JP5261722B2 - Compatibilizer for polymer alloy, polyphenylene ether resin composition and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compatibilizer for producing a polymer alloy by blending a polyphenylene ether-based resin and a liquid crystalline polyester, and a polyphenylene-based resin composition and a film using the same. <P>SOLUTION: The compatibilizer for producing a polymer alloy is obtained by blending a polyphenylene ether-based resin and a liquid crystalline polyester. The compatibilizer includes a segment (A) solely consisting of glycidyl polymethacrylate and a segment (B) solely consisting of polystyrene, and is a block polymer having the following properties: (i) the weight ratio of the segment (A)/the segment (B) ((A)/(B)) is 0.04-1.0; (ii) the number-average molecular weight of the block polymer is 10,000-200,000; and (iii) the molecular weight distribution is 1.0-2.5. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a compatibilizer for polymer alloys, a polyphenylene ether resin composition, and a film.

  In recent years, a polymer alloy technique for mixing a plurality of different polymers has been actively studied as a means for improving the physical properties of polymer compounds. The purpose of the polymer alloy is to obtain a polymer having the characteristics of each constituent polymer by mixing a plurality of different polymers. Since such polymer alloys are composed of existing polymers, the properties of new polymers obtained from polymer blends can be predicted, and the development risk is lower than the development of new polymers. Development of polymer alloys is attracting attention for applications such as electronic components.

  However, in most cases, the polymers to be mixed are incompatible with each other so that the polymers are not compatible with each other. Therefore, there is a limit to dispersion by simple mixing, and the effect of modification may not be obtained. In such cases, it is known to use a compatibilizer to improve the dispersion of both polymer phases.

  On the other hand, the polyphenylene ether resin exhibits excellent properties such as mechanical, electrical properties, heat resistance and the like, but has poor fluidity and is difficult to be molded by melting. Therefore, for example, as disclosed in Patent Document 1, fluidity is improved by blending with a polystyrene-based resin, and it is generally used as a modified polyphenylene ether. However, a polyphenylene ether resin blended with a polystyrene resin has a problem that the original excellent mechanical properties and heat resistance of the polyphenylene ether are lowered.

  Further, a method has been proposed in which the excellent mechanical properties and heat resistance of polyphenylene ether are combined with the excellent fluidity and mechanical properties of liquid crystal polyester. For example, Patent Documents 2 to 3 disclose a polyphenylene resin composition in which a styrene copolymer is blended with a resin composition comprising polyphenylene ether and liquid crystal polyester, but it is still sufficient in balance between fluidity and mechanical properties. That's not true. Patent Document 4 proposes a polyphenylene-based resin composition in which an organic compound containing an isocyanate group is blended with a resin composition composed of polyphenylene ether and liquid crystal polyester. This is not sufficient in terms of physical properties, specific gravity, dimensional stability, in particular, anisotropy of linear expansion coefficient, and increases the cost, which may limit the intended use.

Japanese Patent Publication No. 43-17812 JP 9-111112 A JP 2002-121377 A JP 2002-38003 A

  An object of the present invention is to provide a compatibilizing agent for preparing a polymer alloy by blending a polyphenylene ether resin and a liquid crystal polyester, and a polyphenylene resin composition and a film using the compatibilizer.

The present invention relates to the following invention.
1. A compatibilizer for blending a polyphenylene ether resin and a liquid crystal polyester to prepare a polymer alloy,
Compatibilizer for polymer alloy, which is a block polymer having a segment (A) consisting only of polyglycidyl methacrylate and a segment (B) consisting only of polystyrene, and having the following characteristics (a) to (c) The weight ratio (A) / (B) of (A) to segment (B) is 0.04 to 1.0.
(B) The number average molecular weight of the block polymer is 10,000 to 200,000.
(C) Molecular weight distribution 1.0-2.5.

2. The compatibilizer for polymer alloy as described above, wherein the block polymer is a polymer obtained by polymerization using an organic tellurium compound-based polymerization initiator.
3. Organic tellurium compound polymerization initiator,
(A) an organic tellurium compound represented by formula (1),
(B) a mixture of an organic tellurium compound represented by formula (1) and an azo polymerization initiator,
(C) A mixture of an organic tellurium compound represented by formula (1) and an organic ditellurium compound represented by formula (2), or (d) an organic tellurium compound represented by formula (1), an azo polymerization initiator. And the compatibilizer for polymer alloy as described above, which is any one of a mixture of organic ditellurium compounds represented by formula (2).

（式中、Ｒ^１は、Ｃ_１〜Ｃ_８のアルキル基、アリール基、置換アリール基又は芳香族ヘテロ環基を示す。Ｒ^２及びＲ^３は、水素原子又はＣ_１〜Ｃ_８のアルキル基を示す。Ｒ^４は、アリール基、置換アリール基、芳香族ヘテロ環基、アシル基、アミド基、オキシカルボニル基又はシアノ基を示す。）
（Ｒ^１Ｔｅ）_２ （２）
（式中、Ｒ^１は、上記と同じ。）

(In the formula, R ¹ represents a C _{1 to} C ₈ alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group, or a cyano group.
(R ¹ Te) ₂ (2)
(In the formula, R ¹ is the same as above.)

