JPH0480253A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in rigidity and organic solvent resistance by mixing a hydroxyalkylated phenylene ether resin with an epoxy olefin resin. CONSTITUTION:A phenylene ether resin (a) of an intrinsic viscosity (in chloroform at 30 deg.C) of 0.2-0.8dl/g is reacted with 1-50mol, per mol of the terminal phenolic hydroxyl groups of component (a), of a functionalizing agent (b) in the presence of a basic catalyst optionally in an organic solvent in which component (a) is soluble at 50-200 deg.C to obtain a hydroxyalkylated phenylene ether resin (A). Separately, an alpha-olefin is copolymerized with an epoxy unsaturated monomer to obtain an epoxy olefin resin (B). 10-90wt.% component A is mixed with 90-10wt.% component B.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a phenylene ether resin composition having excellent organic solvent resistance and mechanical strength. Specifically, by mixing a hydroxyalkylated phenylene ether resin and an epoxy group-containing olefin resin, it is possible to combine the heat resistance and mechanical strength that are the characteristics of phenylene ether resins, and the moldability and organic solvent resistance that are characteristics of olefin resins. It is a thermoplastic resin composition that has the following properties and prevents deterioration of impact strength and delamination that generally occurs in incompatible resin mixtures, and is suitable for use in structural members of automobiles and electrical products, etc. Concerning molding materials that meet high performance requirements.

(Prior art) Phenylene ether resin has excellent thermal, mechanical, and electrical properties and is therefore useful as a resin for molding materials, but it has drawbacks in processability, organic solvent resistance, and impact resistance. Therefore, its scope of use is limited. As a method to improve these drawbacks, a method of improving molding processability by mixing other resins, such as styrene polymers, is disclosed in U.S. Patent No. 3.
．． 383.435, but the organic solvent resistance is not improved at all.

On the other hand, various blends with olefin resins, which have excellent organic solvent resistance, have been studied, and a blend of olefin resins and phenylene ether resins has been proposed in Japanese Patent Publication No. 7069/1982, but this is not required in the industrial field. The organic solvent resistance and mechanical strength that fully satisfy the high level of demand are not necessarily met. Furthermore, JP-A-53-7
No. 1158, No. 54-88960, No. 59-1001
Reference No. 59 proposes blending, for example, a block copolymer of styrene and butadiene or a hydrogenated product thereof for the purpose of improving the compatibility of phenylene ether resin and olefin resin. Since the amount is small and the phenylene ether resin is substantially a continuous phase, the organic solvent resistance of the olefin resin is not fully exhibited. Furthermore, in JP-A-58-103557 and JP-A-60-76547, 20% by weight or more of an olefin resin is blended, and a diblock copolymer consisting of an alkenyl aromatic compound and a conjugated diene is used as a compatibilizer. , and other compositions incorporating hydrogenated substances are disclosed. According to this report, the tensile properties and brittleness are improved, but the required levels of rigidity and heat resistance are not fully satisfied.

In addition, one of the present inventors previously developed a crystalline propylene-dialkenylbenzene obtained by polymerizing propylene as a main component and a small amount of a dialkenylbenzene compound as an affinity improver for phenylene ether resin and propylene resin. A propylene-dialkenylbenzene copolymer modified with a styrene monomer obtained by polymerizing a copolymer and a styrene monomer in the presence of a radical polymerization initiator is a phenylene ether resin and a propylene resin. It was discovered that it is effective as an affinity improver for
It was disclosed in issue 7. However, the propylene-dialkenylbenzene copolymer modified with a styrene monomer under radical polymerization conditions does not have a satisfactory addition effect, and if a sufficient amount is added until the affinity is improved,
Although the impact strength is improved, there is a problem that the stiffness, especially the high temperature stiffness, is reduced, and there is a desire for an improvement in the layer (Problem to be solved by the invention) The present invention solves the above problems, The purpose of the present invention is to provide a thermoplastic resin composition having excellent rigidity and organic solvent resistance.

(Means for Solving the Problems) As a result of intensive research on improving compatibility so that a large amount of olefin resin can be blended into phenylene ether resin, the present inventors found that hydroxyl, a highly chemically active functional group, By introducing an alkyl group into a phenylene ether resin and combining it with an olefin resin containing a specific functional group, it is possible to make a wide range of phenylene ether resins and olefin resins, which are originally incompatible, compatible, which both resins originally have. The present invention was completed based on the discovery that a composition having excellent properties can be obtained.

