JPS6211763A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition significantly improved in melt-flow capability as well as with heat resistance, electrical properties, processability, etc., by incorporating polyphenylene ether resin with a cyclopentadiene resin carrying specific polar group. CONSTITUTION:The objective composition can be obtained by blending (A) 30-100pts.wt. of polyphenylene ether resin, (B) 0-70pts.wt. by styrene resin, (C) 3-100pts.wt. by per 100pts.wt. by of the components A plug B, of a polar group-carryoug cyclopentadiene resin prepared by either copolymerization between (i) 100pts.wt. by of a conjugate double band-contg. five-membered ring compound of formula (H is hydrogen; R is 1-3C alkyl ; m and n are each 0 or >=, m+n=6) and/or its Diels-Alder adduct, pref. cyclopentadiene and (ii) 1-50pts.wt. by of compound having both C=C bond and polar group such as hydroxyl or carboxyl group (e.g., acrylic acid) or reaction between a polymer from the component (i) and the component (ii) and (D) 0-200pts.wt. by per 100pts.wt. by of the components A plus B plus C, of inorganic filler.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a novel resin composition containing polyphenylene ether, and more specifically to a novel resin composition containing a cyclopentadiene resin containing a polar group and polyphenylene ether. The present invention relates to a molding resin composition containing the present invention.

The novel resin composition of the present invention maintains the inherent properties of polyphenylene ether, such as good melt flowability and excellent mechanical and thermal properties of molded products,
The present invention provides a material suitable as a molding material.

[Prior art] Polyphenylene ether is a thermoplastic resin with excellent heat resistance, mechanical properties, electrical properties, etc.
No. 6800 and US Pat. No. 3,306,874. However, when used as a molding material, the softening point of polyphenylene ether itself is too high, resulting in poor moldability, and its excellent properties could not be utilized.

Therefore, it has been proposed to add impact-resistant polystyrene to polyphenylene ether in order to improve its moldability, and the resin compositions obtained in this way are used industrially (Tokuko Showa). No. 42-226'69, U.S. Patent No. 3.383
．． Publication No. 435). However, the melt fluidity of this resin composition cannot be said to be sufficient.

It has been proposed8 to add a low molecular weight hydrocarbon resin to polyphenylene needle in order to further improve the melt fluidity (Japanese Patent Publication No. 13584/1984, Japanese Patent Publication No. 11/1983).
No. 29050, Special ml No. 1982-129051, Japanese Patent Application Publication No. 159-126460, and Japanese Patent Publication No. 47-31
Publication No. 36). The low molecular weight hydrocarbon resins mentioned here mean aromatic petroleum resins obtained from petroleum naphtha, cyclopentadiene resins, aromatic/cyclopentadiene copolymer resins, coumaron-indene resins obtained from coal tar, etc. [Problems to be Solved by the Invention] Although it has been observed that the fluidity of molten F11 is improved by adding these low molecular weight hydrocarbon resins, it is still not sufficient and further improvement is required.

In particular, when it contains inorganic fillers such as glass fillers,
Further improvements are needed.

An object of the present invention is to provide a resin composition with improved melt flowability without degrading the excellent mechanical, electrical and thermal properties of polyphenylene ether itself.

[Means for Solving the Problems] As a result of intensive studies by the present inventors regarding the improvement of polyphenylene ether as described above, the inventors of the present invention have found that a cyclopentadiene resin containing phenolic water (V) is added to polyphenylene ether. The present inventors have discovered that the present invention provides heat resistance, electrical properties, additivity, etc., and greatly improves melt fluidity, and that this effect is noticeable even when a T11-free filler is included. .

That is, the present invention includes (a) 30 to 100 parts by weight of polyphenylene ether resin (b) styrene resin O to 101 hanging parts (
C) - General formula [wherein H represents hydrogen, R represents an alkyl group having 1 to 3 carbon atoms, and m and n are 0 or an integer of 1 or more;
= 5] A 5-membered ring compound having a conjugated double bond and/
or its Diels-Alder adduct [component A) 10
(A compound containing a la moiety, water MiJ, a polar group selected from a carboxyl group, a carboxylic acid anhydride group, an ester group, a nitrile group, and an amide group, and a carbon-carbon double bond [
Component B) obtained by copolymerizing 1 to 50 parts by weight, or by reacting 1 to 50 parts by weight of the above (component B) with 100 parts by weight of the resin obtained by polymerizing the [Component A]. The polar Ls-containing cyclopentadiene resin (a)
+ 3 to 100 parts by weight based on 100 parts by weight of total a of (b) and (d) inorganic filler (a) + (b) +
A polyphenylene ether resin composition for molding processing is provided, comprising 0 to 200 parts by weight based on 100 parts by weight of the total fi of (c).