4). It is a polymer alloy obtained by blending a polyphenylene ether resin and a liquid crystal polyester so that the blending ratio of the polyphenylene ether resin is larger than the blending ratio of the liquid crystal polyester using the compatibilizer for the polymer alloy described above. A polyphenylene ether-based resin composition.
5. The above compatibilizer is blended in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of a resin component composed of 60 to 95 parts by weight of a polyphenylene ether resin and 5 to 40 parts by weight of a liquid crystalline polyester. The polyphenylene ether-based resin composition described in 1.
6). The polyphenylene ether resin composition as described above, wherein the polyphenylene ether resin is an unmodified polyphenylene ether.
7). A masterbatch for preparing a polyphenylene ether-based resin composition obtained by kneading a liquid crystal polyester and the above-described compatibilizer.
8). A method for producing a polyphenylene ether-based resin composition, comprising blending a polyphenylene ether-based resin and the above master batch.
9. A film obtained from the polyphenylene ether-based resin composition.

  As a result of intensive studies, the present inventor has found that the above problems can be solved when a specific block polymer is used as a compatibilizing agent, and has completed the present invention.

  According to the present invention, a compatibilizer for preparing a polymer alloy by blending a polyphenylene ether resin and a liquid crystal polyester, a polyphenylene resin composition and a film using the compatibilizing agent, and having good electrical and mechanical properties In addition, it is possible to provide a polyphenylene ether-based resin composition that exhibits thermal characteristics and has particularly excellent heat resistance and excellent fluidity.

The compatibilizer for polymer alloy of the present invention is a block polymer composed of glycidyl methacrylate and styrene, preferably has a segment (A) composed only of polyglycidyl methacrylate and a segment (B) composed only of polystyrene. It is a block polymer having the characteristics (a) to (c).
(A) The weight ratio (A) / (B) of segment (A) to segment (B) is 0.04 to 1.0.
(B) The number average molecular weight of the block polymer is 10,000 to 200,000.
(C) Molecular weight distribution 1.0-2.5

The block polymer can be obtained, for example, by polymerization using an organic tellurium compound polymerization initiator. In particular,
(A) an organic tellurium compound represented by formula (1),
(B) a mixture of an organic tellurium compound represented by formula (1) and an azo polymerization initiator,
(C) A mixture of an organic tellurium compound represented by formula (1) and an organic ditellurium compound represented by formula (2), or (d) an organic tellurium compound represented by formula (1), an azo polymerization initiator. And an organic tellurium compound-based polymerization initiator selected from a mixture of organic ditellurium compounds represented by formula (2).

（式中、Ｒ^１は、Ｃ_１〜Ｃ_８のアルキル基、アリール基、置換アリール基又は芳香族ヘテロ環基を示す。Ｒ^２及びＲ^３は、水素原子又はＣ_１〜Ｃ_８のアルキル基を示す。Ｒ^４は、アリール基、置換アリール基、芳香族ヘテロ環基、アシル基、アミド基、オキシカルボニル基又はシアノ基を示す。） The organic tellurium compound used in the present invention is represented by the formula (1).

(In the formula, R ¹ represents a C _{1 to} C ₈ alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group, or a cyano group.

Specific examples of the group represented by R ¹ are as follows.
Examples of the C _{1 to} C ₈ alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, and n-pentyl. Examples thereof include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms such as a group, n-hexyl group, n-heptyl group and n-octyl group. A preferable alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms. More preferably, a methyl group, an ethyl group, or an n-butyl group is good.

Examples of the aryl group include a phenyl group and a naphthyl group. A preferred aryl group is a phenyl group. The substituent for the substituted aryl, an alkyl group of _C 1 -C _8, alkoxy group of C 1 -C _8, a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carbonyl-containing group represented by -COR ^a (R ^a = C ₁ -C ₈ alkyl group, C ₁ -C ₈ alkoxy group, aryl group, aryloxy group), sulfonyl group, trifluoromethyl group and the like.
A preferred substituted aryl group is a trifluoromethyl-substituted phenyl group.
These substituents may be substituted one or two, and the para position or ortho position is preferable.
Examples of the aromatic heterocyclic group include a pyridyl group, a pyrrole group, a furyl group, and a thienyl group.
Each group represented by R ² and R ³ is specifically as follows.
Examples of the C _{1 to} C ₈ alkyl group include the same alkyl groups as those described above for R ¹ .

Specific examples of each group represented by R ⁴ are as follows.
Examples of the aryl group, substituted aryl group, and aromatic heterocyclic group include the same groups as those described above for R ¹ .
Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.
Examples of the amide group include carboxylic acid amides such as acetamide, malonamide, succinamide, maleamide, benzamide, and 2-fluamide, thioamides such as thioacetamide, hexanedithioamide, thiobenzamide, and methanethiosulfonamide, selenoacetamide, hexanediselenoamide, Examples include selenoamides such as selenobenzamide and methaneselenosulfonamide, N-substituted amides such as N-methylacetamide, benzanilide, cyclohexanecarboxanilide, and 2,4′-dichloroacetanilide.
Examples of the oxycarbonyl group include a group represented by —COOR ^b (R ^b = H, C _{1 to} C ₈ alkyl group, aryl group).

