JPH04311750A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition excellent in compatibility, stable finely dispersed structure, mechanical strength, heat resistance, dimensional stability and molding and processing properties by blending an aminated phenylene ether-based resin with a modified olefinic resin. CONSTITUTION:(A) 10-90wt.% aminated phenylene ether-based resin is blended with (B) 90-10wt.% olefinic resin modified by introducing epoxy group. A component using a random copolymer obtained by combining 2,6-dimethyl-1,4-phenylene ether unit with 2,3,6-trimethyl-1,4-phenylene ether unit is preferable as the component A.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is a phenylene ether resin that is useful as a material for equipment in the automobile, electrical and electronic fields, and is made by blending a phenylene ether resin with an olefin resin modified by introducing an epoxy group. The present invention relates to a high-performance thermoplastic resin composition that combines the heat resistance, mechanical strength, and dimensional accuracy that are characteristic of resins, as well as the moldability and organic solvent resistance that are characteristic of olefin resins.

0002

[Prior Art] Phenylene ether resins having unsubstituted or substituent groups on the phenylene ring, especially poly(2,6-dimethyl-1,4-phenylene ether), have excellent heat resistance and mechanical strength, and are so-called engineering plastics. However, because of its high melt viscosity, it has the undesirable property of being difficult to mold by injection molding or the like. Also, impact strength and solvent resistance are insufficient in many fields of application as heat-resistant engineering plastics.

[0003] It is a well-known idea that when a single resin material cannot sufficiently satisfy the desired properties, one attempt is made to compensate for the insufficient properties by mixing other resin materials. ing. Materials in which the moldability of phenylene ether resins is improved by blending them with styrene resins, which are highly compatible with phenylene ether resins and have good moldability, are widely used in practical applications. Both have poor solvent resistance, and as a result, the mixed composition also does not have sufficient solvent resistance.

Olefin resins have excellent moldability, organic solvent resistance, etc., low specific gravity, and are inexpensive, so they are widely used in the production of molded products, but their heat resistance is not so high and they are used for engineering plastics. This poses an obstacle to its use.

Therefore, if a composition can be obtained that has the good properties of both phenylene ether resin and olefin resin and compensates for the undesirable points, it will be possible to provide an excellent resin material that can be used in a wide range of fields. However, phenylene ether resins and olefin resins are incompatible and have no affinity, so if the two components are simply mixed, the adhesion at the interface of this two-phase structure is not good. . Therefore, the two-phase interface of the obtained molded product becomes a defective part, resulting in a decrease in mechanical strength and impact resistance. Furthermore, these two phases are difficult to form into a uniform and finely dispersed form, and are likely to cause delamination when subjected to shear stress during molding processing such as injection molding.

One of the general methods considered to solve the above problem is to modify each resin with functional groups that react with each other in order to improve the mutual affinity of the two components, and to melt them at high temperatures. This is a method of obtaining a block or graft copolymer through chemical bonding through reaction. From this point of view, the use of many functionalized modified phenylene ether resins has been proposed for the purpose of increasing the reactivity of phenylene ether resins. For example, a method using a carboxyl group- or carboxylic anhydride-functionalized phenylene ether resin (Japanese Patent Application Publication No. 62-500456, Japanese Patent Application Laid-Open No. 63-106
No. 56, No. 63-54427 and No. 63-12805
No. 6 publications, etc.), methods using epoxy group-modified phenylene ether resins (Japanese Patent Application Laid-Open No. 62-257957 and Japanese Patent Publication No. 63-503388, etc.), amide group- and imido group-functionalized phenylene ether resins. Methods using phenylene ether resins functionalized with alkoxysilyl groups (such as Japanese Patent Application Publications No. 63-500803, No. 63-503391, and JP-A-61-16963),
Japanese Patent Application Publication No. 63-503392) etc. are disclosed, and these functionalized phenylene ether resins are used as precursors to produce resins having a structure having functional groups, such as polyamide,
A number of resin compositions with saturated polyesters or functionalized modified olefinic resins have been proposed. However, the actual situation is that the number of functional groups introduced is still insufficient and improvement in compatibility is desired.

[0007]

[Problems to be Solved by the Invention] The present invention improves the compatibility between a phenylene ether resin and an olefin resin, and achieves a stable finely dispersed structure by melt-kneading, and has excellent mechanical strength and heat resistance. The object of the present invention is to provide a thermoplastic resin composition having good properties, dimensional accuracy, moldability, and solvent resistance.

