JPH05105809A - Production of polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a molding improved in appearance and dimensional stability without detriment to its low-temperature resistance. CONSTITUTION:The title process comprises subjecting 100wt.% total of 56-99wt.% polyphenylene ether (a), 0.1-4.9wt.% polyamide (b), 0.1-40wt.% impact modifier (c) and 0.01-10wt.% compound (d) containing an unsaturated group and a polar group in the molecule to primary melt kneading to obtain an intermediate composition (A) containing below 100ppm of unreacted component (d), and subjecting 5-94wt.% component (A) and 6-95wt.% polyamide (B) to secondary melt kneading.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyphenylene ether resin composition having excellent appearance, dimensional stability and impact resistance of molded products.

[0002]

2. Description of the Related Art Polyphenylene ether has been attracting attention as a useful engineering plastic having excellent mechanical properties and heat resistance, and is used as a blend with a styrene resin, but its solvent resistance is extremely poor,
In order to improve this point, a blend with polyamide (Japanese Patent Publication No. 59-41663 etc.) or a blend with polyester (Japanese Patent Publication No. 51-21662 etc.) and the like have been proposed.

Further, in order to improve the impact strength of these blended resins, a combination of polyphenylene ether and polyamide, a compound containing a polar group such as a carboxyl group, an imide group or an epoxy group, and a rubber material as an impact resistance improving material. A composition to which is added (JP-A-56-49753) is proposed.

Further, since such a polyphenylene ether resin composition is being used as an outer panel material for automobiles, it is required to further improve the balance between low temperature impact resistance and rigidity, and therefore, a modified polyphenylene ether intermediate is required. A composition comprising a polyamide and an impact resistance improving material (JP-A-1-19664) has been proposed.

[0005]

A polyphenylene ether resin composition having such excellent properties as heat resistance, low temperature impact resistance, solvent resistance, and dimensional stability is used as an automobile outer panel material, for example, a fender, When used for door panels, etc., large products are molded at high temperatures, so defective molded products due to poor thermal stability such as burns and silver streaks occur on the surface of molded products, and dimensional stability is unsatisfactory. Was often there.

Therefore, the present invention improves the drawbacks of the above resin composition, does not impair low temperature impact resistance, and does not cause burns or silver streaks during high temperature molding. An object is to provide a polyphenylene ether resin composition having excellent stability.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the inventors of the present invention have found that polyphenylene ether, polyamide, an impact resistance improver and an unsaturated group and a polar group in the same molecule. A compound having a group is melt-kneaded in advance to form an intermediate composition in which an unreacted compound having an unsaturated group and a polar group in the same molecule is less than 100 ppm, and then a polyamide is added to this. It was found that the resin composition produced in this way is a resin composition which does not cause the appearance defects such as discoloration and silver streak at the time of high temperature molding, and has excellent physical property balance of low temperature impact resistance and rigidity and dimensional stability. The present invention has been reached.

That is, according to the present invention, (a) polyphenylene ether 56 to 99% by weight (b) based on the total amount of components (a), (b), (c) and (d) having the following composition. Polyamide 0.1-4.9 wt% (c) Impact resistance improver 0.1-40 wt% (d) Compound having both unsaturated group and polar group in the same molecule 0.01-10 wt% The first melt-kneading was carried out to obtain 100 parts of unreacted residual component (d)
to obtain an intermediate composition (A) whose content is less than ppm,

Next, based on the total amount of the intermediate composition (A) and the following polyamide (B), the intermediate compositions (A) 5 to 94 are used.
In the method for producing a polyphenylene ether resin composition, the second melt-kneading is performed in an amount of 2% by weight and 6 to 95% by weight of the polyamide (B). In particular, as the polyamide (B), an amorphous or low crystalline cyclic hydrocarbon-based copolyamide (B-1) having a glass transition temperature of 90 to 250 ° C.
And a crystalline polyamide (B-2) are used together.

The present invention will be described in detail below.

<Polyphenylene ether (a)> The polyphenylene ether (a) used in the present invention has the following formula (I):

[0012]

[Chemical 1]

## STR1 ## wherein n is at least 50 and R ¹ , R ² , R ³ and R ⁴ do not contain a hydrogen atom, a halogen atom or a tertiary α-carbon atom, respectively. Hydrocarbon group, halohydrocarbon group in which halogen atom is substituted through at least 2 carbon atoms, hydrocarbon oxy group, and halohydrocarbon oxy group in which halogen atom is substituted through at least 2 carbon atoms More selected 1
Represents a valent substituent.

Examples of the hydrocarbon group containing no third α-carbon atom include lower alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl; alkenyl groups such as vinyl, allyl, butenyl and cyclobutenyl; phenyl, Examples thereof include aryl groups such as tolyl, xylenyl and 2,4,6-trimethylphenyl; and aralkyl groups such as benzyl, phenylethyl and phenylpropyl.

Examples of the halohydrocarbon group in which a halogen atom is substituted via at least two carbon atoms include, for example, 2
-Chloroethyl, 2-bromoethyl, 2-fluoroethyl, 2,2-dichloroethyl, 2- or 3-bromopropyl, 2,2-difluoro-3-iodopropyl,
2-, 3-, 4- or 5-fluoroamyl, 2-chlorovinyl, chloroethylphenyl, ethylchlorophenyl, fluoroxylyl, chloronaphthyl, bromobenzyl and the like can be mentioned.

Examples of the hydrocarbon oxy group include methoxy, ethoxy, propoxy, butoxy, phenoxy, ethylphenoxy, naphthoxy, methylnaphthoxy, benzyloxy, phenylethoxy, tolylethoxy and the like.

Examples of the halohydrocarbonoxy group in which a halogen atom is substituted through at least two carbon atoms include, for example, 2-chloroethoxy, 2-bromoethoxy, 2-fluoroethoxy, 2,2-dibromoethoxy, 2 -Or 3-bromopropoxy, chloroethylphenoxy,
Examples thereof include ethylchlorophenoxy, iodooxyloxy, chloronaphthoxy, bromobenzyloxy, chlorotolylethoxy and the like.

