert-butylphenyl, 2,4- or 2,6 -Di-tert-butylphenyl, 2,6-di-tert-butyl-4-methylphenyl,
2,6-di-tert-butyl-4-ethylphenyl, octylphenyl, isooctylphenyl, 2-, 3- or 4-nonylphenyl, 2,4-dinonylphenyl,
Examples thereof include biphenyl and naphthyl, and among them, unsubstituted or substituted aryl groups are preferable.

As an example of R, in the general formula (IV), n
When 1, is 1,2-phenylene group; polymethylene groups such as ethylene, propylene, trimethylene, tetramethylene, hexamethylene, etc., and when n is 2, pentaerythrityl represented by the general formula (V). Examples thereof include a tetrayl group having a structure.

[0045]

[Chemical 6]

(In the formula, each Q is a hydrogen atom or a carbon number of 1 to
6 represents an alkyl group)

Of these, preferred as the phosphite triester (C) are trioctyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triisooctyl phosphite, tris (nonylphenyl). ) Phosphite,
Tris (2,4-dinonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenylphosphite, tris (octylphenyl) phosphite, diphenylisooctylphosphite, diphenyliso Decylphosphite, octyldiphenylphosphite, dilaurylphenylphosphite, diisodecylphenylphosphite, bis (nonylphenyl) phenylphosphite, diisooctylphenylphosphite, diisodecylpentaerythritol diphosphite, dilaurylpentaerythritoldiphosphite Fight, distearyl pentaerythritol diphosphite,

(Phenyl) (1,3-propanediol) phosphite, (4-methylphenyl) (1,3-
Propanediol) phosphite, (2,6-dimethylphenyl) (1,3-propanediol) phosphite, (4-tert-butylphenyl) (1,3-propanediol) phosphite, (2,4-diphenylene) -Tert-butylphenyl) (1,3-propanediol) phosphite, (2,6-di-tert-butylphenyl) (1,3-
Propanediol) phosphite, (2,6-di-tert
-Butyl-4-methylphenyl) (1,3-propanediol) phosphite, (phenyl) (1,2-ethanediol) phosphite, (4-methylphenyl)
(1,2-ethanediol) phosphite, (2,6-
Dimethylphenyl) (1,2-ethanediol) phosphite, (4-tert-butylphenyl) (1,2-ethanediol) phosphite, (2,4-di-tert-butylphenyl) (1,2- Ethanediol) phosphite, (2,6-di-tert-butylphenyl) (1,2-
Ethanediol) phosphite, (2,6-di-tert-
Butyl-4-methylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butyl-4-)
Methylphenyl) (1,4-butanediol) phosphite,

Diphenyl pentaerythritol diphosphite, bis (2-methylphenyl) pentaerythritol diphosphite, bis (3-methylphenyl) pentaerythritol diphosphite, bis (4-methylphenyl) pentaerythritol diphosphite, bis (2,4-Dimethylphenyl) pentaerythritol diphosphite, bis (2,6-dimethylphenyl) pentaerythritol diphosphite, bis (2,3,6-
Trimethylphenyl) pentaerythritol diphosphite, bis (2-tert-butylphenyl) pentaerythritol diphosphite, bis (3-tert-butylphenyl) pentaerythritol diphosphite, bis (4
-Tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl)
Pentaerythritol diphosphite, bis (2,6-
Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
Bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (biphenyl) pentaerythritol diphosphite, dinaphthyl pentaerythritol diphosphite A fight etc. are mentioned.

More preferred phosphite triesters having n of 2 are bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite,
Examples thereof include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. The thermoplastic resin composition of the present invention may contain a compound produced by decomposition (hydrolysis, thermal decomposition, etc.) of these phosphorous triesters.

<Composition Ratio of Constituent Components> The blending ratio of the modified PPE as the component (A) and the saturated polyester as the component (B) in the resin composition of the present invention will be described below. From the balance, ingredient (A)
It is preferably 10 to 90% by weight, more preferably 10 to 80% by weight, and further preferably 10 to 5% by weight in the resin composition.
It is 0% by weight. When the content of the component (A) is less than 10% by weight, the effect of improving the heat resistance rigidity is small. On the contrary, if it exceeds 90% by weight,
Solvent resistance and molding processability deteriorate.

Component (B) is preferably 9 in the resin composition.
It is 0 to 10% by weight, more preferably 90 to 20% by weight, and further preferably 90 to 50% by weight. When the content of the component (B) is less than 10% by weight, the effect of improving solvent resistance and molding processability is small. Further, if it exceeds 90% by weight, the heat resistance rigidity is not sufficient.