Specifically, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group, etc. Can be mentioned.
Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.
Each group represented by R ⁴ is preferably an aryl group, a substituted aryl group, an oxycarbonyl group or a cyano group.
A preferred aryl group is a phenyl group.
Preferred examples of the substituted aryl group include a halogen atom substituted phenyl group and a trifluoromethyl substituted phenyl group.
In addition, in the case of a halogen atom, these substituents are preferably substituted by 1 to 5 pieces.
In the case of an alkoxy group or a trifluoromethyl group, one or two substituents may be substituted. In the case of one substitution, the para position or the ortho position is preferable, and in the case of two substitutions, the meta position is preferable. .
Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.

As the preferred organic tellurium compound represented by the formula (1), R ¹ represents a C _{1 to} C ₄ alkyl group or phenyl group, and R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₄ alkyl group. , R ⁴ is preferably an aryl group, a substituted aryl group, or an oxycarbonyl group.
Particularly preferably, R ¹ represents a C _{1 to} C ₄ alkyl group or a phenyl group, R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₄ alkyl group, and R ⁴ represents a phenyl group, A substituted phenyl group, a methoxycarbonyl group, and an ethoxycarbonyl group are preferable.

The organic tellurium compound represented by the formula (1) is specifically as follows.
(Methylterranylmethyl) benzene, (methylterranylmethyl) naphthalene, ethyl-2-methyl-2-methylterranyl-propionate, ethyl-2-methyl-2-n-butylterranyl-propionate, and Patent Documents 5 and 6 All of the described organic tellurium compounds can be exemplified.

The production method of the organic tellurium compound represented by the formula (1) is not particularly limited, and can be produced by a known method described in Patent Documents 5-6 and the like.
WO 2004/14848 WO 2004/14962

For example, the compound of formula (1) can be produced by reacting a compound of formula (3), a compound of formula (4) and metal tellurium.
Specific examples of the compound of the formula (3) are as follows.

〔式中、Ｒ^２、Ｒ^３及びＲ^４は、上記と同じ。Ｘは、ハロゲン原子を示す。〕
Ｘで示される基としては、フッ素、塩素、臭素又はヨウ素等のハロゲン原子を挙げることができる。好ましくは、塩素、臭素が良い。
Ｍ（Ｒ^１）ｍ （４）
〔Ｒ^１は、上記と同じ。Ｍは、アルカリ金属、アルカリ土類金属又は銅原子を示す。Ｍがアルカリ金属の時、ｍは１、Ｍがアルカリ土類金属の時、ｍは２、Ｍが銅原子の時、ｍは１または２を示す。〕

[Wherein R ² , R ³ and R ⁴ are the same as above. X represents a halogen atom. ]
Examples of the group represented by X include halogen atoms such as fluorine, chlorine, bromine and iodine. Preferably, chlorine and bromine are good.
M (R ¹ ) m (4)
[R ¹ is the same as above. M represents an alkali metal, alkaline earth metal or copper atom. When M is an alkali metal, m is 1, when M is an alkaline earth metal, m is 2, and when M is a copper atom, m is 1 or 2. ]

Examples of M include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, and copper. Lithium is preferable.
When M is magnesium, the compound (4) may be Mg (R ¹ ) ₂ or a compound represented by R ¹ MgX (X is a halogen atom) (Grignard reagent). X is preferably chlorine or bromine.
The organic ditellurium compound used in the present invention is represented by the formula (2).
(R ¹ Te) ₂ (2)
(R ¹ represents a C _{1 to} C ₈ alkyl group, aryl group, substituted aryl group or aromatic heterocyclic group.)

The group represented by R ¹ is as shown in Formula (1).
A preferable compound represented by the formula (2) is a compound in which R ¹ is a C _{1 to} C ₄ alkyl group or a phenyl group.

Specifically, the compound represented by the formula (2) includes dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, dicyclopropylditelluride, di-n- Butyl ditelluride, di-sec-butyl ditelluride, di-tert-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis- (p -Nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthylditelluride, dipyridylditelluride and the like. Preferred are dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride, and diphenyl ditelluride.
In the present invention, an azo polymerization initiator may be used for the purpose of accelerating the polymerization rate. The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization.

  For example, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid) (ACVA) 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2-methylamidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [ 2-Methyl-N- 2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methyl) Propionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) and the like.

  These azo initiators are preferably selected as appropriate according to the reaction conditions. For example, in the case of low temperature polymerization (40 ° C. or lower), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), In the case of medium temperature polymerization (40-80 ° C.), 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), dimethyl-2,2 '-Azobisisobutyrate (MAIB), 1,1'-azobis (1-acetoxy-1-phenylethane), 4,4'-azobis (4-cyanovaleric acid) (ACVA), 2,2'- Azobis (2-methylbutyramide), 2,2′-azobis (2-methylamidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], high temperature polymerization ( 1,1'- in the case of 80 ° C or higher) Zobis (1-cyclohexanecarbonitrile) (ACHN), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl) 2-methylpropionamide), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] Is good.