[Detailed Description of the Invention] The polyphenylene ether as component (a) used in the composition of the present invention has the general formula [wherein R, R11, R, R5 and R6 are the same or different tert-butyl groups] Alkyl group having 1 to 4 carbon atoms, aryl group, halogen atom or hydrogen atom, etc. excluding R and R6 are not hydrogen atoms at the same time] The repeating unit is the one represented by
) or a homopolymer consisting of [I] and [II] can be used.

A specific example of the homopolymer of polyphenylene ether is poly(2,6-cymethyl-1,4-phenylene)
Ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4
-phenylene)ether, poly(2-ethyl-5-n-
Propyl-1°4-phenylene)ether, poly(2,
6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-5-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-itubrobyl-1,4-phenylene) ether, poly(2-methyl-
6-chloro-1,4-phenylene)ether, poly(2
-Methyl-6-hydroxyethyl-1,4-phenylene)ether, poly(2-methyl-6-chloroethyl-1)
, 4-phenylene) ether and the like.

The preferred degree of polymerization of the polyphenylene ether resin used in the resin composition of the present invention is a number average degree of polymerization in the range of 45 to 45G. If the number average degree of polymerization is less than 45, the mechanical properties of the resin composition will deteriorate, which is undesirable.
If it exceeds 0, moldability will be significantly reduced, which is not preferable.

This polyphenylene ether resin can be subjected to lff1 by a known method, for example, the method described in Japanese Patent Publication No. 36-1869.

The styrene resin as component (b) used in the composition of the present invention has the general formula [wherein R is a hydrogen atom, a lower alkyl group, or a halogen atom, 2 is a lower alkyl group, a hydrogen atom, or a halogen atom] p is an integer of 1 to 5]. Examples of such polymers include styrene, α, -Methylstyrene, vinyltoluene, vinylethylpenzene, vinylxylene, p-methylstyrene,
L! such as tert-butylstyrene, chlorstyrene, etc.
Examples include those obtained by homopolymerization or copolymerization of at least one selected from among conventional polymers, and if necessary,
Use of copolymers obtained by copolymerizing the above-mentioned structural monomers with at least one selected from other single S bodies, such as acrylonitrile, methyl methacrylate, methacrylate trile, maleic anhydride, etc. Although it is possible, it is desirable that the content of structural monomer units in this copolymer be 10% by weight or more, preferably 90% or more,
Further, copolymers having a composition other than the above are undesirable because they lower the compatibility with polyphenylene ether and lower the mechanical properties of the resin composition.

For example, polystyrene, polychloro[1-styrene, rubber-modified polystyrene (high-impact polystyrene), styrene-
Examples include acrylonitrile copolymer, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, and styrene-α-methylstyrene copolymer. Among them, impact-resistant polystyrene is preferably used, and these include rubber-modified polystyrene modified with one lastomer such as polybutadiene, butadiene-styrene copolymer rubber, and EPDM. Such rubber-modified polystyrene refers to a resin containing a two-phase system in which an elastic phase is dispersed in the form of particles in a polystyrene resin matrix. Such resins can be formed by mechanically mixing an elastomer with a polystyrene resin, or even by copolymerization of an elastomer with a styrenic monomer, with particular preference given to the latter method. These resins are preferably used. Industrially, rubber-modified polystyrene resins are usually produced by graph l-ffi combination of styrenic monostates in the presence of an elastomer.

The cyclopentadiene resin containing a polar group as component (C) used in the composition of the present invention has the general formula [wherein H is hydrogen, R represents an alkyl group having 1 to 8 carbon atoms, m and n is O or an integer greater than or equal to 1, and is m+n-6] 5-membered ring compound having a conjugated double bond and/or its Diels-Alder adduct [Component A]
For 1 part of 100fiff, hydroxyl group, carboxyl group, carboxyl Iff anhydride group, ester group, nitrile group,
1 to 50 parts by weight, preferably 2 to 40 parts, of a compound [component B] containing a polar group selected from amide groups and a carbon-carbon double bond are polymerized, or [component A] is polymerized. [Component B]
) produced by reacting 1 to 50 parts by weight, preferably 2 to 4 parts by weight. The [component A] and [component B]
The copolymerization can be carried out at a reaction temperature of 150 to 300°C, preferably 200 to 280°C, and a reaction time of 10 minutes to 20 hours, preferably 1 hour to 10 hours.