The modified PPE of the component (A) can be partially replaced with unmodified PPE. This native P
The ratio of replacement with PE is 95% by weight or less of the modified PPE.

The blending amount of the phosphite triester as the component (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the total of the components (A) and (B). Below 0.1 parts by weight,
The effect of addition of the component (A) as a compatibilizer is small,
The effect of improving the physical properties of the composition is insufficient. On the other hand, if it exceeds 10 parts by weight, the appearance of the molded product may be difficult, which is not preferable. The preferred range is 0.3 to 5 parts by weight,
It is more preferably 0.5 to 4 parts by weight.

<Additional Components> Components other than the above components (A), (B) and (C) may be added to the resin composition produced in the present invention. For example, 0.01 to 5% by weight of antioxidant, weather resistance improver, alkali soap, metal soap, hydrotalcite; plasticizer, fluidity improver 5
30% by weight; nucleating agent 0.5 to 2% by weight; flame retardant 3 to 15
Weight% can be used as an additional component. Further, addition of 5 to 50% by weight of organic filler, inorganic filler, reinforcing agent, especially glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc. It is effective in improving accuracy. Further, 0.5 to 5% by weight of a colorant and a dispersant thereof can be added.

Further, the addition of an impact strength improver, particularly styrene-butadiene copolymer rubber or its hydride,
Ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, or their α, β-
Unsaturated carboxylic acid anhydride modified product or glycidyl ester or unsaturated glycidyl ether modified product, copolymer or unsaturated epoxy compound composed of unsaturated epoxy compound and ethylene, copolymer composed of ethylene and ethylenically unsaturated compound, etc. Addition is effective in improving the strength of the composition.

The above impact strength improvers may be used alone or in combination of two or more. The blending amount of the impact strength improver varies depending on the physical property value used as a guide, but in the case of improving the balance between rigidity and impact strength of the composition, for example, it is 5 to 40% by weight in the resin composition. Also,
If necessary, other thermoplastic resin such as polystyrene, polycarbonate, polyamide or ABS resin may be added.

In order to enhance the compatibility with the component (C), one or more known auxiliary agents for esterification with phosphite can be used. As this auxiliary agent, for example,
Alkali metal halide salts such as lithium chloride; N-
Amide compounds such as methylpyrrolidone; amines such as pyridine and trioctylamine. The addition amount of these is preferably 0.1 to 5 in molar ratio with respect to phosphorus atoms.

<Production Method of Composition> The production of the resin composition of the present invention is not limited to a particular method, but a melt kneading method is preferable. For this, a kneading method generally used for thermoplastic resins can be applied. For example, if necessary, each component (A), (B) and (C), together with the additives and the like described in the above-mentioned additional components, are uniformly mixed by a Henschel mixer, a ribbon blender, a V type blender or the like. After mixing, they can be kneaded with a single-screw or multi-screw kneading extruder, roll, Banbury mixer, Labo Plastomill (Brabender) and the like.

Each component including the additives described in the above-mentioned additional components may be fed to the kneader at once or sequentially. Further, a mixture of two or more components selected from the components including the additives described in the section of the above-mentioned additional components in advance or kneaded may be used.

The kneading temperature and the kneading time can be arbitrarily selected depending on the desired conditions such as the resin composition and the kind of the kneading machine, but the kneading temperature is preferably 150 to 350 ° C., and the kneading time is preferably 20 minutes or less. Kneading temperature is 350 ° C or kneading time is 20
If it exceeds the limit, thermal deterioration of the phosphite triester, PPE or saturated polyester becomes a problem, and the physical properties of the molded article may deteriorate and the appearance may deteriorate.

<Molding Method of Composition> The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding and blow molding. Various molding methods such as extrusion molding and press molding can be applied.

[0063]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following, parts and percentages are based on weight.

The components used are as follows. PPE: poly (2,6-dimethyl-1,4-phenylene ether): manufactured by Nippon Polyether Co., Ltd., having an intrinsic viscosity of 0.30 dl / g measured in chloroform at 30 ° C. (hereinafter referred to as “H-30”) And 0.41 dl / g (hereinafter referred to as "H-41")

PPE having alcoholic hydroxyl group: Produced by the method shown in the following Reference Examples 1 to 5. Reference Example 1 H-41 (PPE) 50 at 80 ° C. under nitrogen atmosphere
0 g was dissolved in 5 liters of toluene. To this solution was added 500 ml of an ethanol solution in which 50 g of sodium ethoxide was previously dissolved, and then 150 g of glycidol was added dropwise. After stirring for 5 hours at 100 ° C., the reaction mixture was poured into 25 liters of methanol to precipitate the product PPE having an alcoholic hydroxyl group. The product was separated by filtration, washed with methanol and water, and dried under reduced pressure at 80 ° C.