The segment (A) of the block polymer of the present invention is obtained by polymerizing a glycidyl methacrylate monomer. The segment (B) of the block polymer of the present invention can be obtained by polymerizing a styrene monomer.
The segment (A) may contain a small amount (0.05 to 20 mol%) of glycidyl acrylate in addition to glycidyl methacrylate.
In addition to styrene, the segment (B) may contain a small amount (0.05 to 20 mol%) of a vinyl aromatic compound such as α-methylstyrene, vinyltoluene, and pt-butylstyrene.

The compatibilizer for polymer alloy of the present invention polymerizes segment (A) and then polymerizes segment (B). Depending on the order of reaction, the segment (B) -segment (A) can also be obtained.
In the above, after the segment is manufactured, the reaction of the next block may be started as it is, or after the reaction is finished once, the reaction of the next segment may be started after purification.
The proportion of the monomer and the compound of formula (1) used may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the copolymer to be obtained. Usually, the monomer is used in an amount of 20 to 4000 mol with respect to 1 mol of the compound of formula (1). Preferably, it is 70 to 1600 mol.

  The use ratio of the compound of formula (1) and the azo polymerization initiator is usually 0.01-100 mol, preferably 0.1-10 mol, particularly azo polymerization initiator, with respect to 1 mol of the compound of formula (1). Preferably it is 0.1-5 mol.

  When the compound of the formula (1) and the compound of the formula (2) are used in combination, the use amount thereof is usually 0.01 to 100 mol of the compound of the formula (2) with respect to 1 mol of the compound of the formula (1), preferably Is 0.05 to 10 mol, particularly preferably 0.1 to 5 mol.

  When the compound of the formula (1), the compound of the formula (2) and the azo polymerization initiator are used in combination, the amount used is usually 1 mol of the total of the compound of the formula (1) and the compound of the formula (2). The azo polymerization initiator may be 0.01 to 100 mol, preferably 0.1 to 10 mol, and particularly preferably 0.1 to 5 mol.

  The reaction is usually carried out without a solvent, but an organic solvent or an aqueous solvent generally used in radical polymerization may be used. Examples of the organic solvent that can be used include benzene, toluene, anisole, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropaol, chloroform, Examples thereof include carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene and the like. Examples of the aqueous solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, diacetone alcohol and the like. The amount of the solvent used may be adjusted as appropriate. For example, 0.01 to 50 ml, preferably 0.05 to 10 ml, particularly preferably 0.1 to 1 ml of the solvent is used per 1 g of the vinyl monomer. good.

  Next, the mixture is stirred. The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the polymer to be obtained, but are usually stirred at 0 to 150 ° C. for 1 minute to 100 hours. Preferably, stirring is performed at 20 to 100 ° C. for 0.1 to 30 hours. More preferably, stirring is performed at 20 to 80 ° C. for 0.1 to 15 hours. It is a feature of the present invention that a high yield and a precise molecular weight distribution can be obtained even at such a low polymerization temperature and a short polymerization time. At this time, the pressure is usually a normal pressure, but may be increased or decreased.

  After completion of the reaction, the solvent or residual monomer is removed under reduced pressure by a conventional method to take out the target polymer, or the target product is isolated by reprecipitation using a target polymer insoluble solvent. The reaction treatment can be performed by any treatment method as long as there is no problem with the object.

Moreover, since the organic tellurium compound used as an initiator in the present invention is stable to water, the polymer of the present invention can be synthesized by an aqueous polymerization method described in Patent Document 7 and the like.
That is, the emulsion polymerization method uses a surfactant and polymerizes mainly in micelles. You may use dispersing agents, such as water-soluble polymers, such as polyvinyl alcohol, as needed. These surfactants can be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.3 to 50 parts by weight, more preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the total monomers. Moreover, it is preferable that the usage-amount of water is 50-2000 weight part with respect to 100 weight part of all the monomers, More preferably, it is 70-1500 weight part. Although superposition | polymerization temperature is not specifically limited, It is preferable to carry out in the range of 0-100 degreeC, More preferably, it is 40-90 degreeC. What is necessary is just to set reaction time suitably so that a polymerization reaction may be completed according to reaction temperature or the composition of the monomer composition to be used, the kind of surfactant or a polymerization initiator, etc. Preferably within 24 hours.
JP 2006-225524 A

  In the suspension polymerization method, a dispersant is used, and polymerization is mainly performed without using micelles. If necessary, a dispersing aid such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, or manganese sulfate may be used in combination with these dispersing agents. The amount of the water dispersion stabilizer used is preferably from 0.01 to 30 parts by weight, more preferably from 0.05 to 10 parts by weight, particularly preferably from 0.1 to 100 parts by weight based on 100 parts by weight of the total monomers. 5 parts by weight. Moreover, it is preferable that the usage-amount of water is 50-2000 weight part with respect to 100 weight part of all the monomers, More preferably, it is 70-1500 weight part. Although superposition | polymerization temperature is not specifically limited, It is preferable to carry out in the range of 0-100 degreeC, More preferably, it is 40-90 degreeC. What is necessary is just to set reaction time suitably so that a polymerization reaction may be completed according to reaction temperature or the composition of the monomer composition to be used, the kind of water dispersion stabilizer, a polymerization initiator, etc. Preferably within 24 hours.