In addition, the homopolymerization of [Component A] requires a reaction temperature of 150 to 30
0℃, preferably 200-280℃, reaction time 1fi
The reaction time is 10 minutes to 20vfill, preferably 1 hour to 10 hours, or the reaction temperature is 0 to It can be carried out at 80°C, preferably in the range of 20 to 50°C.

Next, the conditions for reacting (component B) with the polymer of [component A] are such that the reaction temperature is 100 to 300°C, preferably 150 to 300°C.
250°C, reaction time 10 minutes to 20 hours, preferably 1
It can be carried out for a period of up to 10 hours.

When carrying out the copolymerization reaction of [Component A] and [Component B] or the homopolymerization of [Component A], aromatic hydrocarbons such as benzene, toluene, and coconut are used as a solvent for [Component A] + [
Component B] or [Component A] 5 to 100 parts
This can be carried out by containing 100 parts by weight. Also,
After the polymerization reaction, the solvent is removed from the reaction product by a conventional method such as distillation, and unreacted monomers and low polymers may be removed if necessary. Particularly when maleic anhydride is used as (component B), it is advantageous to homopolymerize [component A] and then react with [component B].

Examples of the above-mentioned [Component A] include cyclopentadiene and methylcyclopentadiene, and Diels-Alder adducts thereof include dicyclopentadiene,
Cyclopentadiene-methylcyclopentadiene, tricyclopentadiene, etc., and mixtures thereof are preferably used industrially, and among these, cyclopentadiene, dicyclopentadiene, or a mixture of both is particularly preferred. .

Although it is not necessary that cyclopentadiene, dicyclopentadiene, or an alkyl-substituted derivative thereof be of high purity, it is preferable that cyclopentadiene, dicyclopentadiene, or an alkyl-substituted derivative thereof is present in an amount of 80% or more. In addition, by thermally dimerizing cyclopentadiene and methylcyclopentadiene contained in the C5 fraction of high-humidity heat content wI by-product oil such as naphtha, dicyclopentadiene, dimethylcyclopentadiene, cyclopentadiene- After making a mixture of methyl cyclopentadiene co-diazole, cyclopentadiene-isobrene co-diazine, cyclopentadiene-biberylene co-diazine, etc.
Distillation produces C5 olefins, C5 paraffins, etc.
It is also possible to use a concentrated fraction obtained by removing most of the components.

The above (component B) is a compound containing a polar group selected from a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, an ester group, a nitrile group, and an amide group, and a carbon-carbon double bond. The compounds preferably range from 3 to 12 carbon atoms.

Among these compounds, those having a hydroxyl group include allyl alcohol, butynediol, crotyl alcohol, hexenediol, and other unsaturated alcohols, and those having a carboxyl group include acrylic acid,
Unsaturated acids such as methacrylic acid, crotonic acid, maleic acid and itaconic acid; acid anhydrides such as maleic anhydride and itaconic anhydride having a carboxylic anhydride group; vinyl acetate having a Nisder group; Unsaturated Nisdel such as vinyl propionate, methyl acrylate, methyl protonate, methyl methacrylate, ethyl acrylate, and butyl acrylate, and natural unsaturated esters such as linseed oil and tung oil; those having a nitrile group include acrylonitrile; Nitriles such as methacrylonitrile and crotonitrile, and those having an amide group include acid amides such as acrylamide and methacrylamide.

In addition, when producing the above-mentioned cyclopentadiene resin, unsaturated components in the petroleum fraction, especially unsaturated aromatic components, are removed from the component (
It is also possible to use them together within the range of 3 or less, such as a).

For example, styrene, α-methylstyrene, vinyltoluene, indene, methylindene, and mixtures thereof can be used, and from an industrial perspective, the so-called C9 fraction, which is produced as a by-product during the decomposition of naphtha and the like, is preferred.

It is also possible to hydrogenate the resin and use it to improve the hue or odor.

