JP2925646B2 - Resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel resin composition having excellent heat resistance, moldability, and solvent resistance.

[Problems to be Solved by Conventional Techniques and Inventions] Polyphenylene ether has excellent mechanical properties, electrical properties, heat resistance, and transparency, but has a high melt viscosity during heating and high moldability. There is a problem that it is difficult.

Polyphenylene sulfide, on the other hand, has excellent mechanical properties, electrical properties, heat resistance, solvent resistance, flame retardancy, etc., but is inferior in extrusion stability and molding stability, and has high rigidity and brittleness. Have a point.

In order to improve the moldability of polyphenylene ether, for example, Japanese Patent Publication No. 56-34032 proposes a blend of polyphenylene ether and polyphenylene sulfide, but the effect of improving the moldability is seen but the mechanical properties are reduced. And the like. Further, in order to solve these problems, Japanese Patent Laid-Open No. 64-31862,
JP-A-64-36645 proposes that polyphenylene ether is modified with an organic compound having an ethylenic double bond and a carboxyl group or an acid anhydride group and blended with polyphenylene sulfide. However, although the mechanical properties are improved, the effect of improving the moldability is not sufficient.

[Means for Solving the Problems] Under such circumstances, the present inventors have developed heat resistance,
As a result of intensive research on resins with excellent moldability, electrical properties, mechanical properties, and solvent resistance, blending polyphenylene ether and polyphenylene sulfide having specific terminal groups with improved heat resistance and fluidity. By
The present inventors have found that a resin composition having excellent mechanical strength and solvent resistance and having excellent heat resistance and molding processability can be obtained, and thus completed the present invention.

That is, the present invention provides (I) a reduced terminal group represented by the following general formula (a):
It contains 0.01 or more on average for 100 phenylene ether units constituting the resin, and the number average molecular weight is 1,000 to 10
Polyphenylene ether resin 1-99 in the range of 0,000
Weight percent, (Wherein, R _{1 to} R ₅ are each independently a hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group or a substituted aryl group, and R _{6 to} R ₉ are each independently a hydrogen, an alkyl group ,
Substituted alkyl group, alkenyl group, substituted alkenyl group, halogen group, aryl group, substituted aryl group, alkoxy group, N-lactam group, carboxylic acid group, carboxylic anhydride group, carboxylic ester group, carboxylic amide group, nitrile Group, acyloxy group or acyl group.

R ₆ and R ₇ , and R ₈ and R ₉ may be independently bonded to each other to form a ring having a spiro ring structure. (II) a resin composition comprising 1 to 99% by weight of polyphenylene sulfide and / or acid-modified polyphenylene sulfide; and polyphenylene obtained by modifying the polyphenylene ether shown in the above (I) with an α, β-unsaturated carboxylic acid or a derivative thereof. 99-1% by weight of ether resin,
(II) A resin composition comprising 1 to 99% by weight of polyphenylene sulfide and / or acid-modified polyphenylene sulfide.

 Hereinafter, the present invention will be described in detail.

The polyphenylene ether resin used in the present invention has a reduced end group represented by the general formula (a) in an average of 0.01 per 100 phenylene ether units constituting the resin.
It is necessary to contain more than one.

In the case of an average molecular weight (about 10,000 to 30,000) for use as an engineering resin, the average number of reduced end groups is preferably 0.15 or more per 100 phenylene ether units. More preferably, the average is 0.2 or more.

This polyphenylene ether resin generally has a repeating unit excluding its terminal group. The phenylene ether unit is defined as containing a phenylene ether unit, and is not particularly limited. A typical example is the following formula (b); (Wherein, R _{1 to} R ₅ are each independently selected from hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group, and a substituted aryl group.)
Consists of seeds.

When the basic skeleton of such a polyphenylene ether resin is produced by oxidative coupling polymerization of phenols which are industrially advantageous, R ₁ is a lower alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl or Feel, naphthyl. And the like, and R _{2 to} R ₅ are preferably hydrogen or a lower alkyl group.