[0008]

[Means for Solving the Problems] The present invention provides the following components (
A thermoplastic resin composition comprising A) and (B).

(A) Aminated phenylene ether resin
10-90% by weight (B) Olefin resin modified by introducing epoxy groups 90-90% by weight
10% by weight

Olefin resin modified by introducing the aminated phenylene ether resin (A) of the present invention and an epoxy group (hereinafter referred to as modified olefin resin)
The composition with (B) has significantly improved compatibility between both resins, and has excellent mechanical properties, moldability, dimensional accuracy and It is extremely useful as a molding material with solvent resistance. Hereinafter, the structure of the thermoplastic resin composition of the present invention will be explained in detail.

Component (A): Aminated phenylene ether resin The aminated phenylene ether resin used in the present invention is a phenylene ether resin obtained by adding an amino group to a phenylene ether resin using a modifier. It can be produced by reacting a phenylene ether resin and a modifier at a temperature from room temperature to 350° C. in the presence or absence of an organic solvent that can dissolve the phenylene ether resin.

(1) Phenylene ether resin The phenylene ether resin used in the present invention has the general formula (I)

[0013]

[Chemical formula 1]

(In the formula, Q1 each represents a halogen atom, a primary or secondary alkyl group, an alkenyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, and each Q2 represents hydrogen. atoms, halogen atoms, primary or secondary alkyl groups, phenyl groups,
Represents a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group. n represents a number of 10 or more) or a copolymer thereof.

Preferred examples of primary alkyl groups for Q1 and Q2 are methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl. , 2-, 3- or 4-methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, sec-butyl or 1-methylpentyl. A preferable example of the alkenyl group for Q1 is allyl. In many cases, Q1
is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and Q2 is a hydrogen atom.

Suitable homopolymers of the phenylene ether resin (I) include, for example, 2,6-dimethyl-1,
It consists of 4-phenylene ether units. A suitable copolymer is a random copolymer consisting of a combination of the above units and 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable homopolymers or random copolymers are described in the patent literature. Phenylene ether based resins containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and/or impact strength are also suitable. For example, it is a resin in which a vinyl monomer such as a vinyl aromatic compound such as acrylonitrile or styrene, or a polymer such as polystyrene or an elastomer thereof is graft copolymerized on a phenylene ether resin.

The molecular weight of the phenylene ether resin (I) usually corresponds to an intrinsic viscosity of about 0.2 to 0.8 dl/g at 30°C as measured in chloroform.

The phenylene ether resin (I) is usually produced by oxidative coupling of the monomers mentioned above. A number of catalyst systems are known for the oxidative coupling polymerization of phenylene ether resins. There are no particular restrictions on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, cobalt, etc., usually in combination with various other substances.

(2) Amination The method for introducing amino groups into the above-mentioned phenylene ether resin is not particularly limited, but various methods can be used. For example, there is the following method discovered by some of the inventors.

(a) Phenylene ether resin (I) has general formula (IIa) R-(N=C=O)m (I
Ia) (wherein R represents a divalent or higher aliphatic hydrocarbon group having 1 to 32 carbon atoms, an aromatic hydrocarbon group, or an aromatic aliphatic hydrocarbon group, and m is an integer of 2 or more) The isocyanato group of the terminal isocyanate-modified phenylene ether resin obtained by reacting the polyfunctional isocyanate obtained by the reaction with the polyfunctional isocyanate obtained by the general formula (IIIa) is

[0021]

[Case 2]

A method for producing a terminally aminated phenylene ether resin represented by the formula (in which Q1, Q2, R, m and n are the same as above) (Japanese Patent Application No. 180379/1999).

(b) Phenylene ether resin (I) has the general formula (IIb) X-R-NH2 (IIb) (wherein R
represents an aliphatic hydrocarbon group, aromatic hydrocarbon group, or araliphatic hydrocarbon group having 1 to 32 carbon atoms, and X represents a halogen atom) to react with a halogenated primary amine represented by the general formula (IIIb)

[0024]

[Chemical formula 3]

A method for producing a terminally aminated phenylene ether resin represented by the formula (in which Q1, Q2, R and n are the same as above) (Japanese Patent Application No. 2-247378).