The polyphenylene ether used in the present invention includes a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and 2,3,5,6-tetramethylphenol. And a copolymer such as a copolymer of 2,6-diethylphenol and 2,3,6-trimethylphenol. Also,
A modified polyphenylene ether such as one obtained by graft-polymerizing a styrene-based monomer (for example, styrene, p-methylstyrene, α-methylstyrene, etc.) to the polyphenylene ether of the formula (I) may be used.

A method for producing a polyphenylene ether corresponding to the above is known, for example, US Pat. No. 33068.
74, No. 3306875, No. 3257357 and No. 3257358, and Japanese Patent Publication No. 52-
No. 17880 and JP-A No. 50-51197.

The preferred polyphenylene ether is a homopolymer having an alkyl substituent at two ortho positions with respect to the ether oxygen atom bonding position or a copolymer of 2,6-dialkylphenol and 2,3,6-trialkylphenol. .. The polyphenylene ether preferably has an intrinsic viscosity of 0.25 to 0.70 dl / g (measured in chloroform at 30 ° C). Intrinsic viscosity is 0.25dl
If it is less than / g, the impact strength and heat resistance are unfavorable.
If it exceeds 0.70 dl / g, the molding process becomes difficult. Further, in order to improve the molding processability of the resin, a high viscosity polyphenylene ether and a low viscosity polyphenylene ether may be used in combination.

<Polyamide (b)> The polyamide (b) used in the present invention has a —CONH— bond in the polymer main chain and can be heated and melted. Typical examples are nylon-4, nylon-6, nylon-6, and
6, nylon-4,6, nylon-12, nylon-
6,10, and other crystalline or amorphous polyamides containing known aromatic diamine, aromatic dicarboxylic acid and other monomer components can also be used. Here, the amorphous polyamide means that the heat of fusion measured by a differential scanning calorimeter (DSC) does not exceed 1 cal / g.

The preferred polyamide is crystalline nylon-
6,6, nylon-6 or amorphous polyamide, and among them, amorphous polyamide is particularly preferable. Polyamide is
Those having a relative viscosity of 2.0 to 8.0 (measured in 25%, 98% concentrated sulfuric acid) are preferable.

<Impact resistance improver (c)> The impact resistance improver (c) used in the present invention is a rubber substance for the purpose of improving impact resistance, and is, for example, an alkenyl aromatic compound-conjugated diene. Examples thereof include elastomers such as copolymers and polyolefin-based copolymers.

Further, maleic acid, maleic acid monomethyl ester, maleic anhydride,
Α, β-unsaturated dicarboxylic acids such as itaconic acid, itaconic acid monomethyl ester, itaconic anhydride and fumaric acid,
Or endo-bicyclo [2.2.1] -5-heptene-
An alicyclic carboxylic acid such as a 2,3-carboxylic acid or a derivative thereof may be graft-polymerized by using peroxide, ionizing radiation, ultraviolet ray or the like.

If the tensile modulus of elasticity of these elastomers is too high, it becomes insufficient as an impact resistance improver. Therefore, the tensile modulus of elasticity of the elastomer is 5,000 kg / cm ² (ASTM).
D882 or less is preferable.

<Compound (d) Having Unsaturated Group and Polar Group in Same Molecule> The compound (d) having both unsaturated group and polar group in the same molecule used in the present invention is an unsaturated group, ie, A carbon-carbon double bond or a carbon-carbon triple bond,
It is a compound having a polar group, that is, an amide bond contained in a polyamide or a carboxyl group or an amino group existing at a chain end and a functional group showing affinity or chemical reactivity in the same molecule. Examples of such functional groups include carboxyl groups of carboxylic acids, groups derived from carboxylic acids, that is, various salts in which a hydrogen atom or a hydroxyl group of a carboxyl group is substituted, esters, acid amides, acid anhydrides, imides, acids. Examples thereof include azide, acid halide, oxazoline, nitrile, epoxy group, amino group, hydroxyl group and isocyanic acid ester.

Examples of the compound (d) having both an unsaturated group and a polar group in the same molecule include unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, unsaturated epoxy compounds, unsaturated alcohols, unsaturated amines and unsaturated isocyanic acid. Esters and the like are mainly used.

Specifically, maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide,
A reaction product of maleic anhydride and a diamine, for example, one having a structure represented by the following formulas (II) and (III),

[0029]

[Chemical 2]

[0030]

[Chemical 3]

(Wherein R represents an aliphatic group or an aromatic group) methyl nadic acid anhydride, dichloromaleic anhydride,
Unsaturated dicarboxylic acids or their derivatives such as maleic acid amide, itaconic acid, itaconic anhydride; soybean oil, cutting oil,
Natural oils and fats such as castor oil, linseed oil, hemp oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil and sardine oil; epoxidized natural oils and fats such as epoxidized soybean oil;

Acrylic acid, butenoic acid, crotonic acid, vinylacetic acid, methacrylic acid, pentenoic acid, angelic acid, tibric acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4 -Pentenoic acid, 2-hexenoic acid, 2-methyl-2-pentenoic acid, 3
-Methyl-2-pentenoic acid, α-ethyl crotonic acid,
2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2
-Octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10
-Undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4
-Tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid,
Mycolic acid,

2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid, geranium acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12- Octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid,
Eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenoic acid, traacontene Unsaturated carboxylic acids such as acids; or esters, acid amides, acid anhydrides of these unsaturated carboxylic acids;

Alternatively, allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methyl propenyl carbinol, 4-pentene-1.
-Ol, 10-undecen-1-ol, propargyl alcohol, 1,4-pentadiene-3-ol,
1,4-hexadiene-3-ol, 3,5-hexadiene-2-ol, _{2,4-hexadiene-1-ol, C n H 2n-5 OH} , C n H 2n-7 OH, C n H 2n _-9 OH
(However, n is a positive integer), 3-,
Butene-1,2-diol, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-
Unsaturated alcohols such as 3,4-diol and 2,6-octadiene-4,5-diol;

Alternatively, the O of such unsaturated alcohol
Unsaturated amine in which H group is replaced by NH ₂ group; or low polymer such as butadiene and isoprene (for example, one having an average molecular weight of about 500 to 10,000); or high molecular weight substance (for example, an average molecular weight of 10, 000 or more) to which maleic anhydride, phenols are added, or an amino group, a carboxyl group, a hydroxyl group, an epoxy group or the like is introduced; or allyl isocyanate.