That is, the present invention is a thermoplastic resin composition comprising the following components (a) and (b) and the composition.

(a) Hydroxyalkylated phenylene ether resin
10 to 90% by weight (b) Epoxy group-containing olefin resin 90 to 10% by weight The present invention will be described in detail below.

1 bed size ball (1) Hydroxyalkylated phenylene ether resin (
a) The hydroxyalkylated phenylene ether resin (a) used in the present invention is a phenylene ether resin in which the terminal group is functionalized by adding an alcoholic hydroxyl group to the terminal phenolic hydroxyl group. Specifically, a method invented by some of them and for which a patent application has been filed, specifically involves combining a phenylene ether resin and a functionalizing agent in the presence or absence of an organic solvent capable of thickening the phenylene ether resin.
It can be obtained by reacting at a temperature of 50 to 200°C using a basic catalyst.

(a) Phenylene ether resin The phenylene ether resin used in the present invention has the following formula: represents a halohydrocarbonoxy group, and Q2 each represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group. m is 10 or more It is a homopolymer or copolymer having the structure shown in (representing the number of ). Suitable examples of primary alkyl groups for Ql and Q2 include methyl, ethyl, n-propyl, n-butyl, n-amyl,
Isoamyl, 2-methylbutyl, n-hexyl, 2.3
-dimethylbutyl, 2-13- or 4-methylpentyl or heptyl. Examples of secondary alkyl groups are isopropyl, 5ec-butyl or 1-ethylpropyl. In many cases, Ql is an alkyl group or a phenyl group,
In particular, it is an alkyl group having 1 to 4 carbon atoms, and Q2 is a hydrogen atom.

Suitable phenylene ether resin homopolymers include:
For example, it is composed of 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include:
It is a random copolymer consisting of a combination of the above units and 2,3,6-drimethyl-1,4-phenylene ether units. Many suitable homopolymers or random copolymers are described in the patent literature. Phenylene ether resins containing molecular moieties that improve properties such as, for example, molecular weight, bath melt viscosity and/or impact strength are also suitable.

The molecular weight of the phenylene ether resin is usually such that the intrinsic viscosity at 30° C. in chloroform is about 02 to 08 dl/g.

Phenylene ether resins are usually prepared by oxidative coupling of the aforementioned monomers.6 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,
These include at least one heavy metal compound such as copper, manganese, cobalt, etc., usually in combination with various other substances.

(b) The hydroxyalkylated functionalizing agent and the hydroxyalkylated phenylene ether resin (a) obtained thereby can be used, for example, in the following (A
) to (E).

(A) Phenylene ether resin (II) is reacted with glycidol represented by the formula:
and m are the same as above. (n represents a number from 1 to 10) A method for producing a hydroxyalkylated phenylene ether resin (Japanese Patent Application No. 2-45653).

(B) General CH2 in phenylene ether resin (II)
-CH-CH, -X (nrs)\1 (wherein, X represents a halogen atom) is reacted with an epihalohydrin such as epichlorohydrin, and then the obtained terminal glycidyl-modified phenylene ether resin is hydrolyzed. , - A method for producing a hydroxyalkylated phenylene ether resin represented by the formula (in which Ql, Q2 and m are the same as above) (Japanese Patent Application No. 45653/1999).

(C) Phenylene ether resin (II), -119 formula % formula % [1 (wherein, R1 represents an alkylene group having 1 to 10 carbon atoms,
X is the same as above) halogenated alkyl alcohol, for example 2-
A method for producing a hydroxyalkylated phenylene ether resin represented by the formula (wherein Ql, Q2, m and R' are the same as above) by reacting chloroethanol or 3-chloro-1-propanol, etc. Ganpei No. 2-92998).

(D) reacting the phenylene ether resin (II) with an alkylene carbonate represented by the formula (in the formula, R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), such as ethylene carbonate or propylene carbonate,
- A method for producing a hydroxyalkylated phenylene ether resin represented by the formula (in which Q', Q2, m and R2 are the same as above) (Japanese Patent Application No. 2-45655).

(E) Phenylene ether resin (II) is reacted with an alkylene oxide represented by the formula (wherein R3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), such as ethylene oxide or propylene oxide, A method for producing a hydroxyalkylated phenylene ether resin represented by the formula (in which Ql, Q2, m and R3 are the same as above) (Japanese Unexamined Patent Publication No. 128021/1983).

Note that the organic solvents used here include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; These include heterocyclic compounds such as N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone.