The most preferred combination is when R ₁ is a methyl group or a phenyl group and R _{2 to} R ₅ are hydrogen, when R ₁ and R ₂ are a methyl group and R _{3 to} R ₅ are hydrogen. In particular, it is preferable that R ₁ is a methyl group, R _{2 to} R ₅ are hydrogen, and the phenylene ether unit accounts for 90 to 100% of all units.

The most preferable monomers corresponding to the phenylene ether unit having R _{1 to} R ₅ satisfying these conditions include (i) 2,6 dimethylphenol, (ii) 2-methyl-6-phenylphenol, (iii) 2, 3,6-trimethylphenol and the like. A homopolymer of the monomer (i) or the monomer (ii), or a copolymer of the monomer (i) with the monomer (ii) and / or the monomer (iii) is preferably used as the polyphenylene ether polymer as the resin basic skeleton of the present invention. .

Further, in the polyphenylene ether resin used in the present invention, as long as it does not contradict the purpose of improving thermal stability,
Various other phenylene ether units which have conventionally been proposed to be allowed to exist in the polyphenylene ether resin may be included as a partial structure. An example of a proposal to coexist in a small amount is
2- (dialkylaminomethyl) 6-methylphenylene ether unit and 2- (N-alkyl-N-) described in JP-A-63-12698 and JP-A-63-301222.
(Phenylaminomethyl) 6-methylphenylene ether unit.

In addition, those in which a small amount of diphenoquinone or the like is bonded in the main complex of the polyphenylene ether resin are also included.

The molecular weight of the polyphenylene ether resin used in the present invention is 1,000 to 100,000 in number average molecular weight. The preferred range is about 6,000 to 60,000. In particular, about 10,000 applications are preferred for engineering resin applications.
~ 30,000. The number average molecular weight of the present invention is determined by gel permeation chromatography.
It is a number average molecular weight in terms of polystyrene obtained using a standard polystyrene calibration curve.

In the reduced end group represented by the general formula (a) of the polyphenylene ether resin used in the present invention, R _{1 to} R ₅ each independently represent a hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group or a substituted aryl group. It is.

R _{6 to} R ₉ are each independently hydrogen, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a halogen group, an aryl group, a substituted aryl group, an alkoxy group, an N-
Lactam group, carboxylic acid group, carboxylic anhydride group, carboxylic ester group, carboxylic amide group, nitrile group,
It is an acyl group or an acyloxy group. Note that R ₆ , R ₇ , R ₈ and
R ₉ is each independently a or R ₆ its end is free
R ₇ , R ₈ and R ₉ may be independently bonded to each other to form a ring such as a spirocyclic structure.

In the above definitions of R _{1 to} R ₅ , the alkyl group has 1 to 1 carbon atoms.
20, preferably alkyl having 1 to 10 carbon atoms. Examples of the substituent of the substituted alkyl include a halogen such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group; and a lower alkoxy group. Aryl is aryl having 6 to 20 carbon atoms. Examples of the substituent of the substituted aryl include a lower alkyl group; a halogen group such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group; and a lower alkoxy group.

In R _{6 to} R ₉ , the alkyl group is alkyl having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably lower alkyl. Examples of the substituent of the substituted alkyl include a halogen such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group; and a lower alkoxy group. Alkenyl is preferably lower alkenyl such as ethylenyl and 3-propenyl. Representative examples of substituted alkenyl are 1
-Hydroxy-3propenyl. Aryl is aryl having 6 to 20 carbon atoms. Examples of the substituent of the substituted aryl include a lower alkyl group; a lower alkoxy group; a halogen group such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group; and an aminoalkyl group such as a lower alkoxy group.