The compound (d) having both an unsaturated group and a polar group in the same molecule is defined as having two or more unsaturated groups,
It goes without saying that a compound containing two or more (same or different) polar groups is also included, and as the component (d), 2
It is also possible to use more than one compound. Of these, more preferred are maleic anhydride, maleic acid, itaconic anhydride, unsaturated dicarboxylic acids such as itaconic acid and anhydrides thereof, unsaturated alcohols such as oleyl alcohol, and epoxidized natural oils and fats. Are maleic anhydride, maleic acid, oleyl alcohol, epoxidized soybean oil and epoxidized linseed oil, particularly preferably maleic anhydride and a mixture of maleic anhydride and maleic acid.

<Intermediate composition (A)> The above component (a),
(B), (c) and (d) are mixed in the following proportions to form the intermediate composition (A).

That is, the blending ratio of each component is such that the component (a) is 56 to 99% by weight, preferably 60 to 95, relative to the total amount of the components (a), (b), (c) and (d). %, Particularly preferably 62 to 80% by weight. If the component (a) is less than the above range, the heat resistance of the final composition is unsatisfactory, and if it exceeds the above range, the low temperature impact strength of the final composition is unsatisfactory. Become. The component (b) is 0.1 to 4.9% by weight, preferably 0.5 to 4.0% by weight, particularly preferably 1.0 to 4.0% by weight, and the component (b) is in the above blending range. Outside, the low temperature impact strength of the final composition is unsatisfactory.

Component (c) is 0.1-40% by weight, preferably 5-38% by weight, particularly preferably 15-35% by weight.
When component (c) is less than the above range, the low temperature impact strength of the final composition becomes unsatisfactory, and when it exceeds the above range, the heat resistance rigidity of the final composition becomes unsatisfactory. The component (d) is 0.
It is from 0 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.2 to 2% by weight. If the component (d) is less than the above range, the low temperature impact strength of the final composition will be insufficient,
If the content exceeds the above range, the molded product of the final composition at the time of high-temperature molding may suffer from burns and silver streaks, which causes a problem in appearance.

When the unmelted residual component (d) is present in an amount of 100 ppm or more in the intermediate composition (A) formed by first melt-kneading the components (a) to (d), the burned silver streak is formed during high temperature molding. This is not preferable because of poor appearance such as. In order to suppress the occurrence of appearance defects, the amount of unreacted residual component (d) is less than 100 ppm, preferably 80 ppm or less, and particularly preferably 50 ppm or less.

In the intermediate composition (A), in addition to the above essential components (a), (b), (c) and (d), various stabilizers, fluidity modifiers and impact resistance improving fillers ( For example, 1μ
Any optional component such as m or less granular inorganic filler, heat-resistant and rigidity-improving filler (for example, needle-like or fibrous filler having an aspect ratio of 5 or more) can be added within a range that does not significantly impair the effects of the present invention.

In the primary melt kneading of the intermediate composition (A), first, all the respective components are mixed by a Henschel mixer, a super mixer, a ribbon blender, a V type blender, etc., and then this mixture is uniaxially extruder, Using an ordinary kneader such as a twin-screw extruder, Banbury mixer, roll, Brabender plastograph, and kneader, the mixture is melt-kneaded and the unreacted residual component (d) is adjusted to less than 100 ppm.

In order to reduce the residual amount of the component (d), the primary melt-kneaded product is put in a paper bag or the like and stored for a long period of time, or a uniaxial or biaxial with a vent of L / D = 10 to 30 is used. To produce an intermediate composition (A) having an unreacted residual component (d) of less than 100 ppm by vacuum degassing from a vent degassing port downstream of the extruder while melt-kneading using a die extruder. You can

When vacuum degassing is performed using the vent degassing port, the vent degassing vacuum degree is 260 to 0 Torr in order to efficiently remove the unreacted residual component (d) from the molten resin.
Is preferred. Here, the vent degassing vacuum degree specifically represents the pressure of the residual gas in the extruder. The melt-kneading temperature at this time is usually in the range of 200 to 350 ° C.

The unmelted residual component (d) of the primary melt-kneaded, pelletized or powdered product can be adjusted to less than 100 ppm by the following method. (1) Drying under reduced pressure Heat the above pellets or powder into a reduced pressure heating dryer,
Vacuum degree of 0.1 to 10 Torr, temperature of 120 to 16
Dry under conditions of 0 ° C. for 3 to 30 hours. (2) Solvent Washing The above pellets or powders are placed in a pressure-resistant autoclave equipped with a stirrer, an organic solvent, preferably chloroform, is added and the temperature is raised to 60 ° C. with stirring to dissolve uniformly. After this solution is washed with water, it is separated with a separatory funnel, and chloroform in the obtained organic phase is distilled off by steam stripping to obtain an aqueous dispersion slurry. The slurry is dehydrated using a centrifuge, and the solid content is put into a drier and dried at 100 ° C. overnight.

The intermediate composition (A) can be used in the final resin composition in the molten state or pelletized form, or by crushing it into powder and drying it.

<Polyamide (B)> As the polyamide (B) in the second melt-kneading step, the polyamide mentioned as the component (b) in the intermediate composition (A) can be used, but it is amorphous. It is preferable to use the low crystalline cyclic hydrocarbon-based copolyamide (B-1) and the crystalline polyamide (B-2) together from the viewpoints of impact resistance, smoothness of the surface of a molded article, appearance gloss and the like. .. Each will be described below.