  In the miniemulsion polymerization method, a surfactant and a co-surfactant are used, and after the monomers are forcibly dispersed using a homogenizer or an ultrasonic device, the polymerization is performed mainly without passing through micelles. The amount of the surfactant or cosurfactant used is 0.3 to 50 parts by weight, particularly preferably 0.5 to 50 parts by weight, based on the total monomers. The ultrasonic irradiation time is 0.1 to 10 minutes, particularly preferably 0.2 to 5 minutes (Patent Document 7).

The molecular weight of the polymer can be adjusted by the reaction time, the amount of the compound of the formula (1) and the amount of the compound of the formula (2), but a living radical polymer having a number average molecular weight of 10,000 to 200,000 is obtained. Can do.
When used as a resin composition for a compatibilizing agent of the present invention, it is preferable to use a block polymer having a number average molecular weight of 10,000 to 200,000, more preferably a weight average of 40,000 to 200,000. It is preferable to use a block polymer having a molecular weight. If the weight average molecular weight is less than 10,000, there is a possibility that the compatibilizer effect does not appear. If the weight average molecular weight exceeds 20,000, the heat resistance may be reduced.

  The molecular weight distribution (PD = Mw / Mn) of the polymer is controlled between 1.0 and 2.5. Furthermore, it is possible to obtain a compatibilizer for a polymer alloy having a narrower molecular weight distribution of a molecular weight distribution of 1.05 to 2.0, or 1.05 to 1.80. If the molecular weight distribution exceeds 2.5, the effect of the compatibilizer may be reduced.

  The ratio of segment (A) to segment (B) is such that the weight ratio (A) / (B) is preferably from 0.04 to 1.0, more preferably from 0.04 to 0.7. If the weight ratio is less than 0.04, the compatibilizing effect may be reduced. If the weight ratio exceeds 1.0, the melt viscosity may increase and the fluidity may be impaired.

When the organic tellurium compounds represented by formula (1) and formula (2) are used as an initiator, a tellurium atom may remain at the polymer terminal in the form of -TeR ¹ (R ¹ is the same as above).
Since the polymer in which the tellurium atom remains at the terminal is colored and is a metallic element, the remaining tellurium atom is included from the viewpoint of coloring the polymer alloy containing the obtained compatibilizing agent and preventing foreign matter contamination. A metal content is 1000 ppm or less with respect to the whole resin, and it is especially preferable that it is 200 ppm or less.

  The tellurium atom remaining at the molecular end is adsorbed after completion of the polymerization reaction using a radical reduction method such as tributylstannane or a thiol compound, and further activated carbon, silica gel, activated alumina, activated clay, molecular sieves and polymer adsorbent. , A method of adsorbing metal with ion exchange resin, etc., or adding a peroxide such as hydrogen peroxide or benzoyl peroxide, or blowing air or oxygen into the system to oxidize the tellurium atom at the end of the polymer In liquid state such as liquid-liquid extraction method or solid-liquid extraction method that removes residual tellurium compounds by combining with water washing and appropriate solvent, and ultrafiltration that extracts and removes only those with specific molecular weight or less A purification method and these methods can also be combined.

  The polyphenylene ether used in the polyphenylene ether-based resin composition of the present invention is represented by the formula (5).

（式中、Ｒ^５、Ｒ^６は水素原子または炭素数１〜３のアルキル基、Ｒ^７は炭素数１〜３のアルキル基である。）

(In the formula, R ⁵ and R ⁶ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ is an alkyl group having 1 to 3 carbon atoms.)

  This is a phenol compound, and specific examples include 2,6-dimethylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-allylphenol, 2-methyl-6. -Phenylphenol, 2,6-diphenylphenol, 2,6-dibutylphenol, 2,3,6-trimethylphenol, 2,3,6-tripropylphenol, 2,6-dimethyl It is produced by polymerizing -3-ethylphenol, 2,6-dimethyl-3-propylphenol and the like. The above phenol compounds can be used alone or in combination of two or more. Among them, preferable polyphenylene ethers include polyphenylene ether obtained from 2,6-dimethylphenol, and copolymerization of 2,6-dimethylphenol with 2,3,6-trimethylphenol or 2,6-diphenylphenol. The polyphenylene ether which can be mentioned can be mentioned. The polyphenylene ether of the present invention may be one obtained by copolymerizing a styrene monomer to such an extent that the performance thereof is not impaired, or one obtained by mixing a styrene polymer.

  On the other hand, as the liquid crystalline polyester used in the present invention, conventionally known ones can be widely used, and examples thereof include wholly aromatic (co) polyesters, wholly aromatic (co) polyesteramides, and aromatic-aliphatic copolyesters. These may be used alone or in combination of two or more.