The aryl group has a broad meaning of an aromatic radical, and includes a heteroaromatic group such as a pyridyl group and a soriadyl group in addition to aryl in a narrow sense. A typical example of N-lactam is N-2
-Pyrrolidonyl, N-ε-cabrolactamoyl and the like. Representative examples of carboxylic acid amides include carbamoyl, phenylcarbamoyl, seryl, and the like.
Preferred examples of the carboxylic anhydride are acetoxycarbonyl and benzoyloxycarbonyl. Representative examples of carboxylic esters include methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, and the like. Representative examples of the acyl group include acetyl and benzoyl, and preferred examples of acyloxy include acetoxy and benzoyloxy.

As for R _{6 to} R ₉ , it is preferable from the viewpoint of stability that two to three, particularly three of them are hydrogen. In this case, the other group is preferably selected from an aryl group, a substituted aryl group, a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid amide group, a nitrile group, and an N-lactam group. In particular, the case where at least one of R ₈ and R ₉ is an aryl group or a substituted aryl group is preferable from the viewpoint of stability against thermal oxidative deterioration and the production method described later.

Representative examples of aryl or substituted aryl groups in the definitions of R _{6 to} R ₉ include phenyl, tolyl, chlorophenyl, naphthyl, 4-pyridyl, 3,5-diamino- (s)
-A triazyl group or the like.

The structure and binding amount of such reduced terminal groups can be measured by using a nuclear magnetic resonance spectrum. Since the polyphenylene ether resin having a reduced terminal group represented by the general formula (a) has the reduced terminal group, when it is melted (molded), a transition structure represented by the following general formula (e) is generated. It has excellent properties that it is significantly less than polyphenylene ether resin and hardly changes in molecular weight.

(In the formula, R _{1 to} R ₅ are each independently a hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group or a substituted aryl group.) The polyphenylene ether resin used in the present invention is as follows. Can be manufactured.

That is, general formula (c); (Wherein, R _{1 to} R ₅ are the same as defined in the formula (a), and R ₁₀ and R ₁₁ each independently represent hydrogen, an alkyl group, or a substituted alkyl group. The polyphenylene ether-based polymer having a terminal group represented by the following general formula (d): (Wherein, R _{6 to} R ₉ are the same as those defined in the formula (a).) A compound having a carbon-carbon double bond (hereinafter referred to as an unsaturated compound) represented by the following formula: It can be produced by heating to a temperature not lower than the glass transition temperature of the polyphenylene ether-based polymer in the absence.

The alkyl group and substituted alkyl group in R ₁₀ and R ₁₁ in the formula (c) are preferably (C ₁ -C ₂₀ ) alkyl group, (C ₁
-C ₂₀₎ hydroxyl group, (C ₂ ~C ₂₂₎ alkoxyalkyl group, (C ₃ ~C ₂₂₎ acyloxyalkyl group or a (C ₄ ~
C ₂₀ ) is a polyalkylene ether group.

The polyphenylene ether having such a terminal group (c) can be obtained by oxidative coupling polymerization of a phenol compound having at least one benzylic hydrogen at the ortho position of hydroxylation in the presence of a catalyst containing a primary or secondary amine, or It can be obtained by copolymerization (for example, US Pat. No. 4,788,277).

In this case, the obtained polymer is obtained as a mixture of a polyphenylene ether having a terminal group represented by the general formula (c) and a polyphenylene ether having a terminal structure in which a primary or secondary amine is not bonded at a benzyl position. However, in the present invention, it can be used without separation. The use ratio of the former and the latter is not particularly limited, but is preferably 0.4 or more, particularly preferably 0.9 or more, as expressed by the ratio of the number of terminal groups of the former / the number of terminal groups of the latter.

The amount of the reaction between the polyphenylene ether having a terminal group represented by the general formula (c) and the unsaturated compound represented by the general formula (d) in the present invention is preferably represented by the general formula (c) The unsaturated compound of the general formula (d) may be used in an amount of about 2 to 50 equivalents to the polyphenylene ether having a terminal group.

Specific examples of the unsaturated compound (d) for producing the polyphenylene ether resin used in the present invention include styrene, α-methylstyrene, chlorostyrene, methylstyrene, stilbene, cinnamic alcohol, benzalacetone, cinnamic acid Ethyl, cinnamate nitrile, 4-vinylpyridine, 2-vinyl-3,5-diamino (s) -triazine and the like can be mentioned.