(B-1) Amorphous or low crystalline cyclic hydrocarbon-based copolyamide: The present copolyamide is
It has a -CONH- bond in the polymer chain, is amorphous or has low crystallinity, and has a glass transition temperature of 90 to 250 ° C.
And more preferably 90 to 210 ° C., further preferably 100 to 180 ° C., and particularly preferably 110 to 1
It is in the range of 50 ° C. Amorphous and low crystallinity generally mean having no clear melting point or measurable heat of fusion, but in the present invention, those which show some crystallinity when slowly cooled include It may include those exhibiting crystallinity within a range that does not significantly impair the effects of the invention. The glass transition temperature, the melting point and the heat of fusion can be measured using the differential scanning calorimeter described in <Polyamide (b)>.

An example of this is PERKIN-ELMER
There is DSC-II manufactured by the company. Using this device, the heat of fusion heats the sample at a temperature above the expected melting point at a rate of 10 ° C per minute, then the sample is heated to 10 ° C per minute.
The temperature is lowered at a rate of 30 ° C., the temperature is cooled to 30 ° C., the temperature is left for about 1 minute, and then the temperature is raised again at a rate of 10 ° C. per minute. As the heat of fusion, the one that the value measured in the cycle of temperature increase and temperature decrease becomes constant within the experimental error range is adopted. The amorphous or low crystalline polyamide in the present invention is defined as one having a heat of fusion of less than 1 cal / g measured by the above method. According to this method, the heat of fusion of commercial nylon-6 is about 16 cal / g.

The cyclic hydrocarbon-based copolyamide is composed mainly of amide bond constitutional units selected from the structural formulas (IV) to (IX) below, and has the above-mentioned glass transition temperature and amorphous or low crystallinity. It satisfies the crystallinity.

(I) Formula (IV) --HN--W--NH-- (IV) (wherein, W is a divalent group selected from linear or branched aliphatic groups having 2 to 12 carbon atoms)

(Ii) Formula (V) --HN--X--NH-- (V) (wherein X is a metaxylylene group or an aliphatic group containing at least one alicyclic hydrocarbon skeleton having 5 to 22 carbon atoms) Divalent group selected)

(Iii) Formula (VI)

[Chemical 4] (In the formula, each R is a hydrogen atom or a monovalent group selected from aliphatic groups having 1 to 6 carbon atoms, and each R may be the same or different.)

(Iv) Formula (VII)

[Chemical 5] (In the formula, R has the same meaning as defined in formula (VI))

(V) Formula (VIII) --CO--Y--CO-- (VIII) (wherein Y is selected from an aliphatic group having 2 to 22 carbon atoms or an aliphatic group containing an alicyclic hydrocarbon group). Divalent group)

(Vi) Formula (IX) —CO—Z—NH— (IX) (wherein Z is a divalent group selected from an aliphatic group having 4 to 14 carbon atoms or an aromatic group).

The relative viscosity of this polymer (in 98% concentrated sulfuric acid,
(Concentration 1 dl / g, measurement temperature 25 ° C) is preferably 1.0 to
The range is 5.0, more preferably 1.4 to 3.5, and even more preferably 1.6 to 3.0.

Methods for producing these amorphous polyamides are known, for example, JP-A-58-38751 and JP-A-60-21.
Those described in Japanese Patent Nos. 7237 and 60-219227 are applicable.

Specific examples of W in the structural unit (IV) include butylene, hexylene, octylene, decanylene,
Examples include alkylene groups such as 2,2,4- or 2,4,4-trimethylhexylene, 3-methylhexylene, and pentylene, and more preferably butylene group, hexylene group, or 2,4,4-trimethylhexylene. It is a base.

Specific examples of X in the structural unit (V) include metaxylylene (Xa), 4,4'-methylenedicyclohexane-1,1'-diyl (Xb) and 2,2'-.
Dimethyl-4,4'-methylenedicyclohexane-1,
1'-diyl (Xc), 1,5,5-trimethyl-1,
3-cyclohexylene-1-methylene (Xd), cyclohexylene-1,4-dimethylene (Xe), 4-methylenecyclohexylene (Xf), 3-methylenecyclohexylene (Xg), cyclohexylene-1,3-dimethylene A divalent group such as (Xh) may be mentioned. For specific examples of each X, the structural formulas are represented by formula (Xa), formula (Xb), formula (X
c), formula (Xd), formula (Xe), formula (Xf), formula (X
g) and the formula (Xh).

[0061]

[Chemical 6]

Specific examples of R in the structural units (VI) and (VII) include a hydrogen atom or an alkyl group such as methyl, tert-butyl, isopropyl and ethyl.
A hydrogen atom and a methyl group are more preferable, and a hydrogen atom is still more preferable.

Specific examples of Y in the structural unit (VIII) include ethylene, propylene, butylene, hexylene,
Alkylene groups such as octylene and decanylene; cycloalkylene groups such as 1,4-cyclohexylene and 1,3-cyclohexylene, (Xa) in the structural unit (V), (X
b), (Xc), (Xd), (Xe), (Xf), (X
g), (Xh) and the like, more preferably ethylene group, propylene group, butylene group, octylene group, 1,4.
-Cyclohexylene group or 1,3-cyclohexylene group, more preferably ethylene group, propylene group or butylene group.

Specific examples of Z in the structural unit (IX) include butylene, pentylene, hexylene, decanylene,
An alkylene group such as undecanylene; an arylene group such as paraphenylene can be mentioned, more preferably a pentylene group, a hexylene group or an undecanylene group, and still more preferably a pentylene group.