  The wholly aromatic (co) polyester and wholly aromatic (co) polyesteramide are named because any monomer component constituting the polymer chain has at least one aromatic ring. As monomer components, hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxydiphenyl sulfide, Aromatic diols such as 4,4′-dihydroxydiphenylsulfone, 2,6-dihydroxynaphthoyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diamino Diphenyl, 4,4'-diaminodiphenyl Aromatic 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone and other aromatic diamines, terephthalic acid, isophthalic acid, 4,4 Aromatic dicarboxylic acids such as' -dicarboxydiphenyl, 4,4'-dicarboxydiphenyl ether, 2,6-dicarboxynaphthoyl, p-hydroxybenzoic acid, m-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid An aromatic hydroxycarboxylic acid such as 4-hydroxycinnamic acid, an aromatic aminocarboxylic acid such as p-aminobenzoic acid and 6-amino-2-naphthoic acid, and the like are not limited thereto.

  The wholly aromatic (co) polyester is obtained by the method disclosed in, for example, JP-A-56-104932 and JP-A-57-44622, and the wholly aromatic (co) polyesteramide is produced by, for example, US Pat. Each is manufactured according to the method disclosed in Japanese Patent No. 4182842.

  Specific examples of the aromatic-aliphatic (co) polyester include a copolymer of polyethylene terephthalate and p-hydroxybenzoic acid. The liquid crystalline polyester resin used in the present invention preferably has a weight average molecular weight of 5,000 to 200,000, particularly 10,000 to 50,000. If the weight average molecular weight is too small, the mechanical properties of the resulting resin composition tend to be reduced. Conversely, if the weight average molecular weight is too large, it is difficult to produce such a polymer, and the melt viscosity becomes high. Since it becomes difficult to mold the composition, neither is preferred.

  The polyphenylene ether resin composition of the present invention uses the above-mentioned compatibilizer for polymer alloy, and blends the polyphenylene ether resin and the liquid crystal polyester so that the blending ratio of the polyphenylene ether resin is larger than the blending ratio of the liquid crystal polyester. The resulting polymer alloy is preferred.

  The method for producing the polyphenylene ether-based resin composition of the present invention is not particularly limited, but a melt-kneading method is advantageous from an industrial viewpoint. A uniaxial or biaxial extruder, various kneaders, etc. can be used for melt kneading. At the time of kneading, each resin component may be uniformly mixed in advance using a Henschel mixer, a tumbler mixer, or the like, but it is also possible to use a method in which each resin component is separately and quantitatively supplied to the kneading apparatus.

  In the case of using a twin screw extruder, polyphenylene ether and liquid crystal polyester are mixed in advance with a blender or the like, supplied from the feed port on the upstream side of the extruder, and the compatibilizer for polymer alloy is fed to the downstream side. A method of charging from the mouth or a method of mixing all of the blended polymer and the compatibilizer for polymer alloy in advance with a blender and the like and supplying from the feed port are possible, but there is no particular limitation. Although there is no restriction | limiting in particular also in the screw arrangement of an extruder, It is preferable to provide a kneading zone in order to disperse | distribute polymers sufficiently and to make it easy to improve compatibility.

The polyphenylene ether-based resin composition of the present invention is a polymer alloy preparation masterbatch obtained by melt-kneading the above-mentioned compatibilizer for polymer alloy and at least one polymer selected from polyphenylene ether and liquid crystal polyester. It can also be obtained by melt-kneading the master batch and the other polymer. A master batch of the above-mentioned compatibilizer for polymer alloy and liquid crystalline polyester is preferred.
The polyphenylene ether-based resin composition thus obtained has an improved compatibility between the polyphenylene ether-based resin and the liquid crystal polyester.

  Various additives can be blended with the polyphenylene ether-based resin composition of the present invention in accordance with the intended use and purpose within a range not impairing the effects of the present invention. For example, antioxidants, heat stabilizers, UV absorbers, lubricants, mold release agents, colorants such as pigments, flame retardants, antistatic agents, conductivity imparting materials such as ketjen black, mechanical and thermal reinforcing materials Etc. The reinforcing material will be described in more detail. Glass fiber, carbon fiber, alumina fiber, highly elastic polyamide fiber, aluminum borate fiber, potassium titanate fiber, various mineral fibers and other fibrous fillers, talc, silica, calcium carbonate, mica And granular and scaly fillers such as kaolin. These reinforcing materials may be surface-treated with a surface treatment agent such as a silane coupling agent as is well known.

  The polyphenylene ether-based resin composition of the present invention and a film obtained using the same exhibit excellent electrical, mechanical and thermal properties, and have particularly excellent heat resistance. Although it can use suitably for the use which makes use of this characteristic, for example, electrical equipment / electronic / electric transmission related parts, automobile related parts, precision machine related parts, acoustic related parts, OA equipment related parts, chemical equipment related parts and the like can be mentioned. Moreover, it can be used for practically all uses where a polyphenylene ether resin or a liquid crystal polyester has been conventionally used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples, In the range which does not change the summary, it can change suitably.