The cyclopentadiene resin used in the present invention is prepared by the ring and ball method (
It is necessary that the softening point measured according to JIS K 2531-60 is 100°C or higher, preferably 120'' to 200°C, particularly 1300 to 180°C. If it is lower than 100°C, the heat distortion temperature of the polyphenylene ether composition will drop significantly, and the inherent properties of the polyphenylene ether as a molded product will be significantly deteriorated, which is not preferable.

The inorganic filler (d) used in the composition of the present invention refers to powdered fillers, such as oxides such as iron oxide, alumina, magnesium oxide, calcium oxide, and zinc white; aluminum hydroxide, magnesium hydroxide, and bases. Hydration base R oxides such as magnesium carbonate, calcium hydroxide, tin oxide hydrate, zirconium oxide hydrate, etc. Charcoal salts such as calcium carbonate, magnesium carbonate, etc.: talc, clay, bentonite, attapulgite Silicates such as; borates such as barium borate, zinc borate etc; phosphates such as aluminum phosphate, sodium tripolyphosphate etc; sulfates such as gypsum etc.: sulfite M
Salt: Il fibrous fillers, such as glass fibers, potassium titanate fibers, metal-coated glass iam, ceramic fibers,
Examples include wollastonite, carbon fiber, metal carbide fiber, metal cured product 11111, etc., as well as spherical objects such as glass beads, glass balloons, and shirasu balloons, glass powder, glass flakes, metal flakes, and mica. Further, the surface of the inorganic filler may be treated with a silane compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, or the like. Among these, fibrous materials, particularly glass m-fibers, are preferred. These inorganic fillers can be used alone or in a mixture of two or more.

The resin composition of the present invention contains 30 to 10,041 parts of the polyphenylene ether of component (a), preferably 40 to 80 parts.
Part (3), the styrene resin of component (b) O-701 part, preferably O-60 part, component (C), the polar group-containing cyclopentadiene resin, is a mixture of components (a) + (b). Amount 1
3 to 100 parts by weight, preferably 5 to 100 parts by weight
60 parts, the inorganic filler of component (d) is the component (a)
+ (b) + (c) total ω100 heavy weight part heavy weight 0
It may be blended in a proportion of 0 to 200 parts, preferably 0 to 150 parts.

Compositions of the invention can be prepared in any conventional manner. For example, the components may be heated to a temperature at which they can be mixed and dispersed, and mixed using an extruder, kneader, Banbury mixer, or the like.

The resin composition of the present invention has superior melt flowability compared to commercially available modified polyphenylene ether resins, which are mixtures of polyphenylene ether and high-impact polystyrene, and therefore has good moldability. It is characterized by retaining the excellent thermal, mechanical, and electrical properties inherent to ether.

Various molded products can be obtained from the polyphenylene ether resin composition of the present invention by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, and the like.

In addition, known antioxidants, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, blowing agents, etc. that are commonly used in the polyphenylene ether resin composition of the present invention can be added.

[Examples] Examples are shown below to specifically clarify the content of the present invention, but these are just a few examples, and the present invention is limited to these examples unless it goes against the spirit thereof. It's not a thing.

Synthesis Example 1 560 g of dicyclopentadiene with a purity of 96%, 140 J of vinyl acetate and 300 g of mixed xylene were heated and reacted in an autoclave at 260° C. for 4 hours under lυ. After the reaction was completed, the autoclave was cooled, and the contents were distilled to remove unreacted Upper Zimmer 1 low polymer and xylene, and 595 g of Resin I was obtained as a residue. Resin■
It had a softening point of 145.0°C and was found to contain 5 Nisdel groups by infrared scanning.

Synthesis Example 2 525 g of dicyclopentadiene with a purity of 96%, 175 g of methyl methacrylate (MMA)! J and 300 g of mixed xylene were reacted in an autoclave with stirring at 260° C. for 3 hours, and treated in the same manner as in Synthesis Example 1 to obtain 567 g of resin (2). The softening point of resin ■ is I at 138.0°C.
The presence of an ester bond was confirmed from the R spectrum.

Synthesis example 3 490 g of dicyclopentadiene, 21 g of allyl alcohol
0 g and 300 g of mixed xylene were placed in an autoclave, heated and reacted at 270° C. for 4 hours, and treated in the same manner as in Synthesis Example (2) to obtain 560 g of resin (2). The softening point of resin (■) is 132°0°C, and the hydroxyl value is 210 (4KO1l/
g).