(B-2) Crystalline polyamide resin: The crystalline polyamide (B-2) has --CONH-- in the polymer main chain.
It has a bond, can be melted by heating, and has a definite melting point with a measurable heat of fusion. The melting point and the heat of fusion can be measured using a differential scanning calorimeter. Examples include the apparatus and measuring method described in the section of "(B-1) Amorphous or low crystalline cyclic hydrocarbon-based copolyamide". The crystalline polyamide in the present invention has a heat of fusion measured by this method of 1 cal /
Defined as exceeding g.

As a typical example thereof, nylon-
4, nylon-6, nylon-12, nylon-6,
6, nylon-4,6, nylon-6,10, nylon-6,12 or nylon-6, T (polyamide consisting of hexamethylenediamine and terephthalic acid), nylon-
MXD, 6 (polyamide composed of metaxylylenediamine and adipic acid), a mixture of nylon-6 and nylon-6,6, a copolymer of hexamethylenediamine, adipic acid and caprolactam, and the like, among which, among these, More preferably nylon-6,6 or nylon-6
These are commercially available products. For example, there is a product sold under the trade name of Ultramid by BASF AG of West Germany. Relative viscosity of this resin (98%
The concentration in concentrated sulfuric acid is 1 dl / g and the measuring temperature is 25 ° C.), preferably in the range of 1.5 to 8, more preferably 2 to 7.5, and further preferably 2.3 to 6.8.

<Mineral Filler (C) and Glass Fiber (D)> In the second melt-kneading step, in addition to the intermediate composition (A) and the polyamide (B), an impact resistance improving material and / or, for example, Mineral filler (C) and / or glass fiber (D) for improving rigidity, heat resistance and dimensional stability, or various stabilizers, lubricants, colorants, fluidity modifiers, nucleating agents, antifungal agents, etc. Any of the above components can be added and used within a range that does not significantly impair the effects of the present invention.

The mineral filler preferably has an average particle size of 5 μm or less, preferably 4 μm or less, and particularly preferably 2.5 μm or less. The average particle size here is the average maximum particle size of primary particles measured by observation with an electron microscope. The shape of the inorganic filler is spherical, cubic spherical, granular,
There are various types such as needle-like, plate-like, and fiber-like ones, and any of them can be used. Among them, the plate-like one is preferable from the viewpoint of the physical property balance of rigidity and impact resistance and the effect of improving dimensional stability.

As such a mineral filler, metal elements (for example, Fe, Na, etc.) in Group I to Group VIII of the periodic table are used.
K, Cu, Mg, Ca, Zn, Ba, Al, Ti) or silicon elemental substance, oxide, hydroxide, carbonate, sulfate, silicate, sulfite, or various viscosities of these compounds There are minerals and the like. Specifically, for example, titanium oxide, zinc oxide, barium sulfate, silica, calcium carbonate, iron oxide, alumina, calcium titanate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, sulfuric acid. Calcium, sodium sulfate, calcium sulfite, calcium silicate, clay wollastonite, glass beads, glass powder, silica sand,
Examples thereof include silica stone, quartz powder, shirasu, diatomaceous earth, white carbon, iron powder, and aluminum powder, and these may be used in combination.

Among them, talc, mica, kaolin clay, diatomaceous earth and the like having an average particle diameter of 5 μm or less are particularly preferable because they are plate-shaped.

These mineral fillers may be used as they are without treatment, but for the purpose of enhancing the affinity with the resin or the interfacial bond strength, inorganic surface treating agents, highly-fed fatty acids or their derivatives such as esters and salts ( For example, stearic acid, oleic acid, palmitic acid, calcium stearate, magnesium stearate, aluminum stearate, stearic acid amide, ethyl stearate, methyl stearate calcium oleate, oleic acid amide, ethyl oleate, calcium palmitate, palmitic acid. Amide, ethyl palmitate, etc.) or

Coupling agents (eg vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like;
A titanium coupling agent (for example, isopropyl triisostyaroyl titanate, isopropyl trilauryl myristyl titanate, isopropyl isostearoyl dimethacryl titanate, isopropyl tridiisooctyl phosphate titanate, etc.) can be used.

The glass fiber used in the present invention preferably has an average diameter of 15 μm or less, and a glass fiber having an average diameter of 1 to 10 μm further enhances the physical property balance (heat resistance rigidity, impact strength), molding warpage deformation and reheating. It is preferable in that the warp deformation is further reduced. The glass fiber is produced by the following method, for example. First, the molten glass is molded into a glass ball of a predetermined size called a marble, which is heated and softened in a yarn-drawing furnace called a pusher and allowed to flow down from a large number of nozzles of the furnace table, and this base material is spun at a high speed. While being stretched, the sizing agent is attached to the sizing agent by a sizing agent coating device provided on the way to bundle the sizing agent, which is then dried and wound on a rotary drum. At this time, the average diameter of the glass fibers is adjusted to a predetermined value by adjusting the nozzle diameter size, the drawing speed, the drawing atmosphere temperature, and the like.

The length of the glass fiber is not specified, but roving supply, chopped strands of about 1 to 8 mm and the like are also preferable. In this case, the number of focusing is usually 1
The number is preferably from 00 to 5000. Further, so long as the average length after kneading is 0.1 mm or more, so-called milled fiber, a pulverized product of strands called glass powder, or a continuous single fiber sliver-like product may be used. The composition of the raw material glass is preferably alkali-free, and one example is E glass.

When the average diameter of the glass fibers exceeds 15 μm, the degree of improvement in mechanical strength becomes small and the amount of molding warp becomes large, which is not preferable. Here, the average diameter is observed with an electron microscope or the like, and the “average” means a number average.

Here, the sizing agent is usually a film-forming agent,
Although it is composed of a surfactant, a softening agent, an antistatic agent, a lubricant, etc., it may be a surface treatment agent only.