(c) Terminal epoxidized phenylene ether resin is reacted with a polyamine compound to form the general formula (I
IIc)

[0027]

[C4]

A method for producing a terminally aminated phenylene ether resin represented by the formula (wherein Q1, Q2 and n are the same as above; B represents a polyamine residue) (Patent Application No. 2-1)
90436 specification).

(d) Phenylene ether resin (I) is reacted with a compound having (i) a carbon-carbon double bond or a carbon-carbon triple bond and (ii) an amino group simultaneously in the molecule to form an aminated phenylene ether resin. An amino group can be introduced by a method such as a method for producing a resin (Japanese Patent Laid-Open No. 62-257957).

Component (B): Modified olefin resin (1)
Olefin resin The olefin resin used in the modified olefin resin (B) used in the present invention is an α-olefin homopolymer such as ethylene, propylene, butene or hexene, or a copolymer of these α-olefins, or It includes a copolymer of these α-olefins and other copolymerizable unsaturated monomers. Specifically, (very) low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer or ionic crosslinking thereof. body, ethylene-
(meth)acrylic acid ester copolymers, mixtures of these polymers, or graft copolymers of maleic anhydride, (meth)acrylic acid, lower alkyl (meth)acrylic esters (the number of carbon atoms in the alkyl group is 1 to 8), etc. It also includes polymers and the like. Furthermore, it contains an olefin resin having a polyunsaturated compound such as dialkenylbenzene, methyloctadiene or methylhexadiene as a copolymerization component.

(2) Introduction of epoxy groups into olefin resin

The method for introducing epoxy groups into the olefin resin is not particularly limited, and all known methods can be applied.

For example, (i) the olefin resin is treated with a compound having an ethylenic double bond and an epoxy group, specifically glycidyl methacrylate or glycidyl maleate, and the presence of a radical generator such as an organic peroxide. The amount of epoxy groups introduced by this method is preferably 0.01 to 30% by weight, more preferably 0.1 to 30% by weight, based on the content of the compound in the modified olefin resin. It is 10% by weight. If it is less than 0.01% by weight, there is almost no improvement effect according to the present invention, and if it exceeds 30% by weight, it is difficult for the composition to exhibit its mechanical properties.

[0034] In addition, in an olefin resin containing a polyunsaturated compound such as dialkenylbenzene, methyloctadine, or methylhexadiene as a copolymerization component, (ii) ethylenic unsaturation in the olefin resin (a) Oxidation of bonds with peracids such as performic acid, peracetic acid, perbenzoic acid, etc.; (b) Hydrogen peroxide or hydroperoxidation in the presence or absence of catalysts such as vanadium, tungsten, molybdenum compounds. (3) oxidation with alkaline hydrogen peroxide; (d) oxidation with sodium hypochlorite in the presence or absence of a metal porphyrin complex such as a manganese porphyrin complex; iii) A method of adding a compound containing one or more epoxy groups in the molecule, specifically a thiol compound such as thioglycidol or glycidyl thioglycolate, to an ethylenically unsaturated bond in an olefinic resin. There are these (ii) and (iii)
The amount of epoxy groups introduced by the method described above is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more of the ethylenically unsaturated bonds in the olefin resin. If it is less than 1%, there is almost no improvement effect by the present invention.

[0035] These reactions (ii) and (iii) are often carried out with the olefin resin in a dissolved or molten state, but they may also be carried out in a swollen state with a solvent. , aliphatic, alicyclic, aromatic hydrocarbons and their halides, esters with 6 or more carbon atoms, ethers, ketones, and carbon disulfide, and mixed solvents of two or more types are also used. Can be used. The reaction rate with respect to ethylenically unsaturated bonds does not necessarily have to be 100%, and as long as substantial epoxy groups are introduced, there is no problem even if products from side reactions are mixed in.

Thermoplastic resin composition: (1) Blending ratio of component (A) and component (B) Properties such as moldability, mechanical strength, solvent resistance, dimensional accuracy, and high temperature rigidity of the thermoplastic resin composition Although it is often possible to adjust the characteristics of each constituent component and their blending ratio, it is often difficult to reconcile contradictory properties of the development mechanism, such as rigidity and impact strength, for example. For practical purposes, usually
This is done from the perspective of achieving an appropriate balance of various properties such as formability, mechanical strength, and high-temperature rigidity. Therefore, it can be said that the following ranges are practically useful for the blending ratio of each component of the composition in the present invention.