In Examples and Comparative Examples, various physical properties were measured using the following equipment.
¹ H-NMR: Bruker BioSpin AVANCE 500 (500 MHz)
Molecular weight and molecular weight distribution: Gel permeation chromatograph Nippon Waters GPCV-2000 (Column: Tosoh TSK-GEL GMH _XL + TSK-GEL Multipore H _XL- M, polystyrene standard: Tosoh TSK
Standard)
Te content in polymer: ICP / MS

In addition, the polymer used is shown below.
Polyphenylene ether (hereinafter referred to as PPE); manufactured by Mitsubishi Engineering Plastics Co., Ltd .: PX100L
Modified polyphenylene ether (hereinafter referred to as mPPE); manufactured by Daicel Evonik Co., Ltd .: Best Run 1900HE
5 wt% glycidyl methacrylate-containing styrene copolymer (hereinafter SGMA5); NOF Corporation: Marproof G-1005S
10% by weight of glycidyl methacrylate-containing styrene copolymer (hereinafter SGMA10); manufactured by NOF Corporation: Marproof G-1010S

Example 1 and Comparative Examples 1-3
(Synthesis of poly (glycidyl methacrylate) polystyrene diblock polymer, compatibilizer A)
To a 3 L four-necked flask was added 20 g of anisole and 20 g (141 mmol) of glycidyl methacrylate [Wako Pure Chemical Industries, Ltd. Reagent], bubbled with argon gas for 30 minutes, and ethyl-2-methyl-2-n-butylteranyl-propionate. 0.962 ml (4.0 mmol) and 0.8 mg (2.28 mmol) of 1,1′-azobisisobutyronitrile were added and reacted at 60 ° C. for 7 hours. According to NMR analysis, the polymerization rate was 98%.
Next, after the polyglycidyl methacrylate solution obtained above was diluted with 20 ml of tetrahydrofuran, 280 g of toluene and 400 g (3.84 mol) of styrene [Wako Pure Chemical Industries, Ltd. Reagent] were added to a 3 L four-necked flask. In addition, it was mixed with a solution in which argon gas was bubbled for 30 minutes and reacted at 90 ° C. for 64 hours. According to NMR analysis, the polymerization rate was 91%. After diluting the reaction solution to 200 g with tetrahydrofuran, 2.2 g (17.1 mmol) of a tertiary butyl hydroperoxide 69% aqueous solution [Wako Pure Chemical Industries, Ltd. Reagent] was added and stirred at 50 ° C. for 4 hours. The obtained polymer solution was poured into 5 L of methanol. The precipitated polymer was filtered and dried to obtain 386 g of polyglycidyl methacrylate polystyrene diblock polymer (yield 92%). According to GPC analysis, the molecular weight was 100,400 and PD was 2.21. Furthermore, it was polyglycidyl methacrylate / polystyrene = 5/95 (weight ratio) by NMR analysis. Various physical properties were evaluated by the following methods.

(Production and evaluation of polyphenylene ether resin composition)
PPE, LCP, the compatibilizer A (block polymer) obtained by the above method, and the compatibilizer (SGMA5, SGMA10: both are not block polymers) as a comparative example are mixed in the blending amounts shown in Table 1, A target resin composition pellet was obtained by melt-kneading at a cylinder temperature of 300 ° C. and a rotation speed of 120 rpm using a twin-screw extruder (JSW Nippon Steel Works TEX44).
From the resin composition pellets obtained in Example 1 and Comparative Examples 1 to 4 obtained above, the 85t injection molding machine (J85AD manufactured by Nippon Steel Works) equipped with a test piece preparation mold (mold temperature 100 ° C.) was used. Test pieces were produced by injection and injection molding, and compatibility was evaluated by carrying out various tests. The results are also shown in Table 1.
Various evaluations were performed according to the following methods.
(1) Tensile strength: JIS K7113
(2) Tensile elongation at break; JIS K7113
(3) Bending strength: JIS K7171
(4) Bending fracture strain: JIS K7171
(5) Izod impact strength: JIS 7110, notched

  As can be seen from Table 1, in the resin composition of Example 1, the compatibility of the polyphenylene ether and the liquid crystal polyester is greatly improved by adding the block polymer, and the mechanical properties are excellent. On the other hand, in Comparative Example 1 in which no compatibilizer is added, the mechanical strength and breaking strain are very low. Even in Comparative Example 2 in which SGMA5 having the same glycidyl content as that of the block polymer was added, the compatibilizing effect was not sufficient, and the mechanical properties, particularly bending fracture strain, were inferior. Moreover, Example 1 is the compatibilization effect equivalent to the comparative example 3 which added SGMA10, and it turns out that content of glycidyl methacrylate may be 1/2. That is, the effect as a compatibilizer is high.

Example 2 and Comparative Example 4
Using the resin composition pellets obtained above and various test pieces, the characteristics of the polyphenylene ether-based resin composition were evaluated. Table 2 also shows the results.
Various evaluations were performed as follows.
(1) Specific gravity; measured according to JIS K7112.
(2) Glass transition temperature: A temperature at which a test piece cut out from a dumbbell piece is measured from 30 ° C. at 5 ° C. per minute using TMA (SSII Nanotechnology SS6000), and the expansion coefficient increases remarkably during the temperature rising process. Was obtained from the contact intersection line, and used as the glass transition temperature.
(3) Heat resistance: Measured at a load of 18.6 kg / cm ^{2 in} accordance with JIS K7191.
(4) Flowability: The melt viscosity at 320 ° C. was confirmed using a capillary rheometer (1D manufactured by Toyo Seiki Seisakusho). For low shear, a shear rate of 12 (1 / s) was used, and for high shear, a shear rate of 122 (1 / s) was used.
(5) Linear expansion coefficient: A test piece cut out from a dumbbell piece was heated from 30 ° C. to 190 ° C. at 5 ° C. per minute, and the linear expansion coefficient was measured from the amount of displacement of the length. Anisotropy was calculated by dividing the value in the TD direction by the value in the MD direction.