When using these glass fibers, various coupling agents can be used for the purpose of enhancing the affinity with the resin or the interfacial bonding force. The coupling agent usually includes silane-based, chrome-based, titanium-based coupling agents and the like. Among them, those containing a silane coupling agent such as epoxysilane such as γ-glycidoxypropyltrimethoxysilane; vinyltrichlorosilane; aminosilane such as γ-aminopropyltriethoxysilane are preferable. At this time, in order to improve mechanical strength and kneading property, it is possible to perform treatment with various surfactants such as nonionic / cationic / anionic type and dispersants such as fatty acid / metal soap / various resins. preferable.

The intermediate composition (A) and the polyamide (B) are blended in the following proportions. That is, the intermediate composition (A) is 5 to 94 relative to the total amount of the component (A) and the component (B).
%, Preferably 10 to 90% by weight, particularly preferably 20 to 75% by weight. If the intermediate composition (A) is less than the above range, the heat resistance rigidity is insufficient, and if it exceeds the above range, the organic solvent resistance and Insufficient low temperature impact resistance. Polyamide (B) is 6 to 95% by weight, preferably 10 to 90% by weight, particularly preferably 15 to 80% by weight, and when the polyamide (B) is less than the above range, the organic solvent resistance and low temperature impact resistance are unsatisfactory. On the other hand, when it exceeds the above range, the heat resistance becomes unsatisfactory. As polyamide (B) (B-1)
And (B-2) together, (B-1) is 5 to 9
4% by weight, preferably 8 to 80% by weight, particularly preferably 10 to 70% by weight, (B-2) is 1 to 90% by weight, preferably 2 to 80% by weight, particularly preferably 5 to 70% by weight.
Is. In addition, the mineral filler (C) and / or the glass fiber (D) is in a range that does not impair the effects of the present invention, that is, 1 to 60% by weight, preferably 5 to 60% by weight, and particularly preferably 3% by weight based on the whole. It can be used in the range of up to 45% by weight.

To produce the final resin composition of the present invention,
For example, the following melt-kneading can be used for the production using the following methods.

1) After pelletizing or powdering the intermediate composition (A) and the polyamide (B) into a mixture by the same means as in the production of the above intermediate composition (A), L
/ D = a method of producing a final resin composition by melt-kneading using a uniaxial or biaxial extruder of 10 to 30.

2) Polyamide (B) was added to the intermediate composition (A) in the molten state, and the final resin composition was melt-kneaded using a uniaxial or biaxial extruder having L / D = 10-30. Method of manufacturing.

3) Using a vented single-screw or twin-screw extruder with L / D = 30 to 60, each component of the intermediate composition (A) was introduced from the first hopper in a mixture state before melt-kneading. While being degassed from a vent provided between the first hopper and the intermediate hopper of the extruder, at the same time, the polyamide (B) is introduced into the solid or molten state from the intermediate hopper, and the whole is melt-kneaded. A method for producing a final resin composition.

4) L / D = 10-3 for the polyamide (B)
Melt-kneaded with a uniaxial or twin-screw extruder of 0, and the intermediate composition (A) and the intermediate composition (A) in the form of pellets or powder obtained by crushing pellets, or in a molten state, L / D = 10
A method for producing a final resin composition by simultaneously melt-kneading these using a No. 30 single-screw or twin-screw extruder.

In the above method, the secondary melt-kneading temperature is usually in the range of 200 to 350 ° C. The thermoplastic resin composition thus obtained can be extruded into pellets after the second melt-kneading.

The polyphenylene ether resin composition produced by the method of the present invention can be easily molded by a molding method usually applied to thermoplastic resins, that is, an injection molding method, an extrusion molding method, a hollow molding method or the like. it can. Of these, injection molding is preferable.

The polyphenylene ether resin composition produced by the method of the present invention has good mechanical properties and excellent surface appearance and dimensional stability. It is also suitable for parts such as office automation equipment.

[0087]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited in scope by this.

Examples 1 to 4 <Production of Intermediate Composition (A)> (a) Polyphenylene ether: (a-1) Intrinsic viscosity of 0.51 dl / g (measured in chloroform at 30 ° C.) poly (2, 6-dimethyl-1,4-phenylene ether), and (a-2) intrinsic viscosity 0.30 dl
/ G (measured in chloroform at 30 ° C) poly (2,6-
Dimethyl-1,4-phenylene ether) was used.

(B) Polyamide: (b-1) Amorphous nylon (Novamid X21: manufactured by Mitsubishi Kasei Kogyo KK, glass transition temperature 125 ° C., JIS K68)
A relative viscosity of 2.1 according to 10 was used. (B-2) Crystalline nylon (MC112L: manufactured by Kanebo Co., Ltd.,
A relative viscosity of 2.5) according to JIS K6810 was used.

(C) Impact resistance improver: Commercially available hydrogenated styrene-butadiene block copolymer (Kreton G16)
51: Shell Chemical Co., styrene content 33% by weight) was used.

(D) Compound having both unsaturated group and polar group in the same molecule: Commercially available maleic anhydride (reagent grade) was used.

The above components (a), (b), (c) and (d) were thoroughly mixed with a supermixer at the compounding ratio shown in Table 1. Next, this mixture was mixed with TE manufactured by Japan Steel Works
Using an X twin-screw extruder (L / D = 30, with a vent), melt-kneading at a set temperature of 260 ° C., a screw rotation speed of 400 rpm, and a vent degassing vacuum degree of 160 Torr to obtain a resin composition, which is then formed into a strand. It was extruded and pelletized with a cutter. This was dried at 105 ° C. for 8 hours with a hot air dryer. Thus, an intermediate composition (A) was obtained.

The amount of unreacted residual maleic anhydride (d) in this intermediate composition was determined by extracting the intermediate composition with acetone and by infrared spectroscopy. The above results are shown in Table 1.

[0094]

[Table 1]

<Production of Resin Composition> (A) Intermediate Composition: The intermediate composition produced as described above was used.

(B) Polyamide: Crystalline nylon-6
(Ultramid B-4: BASF (Germany), injection molding grade), crystalline nylon-6,6 (Ultramid A3W: BASF (Germany), injection molding grade) and amorphous nylon ( Novamit X21: manufactured by Mitsubishi Kasei Co., Ltd.) was used.