As the unsaturated compound (d), a compound containing no aromatic compound can be used. Specific examples of such unsaturated compounds (d) include acrylic acid; methyl, ethyl, propyl, butyl, isobutyl, t-butyl,
-Ethylhexyl, octyl, isodecyl, lauryl,
Acrylic esters such as lauryl-tridecyl, tridecyl, cetyl-stearyl, stearyl, cyclohexyl, benzyl ester; acrylamide, acrylonitrile, methacrylic acid; methyl, ethyl, propyl, butyl, isobutyl, t-butyl, 2-methacrylic acid
Ethylhexyl, octyl, isodecyl, lauryl, lauryl-tridecyl, tridecyl, cetyl-stearyl, stearyl, cyclohexyl, methacrylic acid esters such as benzyl ester; methacrylamide, methacrylonitrile, itaconic acid; dimethyl, diethyl, dibutyl itaconic acid, Di-2-ethylhexyl, dinolyl,
Itaconic acid diesters such as dioctyl ester; itaconic acid monomethyl, monoethyl, monobutyl, mono2
Monoesters of itaconic acid such as ethylhexyl, mononolyl, monooctyl ester; itaconic anhydride N
N-vinyl compounds such as -vinylpyrrolidone; vinyl ethers such as butyl vinyl ether;

In producing the polyphenylene ether resin used in the present invention, the unsaturated compound (d) is heated before the polyphenylene ether-based polymer having a terminal group represented by the general formula (c) is heated to a glass transition temperature of 180 ° C. or higher. It is preferable to mechanically mix it with.

The method of mixing is not particularly limited, but a method of dry blending with a Henschel mixer or the like, a method of drying after melt blending, a method of dissolving unsaturated compound (d) in polyphenylene ether but dissolving unsaturated compound (d), for example, After dissolving in a solvent such as methanol or pentane and impregnating the polyphenylene ether-based polymer having a terminal group (c) in the form of powder, a method of drying and removing the solvent may be used.

The polyphenylene ether-based polymer and the unsaturated compound (d) mechanically mixed as described above are then mixed with the glass transition temperature of the polyphenylene ether-based polymer (about 208
℃) or more. A preferred temperature range is 20-150 ° C above the glass transition temperature, more preferably 5 ° C.
0-120 ° C. The heating time cannot be unconditionally determined in relation to the temperature, but the heating may be carried out for a time sufficient to complete the desired reaction. Generally, it is about 1 minute to 1 hour, preferably about several minutes. There is no point in making it too long.

Since the reaction for forming the reduced end group represented by the general formula (a) is usually sufficiently fast at a temperature equal to or higher than the glass transition temperature, it is better not to apply unnecessary heat excessively. Further, as described above, the heating needs to be performed in the absence of the radical polymerization initiator. The reaction atmosphere is preferably a nitrogen gas atmosphere or the like.

The modified polyphenylene ether resin used in the present invention is obtained by melting the above-mentioned polyphenylene ether having a specific terminal group and an α, β-unsaturated carboxylic acid or a derivative thereof in the presence or absence of a radical generator. It is obtained by reacting in a state, a dissolved state, and a slurry state. Examples of α, β-unsaturated carboxylic acids or derivatives thereof include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride and the like.

The method for producing such a modified polyphenylene ether resin can be carried out in any of a known molten state and a solution mixed state, and is not particularly limited.For example, when the method is carried out in a molten state, the specific terminal group described above is used. When producing the polyphenylene ether having the same, it can be carried out by a method of blending and extruding and granulating simultaneously or after the production.

The polyphenylene sulfide used in the present invention has a bonding unit: Is a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the formula, and a copolymer containing a repeating unit having the following structure in a range of 30 mol% or less of the repeating unit. is there.