Synthesis Example 4 700 g of dicyclopentadiene and 30 g of mixed xylene
09 was placed in an autoclave, reacted at 260°C for 2 hours, and treated in the same manner as in Synthesis Example 1 until the softening point was 140.5°C.
546g of resin was obtained. This resin was melted by heating at 200°C, 54.0g of maleic anhydride was added, and the reaction was allowed to proceed for 2 hours.The softening point was 181.0°C and the acid value was 56.0 (#
l! A resin (2) with J of OH/9> was obtained.

Synthesis Example 5 Dicyclopentadiene 6655J, I water maleic acid 35
300 g of mixed xylene 9 and d was charged into an autoclave, heated and reacted at 260° C. for 3 hours, and treated in the same manner as in Synthesis Example 1 to obtain 553 g of resin V.

tree 111fV (1: other point c 140.0℃ri[127,
5 (JR9KOII/g).

Synthesis Example 6 560 g of dicyclopentadiene, 140 g of acrylic l, and 300 g of U-combined xylene were placed in an autoclave and reacted by heating at 260° C. for 4 hours, followed by treatment in the same manner as in Synthesis Example 1 to obtain 518 g of resin VtIfi. The softening point of resin ■ is 135.0℃ and the acid value is 15.4 (011/1 for ■).
Met.

Synthesis Example 7 Dicyclopentadiene 560g, acrylonitrile 14
300 g of xylene and mixed xylene were placed in an autoclave, heated and reacted at 260° C. for 3 hours, and treated in the same manner as in Synthesis Example 1 to obtain 525 g of resin (2).

The softening point of the resin Vl was 130.5°C, and nitrile male absorption was observed in the IR spectrum.

Next, a polyphenylene ether resin composition was prepared by the following method using the resins obtained in Synthesis Examples 1 to 7 above and the control resin, and physical property tests were conducted. The results are shown in Table 1.

[Preparation of composition] The ingredients were mixed in a Henschel mixer, and the cylinder temperature was 2.
The mixture was melted into pellets using a twin-screw extruder at 80 to 300°C. This pellet was molded using an injection molding machine with a cylinder temperature of 250 to 300°C to obtain a test piece.

[Physical property test] i) Melt index = Measured at 260°C and 10Ky.

11>Tensile strength and elongation: Tested using a No. 5 dumbbell according to ASTM-D-638.

1ii) Notched Izo impact strength; ASTM-D-
256 using a test piece measuring 1/8 x 1/2 x 21/2 inches.

iV) Thermal change J[[Iu:ASTM-D-648Lt%U
T18, carried out under a pressure of 6/(g/Cd).

Note 1) Polyphenylene ether; 25% in chloroform
Poly(2,6
-Simethyl-1,4-phenylene) ether 2) Styrene resin; manufactured by Mitsubishi Monsanto Chemical Industries, Ltd. I-impact resistant polystyrene "Dialext + TJ (trade name) 3) Inorganic filler; Nittobo (manufactured by I4, chopped glass rO8-4713J) - 4) Control resin: Aromatic hydrocarbon resin "Vetrozin 150J (trade name), manufactured by Mitsui Petrochemicals (trade name)" As shown in the above results, the compositions of Examples 1 to 14 have significantly improved dissolution/flowability.

Claims (1)

[Claims] (a) 30 to 100 parts by weight of polyphenylene ether resin (b) 0 to 70 parts by weight of styrene resin (c) General formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, H is hydrogen, R represents an alkyl group having 1 to 3 carbon atoms, m and n are integers of 0 or 1 or more, and m+n=
6] A 5-membered ring compound having a conjugated double bond and/
or its Diels-Alder adduct [component A] 10
0 parts by weight, and a compound containing a polar group selected from a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, an ester group, a nitrile group, and an amide group and a carbon-carbon double bond [Component B] 1 to 50 parts by weight or by reacting 1 to 50 parts by weight of the above [component B] with 100 parts by weight of the resin obtained by polymerizing the above [component A]. )+(
3 to 100 parts by weight based on 100 parts by weight of the total amount of b), and 0 to 200 parts by weight of the inorganic filler (d) based on 100 parts by weight of the total amount of (a) + (b) + (c). A polyphenylene ether resin composition for molding processing.