Impact resistance improver: Commercially available styrene-butadiene block copolymer (KX65: Shell Chemical Co., styrene content 28% by weight), commercially available maleic anhydride-modified ethylene-propylene rubber (T7741P: Nippon Synthetic Rubber). And a commercially available hydrogenated styrene-butadiene block copolymer (Kreton G1651: Shell Chemical Co., styrene content 33% by weight) were used.

(C) Mineral filler: Commercial talc (L
MS-100: Fuji Talc Industry Co., Ltd., average particle size 1.8-
2.0 μm) was used.

The above components were thoroughly mixed in a supermixer at the compounding ratios shown in Table 2. Then, using a TEX twin-screw extruder manufactured by Japan Steel Works, this was set at 240
After melt-kneading at ℃ and screw rotation speed of 400 rpm, pelletized.

<Physical property evaluation test> From the pellets of the above resin composition, an in-line screw type injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS-90B type) was used, and the cylinder temperature was 280 ° C and the mold cooling temperature was 70 ° C. Injection molding,
A test piece was prepared.

In the injection molding, a vacuum dryer was used immediately before that, and drying was performed for 48 hours under the conditions of a vacuum degree of 0.1 Torr and 80 ° C. The injection-molded test piece was placed in a desiccator immediately after molding and allowed to stand at 23 ° C. for 4 to 6 days, and then an evaluation test was conducted. The results are shown in Table 2.

The physical properties and various characteristics were measured by the following methods. (1) Appearance of molded product A molded product of a flat plate of 150 x 150 x 3 mm was observed for the state of occurrence of discoloration and silver streak. Double Maru: Very good ○: Good Δ: Slightly inferior ×: Inferior

(2) Izod impact strength ISO R180-1969 (JIS K7110)
(Izod impact strength with notch) was measured using an Izod impact tester manufactured by Toyo Seiki Seisakusho. In addition,
The measurement atmosphere temperature was 23 ° C and -30 ° C.

(3) Flexural Modulus ISO R178-1974 Procedure 12 (JIS
According to K7203), it measured using the Instron tester. The measurement temperature was 23 ° C.

[0105]

[Table 2]

Example 5 With the composition shown in Table 1, the vent degassing vacuum degree was 760To.
Pellets were obtained in the same manner as in Example 1 except that rr was used. Put these pellets in a vacuum heating dryer, and vacuum degree 5To
The intermediate composition (A-4) was obtained by drying for 10 hours under the conditions of rr and a temperature of 130 ° C.

The amount of unreacted residual maleic anhydride (d) in the intermediate composition (A-4) was 80 ppm.

Using the resulting intermediate composition, a resin composition was prepared and a physical property evaluation test was conducted in the same manner as in Example 1 except that G1651 was used as the impact resistance improver in place of T-7741P. The results are shown in Table 2.

Example 6 Pellets of the intermediate composition produced by the same method as in Example 5 were placed in a pressure resistant autoclave equipped with a stirrer, and chloroform was added thereto, and the temperature was raised to 60 ° C. with stirring to uniformly dissolve them. After washing this with water, chloroform in the separated organic phase was distilled off by steam stripping to obtain an aqueous dispersion slurry. This slurry was dehydrated with a centrifuge, the solid content was put into a drier, and dried at 100 ° C. overnight to obtain an intermediate composition (A-5).

The amount of unreacted residual maleic anhydride (d) in the intermediate composition was 20 ppm. Using the obtained intermediate composition (A-5), a resin composition production and physical property evaluation test were conducted in the same manner as in Example 4, and the results are shown in Table 2.

Example 7 An intermediate composition (A-6) was obtained in the same manner as in Example 1 except that the crystalline nylon (b-2) was used instead of the amorphous nylon (b-1). It was

The amount of unreacted residual maleic anhydride (d) in the intermediate composition (A-6) was 5 ppm. Same as Example 1 except that the obtained intermediate composition (A-6) was used and the amorphous nylon (X21) was used as the polyamide (B) instead of the crystalline nylon-6 (B-4). The resin composition was manufactured and a physical property evaluation test was conducted, and the results are shown in Table 2.

Example 8 Using the intermediate composition (A-6) obtained in Example 7, a resin composition was prepared and a physical property evaluation test was conducted in the same manner as in Example 1. The results are shown in Table 2.

Comparative Examples 1 to 6 Resin compositions were produced using the same compounding apparatus as in Examples 1 to 3 with the composition ratios shown in Tables 1 and 2 and different production steps.
That is, in Comparative Examples 1 to 3, during the production of the intermediate composition, the vent degassing vacuum degree was melt-kneaded at 760 Torr (atmospheric pressure),
In Comparative Examples 4 and 6, melt kneading was performed at vent degassing vacuum degrees of 560 Torr and 160 Torr, respectively, and Comparative Examples 1, 2 and 4 were used.
Then, the final resin composition was produced in the same manner as in Examples 1, 3 and 4. In Comparative Example 5, the manufacturing process of the intermediate composition was omitted and melt kneading was performed in one step.

In Comparative Example 6, the same composition components as in Example 1 were used except that the polyamide of the component (b) was not mixed in the step of producing the intermediate composition (A), and the final resin was prepared in the same production process. A composition was produced.

Examples 9 to 15 <Production of intermediate composition (A)>
Next, a TEX twin screw extruder (L / D = 30, manufactured by Japan Steel Works, Ltd.,
(With a vent), the set temperature is 260 ° C., the screw rotation speed is 400 rpm, and the vacuum degree of the vent vents at three locations is 60 Torr when the intermediate composition is (A-11), (A-12) and (A-13). ) For 160 Torr, (A-14) for 60
Example 1 except that each was held in Torr and melt-kneaded
It carried out similarly to --4 and obtained the intermediate composition (A). The results are shown in Table 3.