(R represents an alkyl group, a nitro group, a phenyl group, or an alkoxy group.) As a method for producing the above-mentioned polyphenylene sulfide, sulfurization in an amide-based solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone-based solvent such as sulfolane is used. A method of reacting sodium with p-dichlorobenzene is suitable, but is not particularly limited as long as it can be obtained by a known method.

The structure of the polyphenylene sulfide used in the present invention may be linear or branched, or may be a mixture of these structures.

The acid-modified polyphenylene sulfide used in the present invention is obtained by modifying the above-mentioned polyphenylene sulfide with an acid compound. Examples of the acid compound include acrylic acid, methacrylic acid, maleic acid,
Unsaturated carboxylic acids represented by fumaric acid, maleic anhydride and the like, and anhydrides thereof are exemplified. In addition, saturated aliphatic carboxylic acids, aromatic-substituted carboxylic acids and the like can also be mentioned. In addition, inorganic acid compounds represented by hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid and the like can also be mentioned.
The method of acid modification is a polyphenylene sulfide in a molten or non-molten state, in which 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, more preferably 0.5 to 5 parts by weight of an acid compound is mixed with 100 parts by weight of polyphenylene sulfide However, when denatured in a non-molten state, the modification may be performed in the presence of water, a solvent, or the like.

The blending ratio of the polyphenylene ether resin or the modified polyphenylene ether resin of the present invention and polyphenylene sulfide and / or acid-modified polyphenylene sulfide is preferably 1 to 99% by weight / 99 to 1% by weight. Preferably it is 20 to 80% by weight / 80 to 20% by weight.

Such a composition ratio can be attained simultaneously with the production of the stabilized polyphenylene ether resin containing reduced end groups, or by a method of blending and extruding and granulating after the production.

A vinyl aromatic resin may be added to this composition as long as the characteristics are not impaired.

Examples of the vinyl aromatic resin include a homopolymer of styrene and a copolymer with another ethylenically unsaturated monomer as long as the compatibility of the composition is not impaired.

Examples of specific comonomers include α-methylstyrene, acrylonitrile, methacrylonitrile, acrylates, methacrylates, maleic anhydride, N-alkylmaleimides, N-arylmaleimides, vinyloxazoline and the like. is there.

In addition to the above, the resin composition of the present invention can be used by appropriately adding an inorganic filler such as glass fiber, various stabilizers, a plasticizer, a flame retardant, a pigment, and the like according to a known method.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

 In addition, each measurement was performed as follows.

¹ H-nuclear magnetic resonance spectrum Measured by CDX ₃ as a solvent with GX-270 manufactured by JEOL Ltd., and tetramethylsilane is used as a reference.

Free phenolic OH group in the polymer Measured according to a method such as EHUD SHCHORI [described in Journal of Applied Polymers Science; Applied Polymer Symposium, pages 34, 103 to 117 (1978)].

 Tensile strength Measured according to ASTM D-638.

Heat denaturation temperature Measured at a weight of 18.6 kg / cm ² according to ASTM D-648.

Solvent resistance A 1/8 inch thick injection molded dumbbell specimen was immersed in cyclohexane for 60 minutes at room temperature, and the presence or absence of cracks was observed.

Example 1 The raw material polyphenylene ether was prepared according to US Pat. No. 4,788,
According to the method described in Japanese Patent Application No. 277 (Japanese Patent Application No. 62-77570), 2,6-xylenol is produced by oxidative coupling polymerization in the presence of dibutylamine.

The resulting polyphenylene ether viscosity is 0.545 and the glass transition temperature is about 208 ° C. As a result of analysis by ¹ H-nuclear magnetic resonance spectrum, formula (i) was obtained; It was confirmed that there were 0.32 terminal groups per 100 of the following main repeating units (h).

It is also confirmed that the amount of free phenolic hydroxyl groups is 0.34 per 100 main repeating units (h).

After adding 10 parts by weight of styrene to 100 parts by weight of this polyphenylene ether and uniformly blending with a Henschel mixer, a twin-screw extruder having a screw diameter of 30 mmφ (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) The mixture was melt-kneaded at 300 ° C. and pelletized through a water tank.