PPE having this alcoholic hydroxyl group
Shows a peak derived from a hydroxyl group near 3380 cm ^-1 in its infrared absorption spectrum. Further, when the phenolic hydroxyl group at the molecular end of PPE was quantified, 59% thereof was reacted. The reaction rate of the terminal phenolic hydroxyl group of PPE is shown in the Journal of Applied Polymer Sci.
ence: Applied Polymer symposium, Volume 34 (1978) 10
According to the method described on pages 3 to 117, the phenolic hydroxyl group before and after the reaction was quantified and calculated. The PPE having an alcoholic hydroxyl group obtained here is designated as A of the modified PPE.

Reference Example 2 The procedure of Reference Example 1 was repeated except that 75 g of sodium ethoxide and 250 g of glycidol were used. The reaction rate of the phenolic hydroxyl group at the molecular end of PPE was 74%. PPE having alcoholic hydroxyl group obtained here
Is B of the modified PPE.

Reference Example 3 Under a nitrogen gas atmosphere, 75 parts of 2-allyl-6-methylphenol was dissolved in 400 parts of anhydrous tetrahydrofuran,
At 5 ° C., 503 parts of a tetrahydrofuran solution of borane having a concentration of 1 mol / liter was dropped, and the mixture was further reacted at 29 ° C. for 1 hour. 30 parts of pure water was added, and further 300 parts of 10% sodium hydroxide aqueous solution was added. To this, 51 parts of 30% hydrogen peroxide water was added dropwise at 40 ° C., and then reacted at 50 ° C. for 1 hour.

The reaction product was neutralized with concentrated hydrochloric acid, extracted with diethyl ether, and then dehydrated with anhydrous sodium sulfate. Finally remove diethyl ether, 135 ℃, 1-2mmHg
2- (3-hydroxypropyl)
A mixture of -6-methylphenol and 2- (2-hydroxypropyl) -6-methylphenol in a molar ratio of 92 :.
Obtained in a ratio of 8. The yield was 84%.

136 parts of this phenol derivative, 2,6-
886 parts of dimethylphenol and sodium hydroxide 9.
One part was dissolved in 2890 parts of xylene and 766 parts of methanol. Next, 20.5 parts of diethanolamine, 12.6 parts of dibutylamine, and 0.48 part of manganese chloride tetrahydrate dissolved in 316 parts of methanol were added in this order. The polymerization reaction was divided into two stages, and in the former stage, the temperature was kept at 40 ° C. and oxygen gas was introduced at a flow rate of 0.8 liter / min to carry out the reaction, until the solid was precipitated. In the latter stage, the temperature was kept at 30 ° C., the oxygen gas flow rate was 0.8 liter / min and the nitrogen gas was 8
It was set to the point where the precipitation of the polymer introduced at the rate of 1 / min stopped. The polymer was washed with hydrochloric acid-methanol to deactivate the catalyst. The resulting modified PPE had a yield of 95%, a hydroxyl group content of 7.1 mol% and a number average molecular weight of 9900.

The hydroxyl group content is represented by the ratio of the number of alcoholic hydroxyl groups to the number of polymer units, and is ¹ H--N
It was measured by MR. The number average molecular weight is a polystyrene conversion value measured by gel permeation chromatography (GPC). The PPE having an alcoholic hydroxyl group obtained here is referred to as C of the modified PPE.

Reference Example 4 82 parts and 2,6 of the phenol derivative obtained in Reference Example 3
-A procedure similar to that of Reference Example 3 was performed except that 940 parts of dimethylphenol was used. The yield of the modified PPE obtained was 93.
%, Hydroxyl group content: 4.5 mol% and number average molecular weight: 10
It was 500. The PPE having an alcoholic hydroxyl group obtained here is referred to as D of the modified PPE.

Reference Example 5 To 3 kg of H-30 (PPE), 30 g of 2-hydroxyethyl methacrylate was added, mixed well, and then melt-kneaded at 240 to 280 ° C. with a twin-screw extruder and pelletized. The obtained PPE having an alcoholic hydroxyl group is referred to as E of the modified PPE.