Component (A): Aminated phenylene ether resin
10-90% by weight Component (B): Modified olefin resin
90-10% by weight Within these ranges, the selection of the blending ratio is determined by the required performance of the final molded article.

Component (A) used in the present invention may be an aminated phenylene ether resin alone or a mixture of the same modified phenylene ether resin and an unmodified phenylene ether resin. Moreover, the component (B) used in the present invention may be a modified olefin resin alone or a mixture of the same modified olefin resin and an unmodified olefin resin.

(2) Additional Components Other additional components may be added to the thermoplastic resin composition of the present invention. For example, antioxidants, weather resistance improvers, nucleating agents, flame retardants, slip agents, plasticizers, styrene resins, fluidity improvers, mold release agents, pigments, dispersants, etc. can be used as additional components. In addition, organic/inorganic fillers, reinforcing agents,
For example, glass fiber, mica, talc, wollastonite,
Addition of potassium titanate, calcium carbonate, silica, etc. is effective in improving rigidity, heat resistance, dimensional accuracy, dimensional stability, etc. Furthermore, the addition of rubber components, particularly styrene-butadiene copolymer rubber and its hydrogenated products, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, etc., can improve the impact strength of the composition. Particularly effective. The amount of rubber blended varies depending on the target physical property value, but for example, in the case of improving the balance between rigidity and impact strength of the composition, it is 5 to 5 parts by weight per 100 parts by weight of the resin component of the composition.
It is 30% by weight.

(3) Method for mixing the composition The thermoplastic resin composition of the present invention can be prepared by kneading and mixing the above-mentioned components using various kneaders, such as a single screw extruder, a twin screw extruder, a Banbury mixer, etc. can be used. Further, the order of mixing may be any possible order, but when mixing by melt kneading, it is preferable to mix sequentially starting from the one with the highest viscosity.

[0041]

[Examples] The present invention will be explained in detail below with reference to Examples, but the scope of the present invention is not particularly limited by these examples.

Production Example 1: Production of aminated phenylene ether resin Poly(2,6-dimethyl-1,4-phenylene ether) (manufactured by Nippon Polyether Co., Ltd., intrinsic viscosity measured in chloroform at 30°C: 0. 3dl/g) 500g
5 liters of toluene was added to the mixture, and the mixture was heated and stirred at 70°C under a nitrogen atmosphere to dissolve the phenylene ether resin. Subsequently, 175 g of a 50% aqueous sodium hydroxide solution as a basic catalyst and 50 g of trioctylmethylammonium chloride as a phase transfer catalyst were added, and the mixture was heated to 90°C.
The temperature of the mixture was raised to 100 mL and stirring continued for 30 minutes. followed by 3
-75 g of chloropropylamine was dissolved in 250 ml of water and added over 15 minutes. After further heating and stirring for 7 hours, the reaction mixture was poured into 25 liters of methanol to precipitate the produced modified resin. After filtering this, water 2
It was washed with 5 liters of water and further washed with 25 liters of methanol. The mixture was dried under reduced pressure at 80° C. to obtain an aminated phenylene ether resin. The recovery rate was 99%. Confirmation of the amino group and reaction rate of the terminal phenolic hydroxyl group of the phenylene ether resin were confirmed by adding a 1.5% by weight carbon tetrachloride solution of the aminated phenol ether resin to an optical path length of 10
This was carried out by measuring the infrared (absorption) spectrum using a mm quartz cell. Absorption due to amino group was observed at the position of 3380 cm-1. The reaction rate was calculated from the absorbance (3622 cm-1) of the terminal phenolic hydroxyl group of the phenylene ether resin before and after the reaction, and was 100%. Furthermore, according to nuclear magnetic resonance absorption spectroscopy, the number of halogenated primary amines added is
It turned out to be one molecule.