Examples of the basic catalyst include alcoholades such as sodium methoxide and sodium ethoxide; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and alkali metal carbonates such as sodium carbonate and potassium carbonate.

The reaction amount ratio of the phenylene ether resin and the functionalizing agent used in these reactions is 1 to 50 mol of the functionalizing agent per 1 mol of the terminal phenolic hydroxyl group of the phenylene ether resin, and the amount of the basic catalyst used is: The amount is 05 to 50 parts by weight based on 100 parts by weight of the phenylene ether resin.

Hydroxyalkylated phenylene ether resins (IA) to (I) obtained by the methods shown in (A) to (E) above.
Among E), in the present invention, CIA having two or more alcoholic hydroxyl groups having different reaction activities and reactivities
+ or (I,) is preferred, (IA1 is particularly preferred).

(c) Mixed use The hydroxyalkylated phenylene ether resin used in the present invention may be used alone or as a mixture with an unmodified phenylene ether resin. The mixing ratio of the unmodified phenylene ether resin can be arbitrarily set depending on the mixing ratio with the epoxy group-containing olefin resin.Normally, the mixing ratio of the hydroxyalkylated phenylene ether resin and the unmodified phenylene ether resin is 100:0. A range of 610 to 00% by weight is preferred. If the proportion of the modified resin is less than 10% by weight, the effect of improving compatibility will be reduced, which is not preferable.

(2) Epoxy group-containing olefin resin (b) The epoxy group-containing olefin resin (b) used in the present invention is ethylene, propylene, butene-1, pentene-1, hexene-1,3-methylbutene-1,4- Methylpentene-1
, copolymerization of an α-olefin such as heptene-1 or octene-1 with an unsaturated monomer having an epoxy group, or graft polymerization of a single or copolymer of the α-olefin and an unsaturated monomer containing an epoxy group. An α-olefin polymer into which an epoxy group has been introduced can be used.

Examples of unsaturated monomers having an epoxy group include glycidyl methacrylate, butyl glycylate,
Examples include butyl glycidyl fumarate, propyl glycidyl maleate, and glycidyl acrylate.

In addition, during this copolymerization, other than the above-mentioned unsaturated monomer having an epoxy group, such as methyl acrylate, methyl methacrylate, or vinyl acetate, may be copolymerized in an amount not exceeding a majority amount. Furthermore, homopolymers of α-olefins, copolymers with different types of α-olefins, or composites thereof in which epoxy groups are introduced by oxidizing unsaturated bonds may also be used. It can be used as an epoxy group-containing olefin resin in the composition of the invention. For example, an epoxy group is introduced into a carbon-carbon unsaturated group present in an α-olefin by a well-known method, such as an oxidation reaction using hydrogen peroxide or organic perM (perbenzoic acid, performic acid, peracetic acid, etc.). corresponds to this.

Among these, glycidyl methacrylate is most preferable as an unsaturated monomer having an epoxy group to be copolymerized with α-olefin, and the content of the unsaturated monomer is such that the unsaturated child component is in the range of 1 to 20% by weight. , graft copolymerized with olefin resin or 0.1-1
It is copolymerized with an olefin monomer in a range of 5% by weight. Below this range, chemical activity is poor;
The compatibilizing ability is insufficient, and if it exceeds this range, problems may arise in the moldability and appearance of the final composition, which is not preferable.

The epoxy group-containing olefin resin used in the present invention may be used alone or in a mixture with an unmodified olefin resin. The mixing ratio of the unmodified olefin resin is determined by the epoxy group content of the epoxy group-containing olefin resin. That is, the mixing ratio can be set arbitrarily as long as the content of the epoxy group-containing monomer units in the mixture is 0.1% by weight or more.

Other additional components can be added to the resin composition according to the present invention. For example, adding well-known additives such as antioxidants, weather resistance improvers, nucleating agents, and flame retardants to olefin resins,
Known antioxidants, weatherability modifiers, plasticizers, fluidity modifiers, and the like can be used as additional components in the phenylene ether resin. In addition, the addition of organic/inorganic fillers and reinforcing agents, especially glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, and silica, improves rigidity, heat resistance,
This is effective in improving dimensional accuracy, etc. For practical purposes, various known colorants or dispersants thereof can be used.