  As can be seen from Table 2, it can be seen that the resin composition obtained in Example 2 has a low specific gravity, excellent heat resistance, and excellent dimensional stability. Further, in Comparative Example 4 in which SGMA10 having the same compatibilizing effect was added, an increase in melt viscosity was observed, and the fluidity improvement effect of polyphenylene ether, which is the original purpose, was poor.

Example 3 and Comparative Examples 5-7
Using the resin composition pellets obtained above, a film with a thickness of 100 μm was obtained. Film processing was performed by a melt extrusion method using a lab plast mill (manufactured by Toyo Seiki Seisakusho; 4C150 equipped with a single screw extruder D2025). The resin melted at a cylinder temperature of 310 ° C. was extruded from a T-die, cooled and stretched through a cooling roll set at 200 ° C., and then wound up by a take-up machine. Various evaluations were performed as follows.
(1) Electrical characteristics: The dielectric constant and dielectric loss tangent of a frequency of 3 GHz were measured by a cavity resonance method.
(2) Folding resistance: MIT method (manufactured by Toyo Seiki Seisakusho; MIT-DA), a load of 2.45 N, a bending surface R: 0.8 mm, a bending angle: 135 °, a bending speed: 175 times per minute Measured with In addition, the test piece was 15 mm wide × 110 mm long × 100 μm thick, and the film was cut out in the stretching direction and the vertical direction thereof, and measurement was performed.
(3) Stretchability: Using a viscoelasticity measuring device (TA Instruments; RSA3), a tensile test was performed at 210 ° C. and a tensile speed of 3 mm / min.

  As can be seen from Table 3, Example 3 is a film that is excellent in electrical characteristics, particularly low dielectric constant and low dielectric loss tangent, and balanced from the viewpoint of folding resistance and stretchability.

The compatibilizing agent of the present invention can be suitably used to prepare a polymer alloy by blending a polyphenylene ether resin and a liquid crystal polyester, and the obtained polyphenylene ether resin composition can be used for, for example, automobile parts, electric / electronic parts. It is useful for such applications.

Claims (7)

A compatibilizing agent for preparing a polymer alloy by blending a polyphenylene ether-based resin and a liquid crystal polyester, having a segment (A) consisting only of polyglycidyl methacrylate and a segment (B) consisting only of polystyrene, Using a compatibilizer for polymer alloy, which is a block polymer having the characteristics of (A) to (C), the blending ratio of the polyphenylene ether resin and the liquid crystalline polyester is larger than the blending ratio of the liquid crystalline polyester. A polyphenylene ether-based resin composition, which is a polymer alloy obtained by blending.
(A) The weight ratio (A) / (B) of segment (A) to segment (B) is 0.04 to 1.0.
(B) The number average molecular weight of the block polymer is 10,000 to 200,000.
(C) Molecular weight distribution 1.0-2.5. The polyphenylene ether-based resin composition according to claim 1, wherein the block polymer is a polymer obtained by polymerization using an organic tellurium compound-based polymerization initiator. Organic tellurium compound polymerization initiator,
(A) an organic tellurium compound represented by formula (1),
(B) a mixture of an organic tellurium compound represented by formula (1) and an azo polymerization initiator,
(C) A mixture of an organic tellurium compound represented by formula (1) and an organic ditellurium compound represented by formula (2), or (d) an organic tellurium compound represented by formula (1), an azo polymerization initiator. And a polyphenylene ether-based resin composition according to claim 2, which is a mixture of organic ditellurium compounds represented by formula (2).

(In the formula, R ¹ represents a C _{1 to} C ₈ alkyl group, an aryl group, a substituted aryl group or an aromatic heterocyclic group. R ² and R ³ represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. R ⁴ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group, or a cyano group.
(R ¹ Te) ₂ (2)
(In the formula, R ¹ is the same as above.) The compatibilizer is blended within a range of 0.01 to 10 parts by weight with respect to 100 parts by weight of a resin component comprising 60 to 95 parts by weight of a polyphenylene ether resin and 5 to 40 parts by weight of a liquid crystalline polyester. Item 4. The polyphenylene ether-based resin composition according to any one of Items 1 to 3 . The polyphenylene ether resin composition according to any one of claims 1 to 4, wherein the polyphenylene ether resin is an unmodified polyphenylene ether. A method for producing the polyphenylene ether-based resin composition according to any one of claims 1 to 5,
Method for producing a polyphenylene ether-based resin composition characterized by blending a luma masterbatch obtained, and a polyphenylene ether resin by kneading a liquid crystal polyester and the compatibilizing agent. Film obtained from a polyphenylene ether-based resin composition according to any one of claims 1 to 5.