As a result of ¹ H-nuclear magnetic resonance spectrum analysis of the pellet thus obtained, the following formula (s) was obtained; Is the main repeating unit (h) per 100
The presence of 0.25 is confirmed from the signal area value of 5.02 ppm.

It was also confirmed that the amount of free phenolic hydroxyl groups was 0.45 per 100 main repeating units (h). The number average molecular weight determined by GPC was 24,500, and the viscosity was 0.547.

After 40 parts by weight of the thus obtained pellets and 60 parts by weight of polyphenylene sulfide [T-4, manufactured by Topren Co., Ltd.] were uniformly blended with a Henschel mixer, the mixture was again placed in a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works). Melt and knead at 300 ° C,
Pelletize through water bath. The pellet was molded at 310 ° C. using an injection molding machine (IS80EPN, manufactured by Toshiba Machine Co., Ltd.) to prepare a test piece. Using this test piece, tensile strength, heat deformation temperature, and solvent resistance were evaluated. In addition, 1 g of the obtained pellet was subjected to Soxhlet extraction with chloroform for 8 hours, and the ratio of the extraction residue was determined. Table 1 shows the results.

Example 2 After adding 4 parts by weight of styrene to 40 parts by weight of the polyphenylene ether resin used in Example 1 and 60 parts by weight of polyphenylene sulfide (manufactured by Topren Co., Ltd., T-4), the mixture was uniformly blended with a Henschel mixer. In a 30 mmφ twin-screw extruder [PCM-30, manufactured by Ikegai Iron Works Co., Ltd.], the mixture was melt-kneaded at 300 ° C. and pelletized through a water tank.

These pellets were injected into an injection molding machine [Toshiba Machine Co., Ltd., IS80
EPN] was molded under the condition of 310 ° C.] to prepare a test piece, which was evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 A test piece was prepared and evaluated in the same manner as in Example 2 except that styrene was not used. Table 1 shows the results.

Example 3 10 parts by weight of styrene was added to 100 parts by weight of the polyphenylene ether used in Example 1, and the mixture was uniformly blended with a Henschel mixer. ] Melted and kneaded at 300 ° C in medium and pelletized through a water tank to 100 parts by weight of maleic anhydride 1.5
Parts by weight were added and pelletized through a twin screw extruder. A composition was prepared from 40 parts by weight of the obtained pellets and 60 parts by weight of polyphenylene sulfide (manufactured by Toprene, T-4) in the same manner as in Example 1, and evaluated. Table 2 shows the results.

[Effects of the Invention] The present invention is a resin composition that retains excellent mechanical strength and solvent resistance, and has moldability and heat resistance.

Claims (2)

(57) [Claims] (I) An average of 0.01 or more reduced terminal groups represented by the following general formula (a) based on 100 phenylene ether units constituting a resin, and having a number average molecular weight of 1,000 99-1% by weight of a polyphenylene ether resin in the range of ~ 100,000; (Wherein, R _{1 to} R ₅ are each independently a hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group or a substituted aryl group, and R _{6 to} R ₉ are each independently a hydrogen, an alkyl group ,
Substituted alkyl group, alkenyl group, substituted alkenyl group, halogen group, aryl group, substituted aryl group, alkoxy group, N-lactam group, carboxylic acid group, carboxylic anhydride group, carboxylic ester group, carboxylic amide group, nitrile Group, acyloxy group or acyl group. R ₆ and R ₇ , and R ₈ and R ₉ may be independently bonded to each other to form a ring having a spiro ring structure. (II) A resin composition comprising 1 to 99% by weight of polyphenylene sulfide and / or acid-modified polyphenylene sulfide. (I) 99-1% by weight of a modified polyphenylene ether resin obtained by modifying the polyphenylene ether resin according to claim 1 with an α, β-unsaturated carboxylic acid or a derivative thereof; A resin composition comprising 1 to 99% by weight of phenylene sulfide and / or acid-modified polyphenylene sulfide.