Furthermore, impact strength improvers, especially styrene-butadiene copolymer rubber or its hydride, ethylene-propylene-
Addition of (diene) copolymer rubber, etc. is effective in improving the impact strength of the composition. The above-mentioned impact strength improvers may be used alone or in combination of two or more types.The blending amount of the impact strength improver varies depending on the target physical properties, but for example, In order to improve the balance between rigidity and impact strength, the amount is 5 to 30 parts by weight per 100 parts by weight of the resin component of the composition.

1 hill, 2, 2 bottoms, and the thermoplastic resin composition of the present invention has good compatibility regardless of the composition ratio of component (a), the modified phenylene niter resin, and component (b), the epoxy group-containing olefin resin. However, in view of the balance between mechanical strength and organic solvent resistance, the composition ratio of component (a) and component (b) is in the range of 10:90 to 90:10 by weight, preferably 20:80 to 80. 70 to 20, more preferably 30 to 70
It's 0-30.

If the modified phenylene ether resin is less than 10% by weight, the rigidity will not be sufficient, and if it exceeds 90% by weight, the organic solvent resistance will be poor, which is not preferable.

As the method of melt cross-mixing to obtain the thermoplastic resin composition of the present invention, any cross-crossing method generally used for thermoplastic resins can be applied. For example, after uniformly mixing the powdered or granular components together with the additives described in the additional ingredients section if necessary using a Henschel mixer, ribbon blender, type blender, etc., the mixture is subjected to axial or multi-axial kneading extrusion. It can be kneaded using a machine, roll, Banbury mixer, etc.

The molding method for the thermoplastic resin composition of the present invention is not particularly limited, and may include molding methods used for thermoplastic resins, such as injection molding, blow molding, extrusion molding,
Molding methods such as sheet molding, thermoforming, rotational molding, lamination molding, and press molding can be applied.

(Example) The components used are as follows.

Phenylene ether resin Poly (2,6-dimethyl-1,4-phenylene ether) prototyped by Nippon Polyether ■ has an intrinsic viscosity of 0.31 dI/g measured in chloroform at 30°C.
and 0.51d! ! /g (in the table, PPE [71] = 0.31, PPE [η co =
Q, abbreviated as 51).

Furthermore, it was modified by the following method.

Modified PPE-1 Phenylene ether resin 5 with intrinsic viscosity 0.31 dl/g
Add toluene at 5°C to 00g and heat to 100g under nitrogen atmosphere.
The solution was completely dissolved by stirring at 100'C. After adding 75 g of sodium ethoxide as a catalyst and 500 g of methanol to this liquid (6), 250 g of glycidol was added dropwise over 30 minutes. Furthermore, the mixture was stirred at 100'C for 7 hours. The reaction mixture was poured into methanol at 25°C to precipitate the hydroxyalkylated phenylene ether resin product.The product was separated in a furnace, washed twice with methanol, and then dried under reduced pressure at 80°C.

This hydroxyalkylated phenylene ether resin has an infrared absorption spectrum near 3.380 cm-'.
It showed absorption derived from hydroxyl groups. Furthermore, when the phenolic hydroxyl group of the terminal group was quantified, it was found that 90% had reacted.

The reaction rate of the terminal phenolic hydroxyl group of phenylene ether resin was reported in the Journal of Applied Polymer Science Applied Polymer Symposium.
r 5science: Applied Polymer
Symposium, vol. 34, (1978>, 1
The terminal phenolic hydroxyl groups before and after the reaction were quantitatively determined and calculated according to the method described on pages 03 to 117.

Modified PPE-2 In the same manner as in the production of modified PPE-1 except that a phenylene ether resin with an intrinsic viscosity of 0.51 dI/g was used,
A hydroxyalkylated phenylene ether resin was obtained.

When the phenolic hydroxyl group of the terminal group was quantified,
The reaction rate was 82%.

Modified PPE-3 Phenylene ether resin 4 with intrinsic viscosity 0.31 dI/g
00g was dissolved in chlorobenzene 4j2, then 44g of ethylene carbonate and 4g of potassium carbonate were added, and 1
Stirring was continued for 8 hours at 20°C.

After cooling the reaction solution, it was slowly poured into methanol 20I2 to precipitate the produced hydroxyalkylated phenylene ether resin. Precipitated polymer? After being separated, it was washed with 2 Cl of pure water, then washed twice with methanol I54, and dried under reduced pressure at 80°C.

This hydroxyalkylated phenylene ether resin exhibited an absorption considered to originate from hydroxyl groups near 3.600 cm-' in the infrared absorption spectrum. In addition, quantification of the phenolic hydroxyl groups in the terminal groups before and after the reaction revealed that 54% of the terminal groups had reacted.