Production Example 2: Production of modified olefin resin (1) Propylene resin homopolymer powder (ASTM D1
250 g of melt flow rate (MFR) at 230°C measured in accordance with 238 (1 g/10 min) and 100 g of glycidyl methacrylate were placed in a 10 liter glass flask equipped with a stirrer that had been sufficiently purged with nitrogen in advance. Add 5 liters of chlorobenzene to 110
The mixture was heated and stirred at ℃ to dissolve. Add 5 chlorobenzene to this solution.
25 g of benzoyl peroxide dissolved in 0.00 ml was added dropwise over 2 hours.
Allowed time to react. The obtained reaction product was poured into 15 liters of acetone, and the product was precipitated and filtered and washed for 3 times.
After carrying out this process twice, the mixture was then dried under reduced pressure to obtain a graft-modified propylene resin. The glycidyl methacrylate content of this graft-modified propylene resin was found to be 0.75% by weight by infrared spectroscopic analysis, and the MFR was 14 g/10 min. The resin obtained thereby is referred to as modified olefin resin (1).

Production Example 3: Production of modified olefin resin (2) Copolymer of propylene and 7-methyl-1,6-octadiene (7-methyl-1,6-octadiene content: 2.7
Mol%, crystallinity 45% by X-ray diffraction method, MFR: 1
．． 7 g/10 minutes) and 75 g of glycidyl methacrylate were placed in a 10 liter glass flask equipped with a stirrer and the atmosphere was replaced with nitrogen, and 5 liters of xylene was added thereto and heated to 110° C. with stirring to dissolve. To this solution, 25 g of benzoyl peroxide dissolved in 500 ml of xylene was added dropwise over 2 hours, and after the dropwise addition was completed, the reaction was further carried out at 110°C for 3 hours. The obtained reaction product was poured into 15 liters of acetone, and the product was precipitated and filtered and washed three times, and then,
This was dried under reduced pressure to obtain a graft-modified olefin copolymer. The glycidyl methacrylate content of this product was found to be 1.2% by weight by infrared spectroscopic analysis. Also, MFR is
It was 2g/10 minutes. The copolymer thus obtained is referred to as a modified olefin resin (2).

Examples 1 to 5 and Comparative Examples 1 to 2 Aminated phenylene ether resin obtained in Production Example 1, modified olefin resins (1) and (2) obtained in Production Examples 2 and 3, unmodified polyphenylene Using ether (manufactured by Nippon Polyether Co., Ltd., chloroform, intrinsic viscosity 0.3 dl/g at 30°C) and ethylene-propylene rubber (EPR), in a plastomill manufactured by Toyo Seiki Co., Ltd. with an internal volume of 60 ml, Table 1 was prepared.
The following composition was melt-kneaded for 10 minutes at 230° C. and 180 rpm. The following physical properties were evaluated for the obtained thermoplastic resin composition.

(1) Dispersion form Using a scanning electron microscope model S-2400 manufactured by Hitachi, Ltd.
A cross section of the resin composition was observed.

(2) Izod impact strength resin composition
A sheet with a thickness of 2 mm was prepared by press molding at 60° C., and the unnotched Izod impact strength at 23° C. was measured by stacking three test pieces with a thickness of 2 mm according to JIS K7110.

(3) Organic solvent resistance Bergen's 1/4 ellipse method [SPE Journal 667 (
1962)]. That is, when a test piece with a thickness of 2 mm was fixed in a quarter oval jig with a major axis of 24 cm and a minor axis of 8 cm, and immersed in commercially available gasoline for 5 minutes,
The minimum strain value at which cracks occur was determined as the critical strain value.

[0049] At this time, make sure that no cracks occur.
Those with a critical strain value of 1.5% or more were evaluated as ■ (good), those with a critical strain value of 1.0 to 1.5% were evaluated as Δ (fair), and those with a critical strain value of less than 1% were evaluated as × (poor).

The above test results are shown in Table 1. As is clear from these results, when aminated phenylene ether resin and modified olefin resin are blended, homogeneous dispersion of fine, almost spherical phenylene ether resin is observed, and the impact resistance strength is significantly increased. A thermoplastic resin composition with improved solvent resistance was obtained.

[0051]

[Table 1]

[0052]

[Effects of the Invention] As described above, the thermoplastic resin composition of the present invention containing an aminated phenylene ether resin and a modified olefin resin has significantly improved compatibility between the two resins, as shown in Table 1. Both components exhibit excellent dispersion morphology and have excellent mechanical strength and organic solvent resistance.

Claims (1)

[Claims] 1. A thermoplastic resin composition comprising the following components (A) and (B). (A) Aminated phenylene ether resin
10-90% by weight (B) Olefin resin modified by introducing epoxy groups 90-90% by weight
10% by weight