[0117]

[Table 3]

<Production of Resin Composition> (A) Intermediate Composition: The intermediate composition produced as described above was used. (B-1) Amorphous or low crystalline cyclic hydrocarbon-based copolyamide: Amorphous nylon (Novamit X21:
Mitsubishi Kasei Co., Ltd., glass transition temperature 125 ℃, JIS
A relative viscosity of 2.1) according to K6810 was used.

(B-2) Crystalline polyamide resin: Nylon-6 (MC112L: manufactured by Kanebo Co., Ltd., JIS K6810)
A compliant relative viscosity of 2.5) was used. (C) Mineral filler: Commercially available talc (manufactured by Fuji Talc Co., average particle size 1.3 μm) was used. (D) Glass Fiber A commercially available chopped strand glass fiber (manufactured by Asahi Fiber Glass, diameter 10 μm, length 3 mm) was used.

Impact resistance improver: A commercially available styrene-butadiene block copolymer (KX65: manufactured by Shell Chemical Co., styrene content 28% by weight) was used.

In the compounding ratios shown in Table 4, the above (A) and (B
The components (-1) and (B-2) were thoroughly mixed with a super mixer. Next, when these are melt-kneaded using a TEX twin-screw extruder manufactured by Japan Steel Works at a set temperature of 230 ° C. and a screw rotation speed of 250 rpm, the components (C) and (D) are transferred from the intermediate hopper of the kneader. Feeded and pelletized.

<Physical Properties and Evaluation Test> The physical properties evaluation test was carried out in the same manner as in Example 1, but the items not carried out in Example 1 were carried out by the methods shown below. The results are shown in Table 4.

(1) Gloss According to JIS D8741, it was measured using a gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. (2) Surface smoothness The center of the JIS sheet was measured using a surface roughness meter (ET-30HK manufactured by Kosaka Laboratory Ltd.), and the 10-point average roughness (R
Z) was determined. (3) Linear expansion coefficient The linear expansion coefficient was measured according to ASTM D696. However, the measurement temperature range is 23 to 80 ° C. (4) Heat distortion temperature (HDT) Using an HDT tester manufactured by Toyo Seizo Seisakusho, JIS
It was evaluated according to K7207 under a load of 4.6 kg.

[0124]

[Table 4]

Comparative Example 7 In Comparative Example 7, the resin composition was produced by changing the production process with the blending composition ratios shown in Tables 3 and 4. That is, in the manufacturing process of the intermediate composition, the vent degassing vacuum degree was melt-kneaded at 760 Torr (atmospheric pressure), and the manufacturing method of the final resin composition was performed in the same manner as in Example 9. The results are shown in Table 4.

Comparative Example 8 Using the compounding ingredients shown in Table 4, except that the step of producing the intermediate composition was omitted and the amorphous nylon was not compounded in the step of producing the resin composition by melt kneading in one step. A final resin composition was produced in the same manner as in Examples 9 to 15. The results are shown in Table 4.

Comparative Example 9 [0127] A commercially available styrene-butadiene block copolymer (KX65: Shell Chemistry) was used as an impact resistance improver in the step of producing a resin composition by omitting the step of producing the intermediate composition and performing melt kneading in one step. Instead of using a styrene content of 28% by weight), a blended component shown in Table 4 was used, except that a commercially available hydrogenated styrene-butadiene block copolymer (Kreton G1651: Shell Chemical Co., Ltd.) was blended. Example 9
The final resin composition was prepared in the same manner as described above. The results are shown in Table 4.
It was shown to.

[0128]

From the results of the above-mentioned evaluation test, an intermediate composition having an unreacted residual component (d) of less than 100 ppm was prepared in advance from a melt-kneaded composition mainly composed of polyphenylene ether. The resin composition of the present invention produced by melt-kneading a polyamide with a product does not impair low-temperature impact resistance and does not cause burns or silver streaks during high-temperature molding, and has a smooth surface of the molded article and a glossy appearance. Shows that the dimensional stability is excellent and the dimensional stability is excellent. Therefore, its use is wide and it can be an industrially useful material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C08L 9/06 LBR A 8016-4J LBT B 8016-4J 53/02 LLZ 7142-4J 71/12 LQP 9167-4J 77/00 LQV 9286-4J // C08L 71:12 (72) Inventor Shigekazu Oi 1 Toho-cho, Yokkaichi-shi, Mie Prefecture Yokkaichi Research Institute, Mitsubishi Petroleum Corporation (72) Inventor Yoshihiro Kurasawa Mie 1 Toho-cho, Yokkaichi-shi, Japan Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (4)

[Claims] 1. A component (a) having the following composition:
(A) Polyphenylene ether 56 to 99% by weight (b) Polyamide 0.1 to 4.9% by weight (c) Impact resistance improver with respect to the total amount of (b), (c) and (d). 1 to 40% by weight (d) 0.01 to 10% by weight of a compound having both an unsaturated group and a polar group in the same molecule is first melt-kneaded to obtain 100 parts of unreacted residual component (d).
An intermediate composition (A) having a content of less than ppm is obtained, and then 5 to 94% by weight of the intermediate composition (A) and the polyamide (B) 6 relative to the total amount of the intermediate composition (A) and the following polyamide (B). To 95 wt% is secondarily melt-kneaded with the polyphenylene ether resin composition. 2. As the polyamide (B), an amorphous or low crystalline cyclic hydrocarbon-based copolyamide (B-1) having a glass transition temperature of 90 to 250 ° C. and a crystalline polyamide (B-2). The manufacturing method according to claim 1, wherein 3. The primary melt-kneading is performed by vacuum degassing from a vent degassing port downstream of the same extruder while melt-kneading with a kneading extruder to reduce unreacted residual component (d) to less than 100 ppm. The manufacturing method according to claim 1 or 2. 4. The process according to claim 1, wherein the pelletized or powdered product after the first melt-kneading is dried under reduced pressure or washed with a solvent so that the unreacted residual component (d) is less than 100 ppm.