PPE having an epoxy group: Reference Example 6 below
It was manufactured by the method shown in. Reference Example 6 N- in place of 2-hydroxyethyl methacrylate
[4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide
It carried out like Reference Example 1. The obtained PPE having an epoxy group is designated as F of modified PPE.

PPE having an acid anhydride group: Reference Example 7 below
It was manufactured by the method shown in. Reference Example 7 The procedure of Reference Example 1 was repeated except that maleic anhydride was used instead of 2-hydroxyethyl methacrylate. The obtained PPE having an acid anhydride group is designated as G of modified PPE.

Saturated polyester: Polybutylene terephthalate: Novador 5010 grade, manufactured by Mitsubishi Kasei
The polystyrene equivalent number average molecular weight measured by GPC is 30,000, and the weight average molecular weight is 99,000 (hereinafter referred to as “P
"BT")

Phosphorous acid triester: The following phosphorous acid triesters were used. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite: manufactured by Asahi Denka Co., Ltd., trade name: MARK PEP-36, referred to as "a" in the table. Triphenyl phosphite: commercially available product, referred to as "b" in the table. Distearyl pentaerythritol diphosphite:
Asahi Denka Co., Ltd., trade name: MARK PEP-8, indicated as "c" in the table. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite: Asahi Denka Co., Ltd., trade name: M
ARK PEP-24G, referred to as "d" in the table.

Examples 1 to 13 and Comparative Examples 1 to 9 According to the composition ratios shown in Table 1, Table 2, Table 3 and Table 4, each component was set using a Labo Plastomill kneader (manufactured by Toyo Seiki Seisakusho Co., Ltd.). The mixture was kneaded at a temperature of 250 ° C. and a rotation speed of 180 rpm for 10 minutes and then pulverized to obtain a granular resin composition. The properties of the composition obtained are characterized by an injection molding machine [CS183MMX manufactured by Custom Scientific).
Minimax] was used to measure and evaluate a test piece injection-molded at a temperature of 280 ° C. by the following method. The results are shown in Table 1,
The results are shown in Table 2, Table 3 and Table 4, respectively.

(1) Impact resistance strength: A test piece having a length of 31.5 mm, a width of 6.2 mm and a thickness of 3.2 mm was injection-molded, and the Izod impact tester [Minimax CS-made by Custom Scientific Co., Ltd. 138TI type] was used to measure the Izod impact strength without a notch at 23 ° C.

(2) Tensile strength: Tensile test pieces having a parallel length of 7 mm and a parallel portion diameter of 1.5 mm were injection-molded, and a tensile tester (Custom Scientific CS-183T) was used.
Using E type), a tensile test was conducted under a condition of a tensile speed of 1 cm / min to measure the breaking strength and the breaking elongation. When kneading and molding, PBT and composition should be 1
The one dried under reduced pressure at 20 ° C. for 5 hours was used.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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The thermoplastic resin composition of the present invention has a modified P content.
By blending PE (A), saturated polyester (B) and phosphorous acid compound (C) together, component (A)
The compatibility between the component (B) and the component (B) is remarkably improved, and a molded article having high rigidity and an excellent mechanical strength balance, which has the characteristics inherent in each, is provided.

Claims (3)

[Claims] 1. A thermoplastic resin composition containing the following components (A), (B) and (C). (A) Modified polyphenylene ether having a functional group that reacts with an ester group, a carboxyl group or an alcoholic hydroxyl group (B) Saturated polyester (C) Phosphorous triester is a component (A) and a component (B).
0.1 to 10 parts by weight for 100 parts by weight in total 2. A phosphite triester is represented by the general formula (I): (In the formula, n represents 1 or 2, Ar represents an unsubstituted or substituted aryl group having 6 to 30 carbon atoms, and when n is 2, Ar
May be the same or different. R represents an alkylene group having 2 to 18 carbon atoms or an arylene group when n is 1, and represents an alkanetetrayl group having 4 to 18 carbon atoms when n is 2. The thermoplastic resin composition according to claim 1, wherein Ar and R are compounds represented by oxygen atom, nitrogen atom, sulfur atom and halogen atom). 3. The thermoplastic resin composition according to claim 1, wherein the modified polyphenylene ether is a modified polyphenylene ether having a functional group selected from an alcoholic hydroxyl group, an epoxy group and an acid anhydride group.