Modified PPE-4 Phenylene ether resin 40 with intrinsic viscosity 0°31#/g
0g toluene 4! was added and stirred at 95° C. under a nitrogen atmosphere to completely dissolve the mixture. Subsequently, 800 g of 3-chloropropanol and 30 g of sodium ethoxide were added, followed by continued heating and stirring for 7 hours. The reaction mixture was poured into a large amount of methanol to precipitate the resulting hydroxyalkylated phenylene ether resin. Subsequently, the separated polymer was washed with water, further washed twice with methanol, and dried under reduced pressure at 85°C.

This hydroxyalkylated phenylene ether resin has an infrared absorption spectrum near 3.600 cm-'.
It showed absorption thought to be derived from hydroxyl groups. Furthermore, quantitative determination of the phenolic hydroxyl groups in the terminal groups before and after the reaction revealed that 64% of the terminal groups had reacted.

Epoxy group-containing olefin resin Mitsubishi Yuka's prototype: Glycidyl methacrylate (hereinafter abbreviated as GMA) was grafted onto propylene resin at 130°C for 3 hours using xylene as a solvent and benzoyl peroxide as an initiator. Polypropylene-GMA graft copolymer (GMA) obtained by polymerization and then dissolving and removing the GMA homopolymer with acetone
(abbreviated as GMA-PP in the table).

Propylene Resin A propylene resin (trade name: Mitsubishi Polypro MA3) manufactured by Mitsubishi Yuka ■ was used (abbreviated as PP in the table).

Examples 1 to 8 and Comparative Examples 1 to 6 According to the formulation shown in Table 1, predetermined amounts of each component were mixed at 280° using a Lab Blast Mill kneader manufactured by Toyo Seiki Seisakusho.
The mixture was melted and kneaded at C to form a composition, which was then pulverized using a pulverizer. This powder sample was pressure-molded at 280°C using a hydraulic compression molding machine manufactured by Toyo Seiki Seisakusho to form a sheet, which was used as a specimen for physical property evaluation.

Each physical property value and various properties were measured and evaluated as follows, and the results are shown in Table 1.

(1) Dispersion form A portion was cut out from the test piece, subjected to ion etching, and then the dispersed particle size was observed using a scanning electron microscope (S-2400, newly manufactured by Hitachi).

(2) Flexural modulus I SOR178-1974 Procedure 12
It was measured using an Instron J type tester according to (JIS K7203).

(3) Izot impact strength ISOR18O-1969 (JIS K7110)
Using an Izot impact tester manufactured by Toyo Seiki Seisakusho in accordance with the unnotched Izot impact strength, three 2 mm thick specimens were stacked and fixed with cellophane tape for measurement.

(4) Organic diathermist resistance Bergen's genus ellipse method [SPE Journal 667 (196
2)]. Specifically, a test piece with a thickness of 2 mm was fixed in a quarter-ellipse jig with a major axis of 24 cm and a minor axis of 8 cm, and was immersed in commercially available gasoline for 5 minutes. The strain was determined as the critical strain.

At this time, if no cracks occur, 0 (extremely good)
, those with a critical strain value of 1.5% or more are rated O (good), and 1.
It was judged as 0 to 1.5% Δ (fair) and less than 1.0% × (poor).

In addition, from the powdered sample, an injection molding machine manufactured by Custom Scientific (C5-183MMX MINI) was used.
MAX) at 280°C to injection mold a test piece with a width of 6.2 mm, a length of 32 mm, and a thickness of 3.2 mm, and examine the appearance of the test piece, focusing on the presence or absence of delamination. evaluated.

In this case, select ○ (good) if there is no problem in practical use. Something that is problematic (Bad) It was determined that Ta.

(Effect of the invention) As shown in the Examples and Comparative Examples, by blending both the hydroxyalkylated phenylene ether resin (a) and the epoxy group-containing olefin resin (b), it is possible to blend both of them at the same time. Compared to the comparative example in which no component (a It is clear that a thermoplastic resin composition having high rigidity, excellent organic solvent resistance, and mechanical strength was obtained, which combines the characteristics originally possessed by component (b) and component (b).

Claims (1)

[Scope of Claims] A thermoplastic resin composition comprising the following components (a) and (b) and the composition. (a) Hydroxyalkylated phenylene ether resin 1
0 to 90% by weight (b) Epoxy group-containing olefin resin 90 to 10% by weight