JP3336094B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether resin composition having a good balance of impact resistance, molding appearance and molding workability.

[0002]

2. Description of the Related Art Polyphenylene ether resin (hereinafter referred to as P
Sometimes PE. ) Is a resin excellent in heat resistance, mechanical strength, electrical properties, etc., but has insufficient molding workability and impact resistance, and generally contains rubber-reinforced polystyrene resin (HIPS) as an improved product. It is used. However, rubber-reinforced polystyrene used in PPE cannot increase the rubber content due to restrictions in the production process, and generally has a rubber content of 5-1.
It is as low as about 0% by weight. Therefore, sufficient impact resistance cannot be imparted to PPE. To compensate for this drawback, hydrogenated styrene-butadiene-styrene block copolymers (hereinafter referred to as SEBS) have been studied. However, they have the effect of improving the impact resistance but have a problem of poor molded appearance.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a PPE composition having a good balance of impact resistance, molding appearance and molding workability by using a hydrogenated block copolymer having a specific structure. The purpose is to:

[0004]

According to the present invention, there are provided (a) 1 to 99% by weight of a polyphenylene ether resin, and (b)
(A) 37 to 70 % by weight of a block segment composed of a vinyl aromatic compound polymer, (B) 65 to 100% by weight of a conjugated diene compound having a 1,2-vinyl bond amount of 30% by weight or more, and other monomers 35 (C) 5 to 30% by weight of a polybutadiene block segment having a 1,2-vinyl bond content of less than 30% by weight (provided that (A) + (B) +
(C) = 100% by weight] and a hydrogenated block copolymer 1 in which the double bond of the conjugated diene portion is saturated by 80% or more.
A total of 1 to 99 parts by weight of (a) polyphenylene ether resin and (c) 99 to 0 parts by weight of a polystyrene resin; To 1% by weight of a resin composition. Hereinafter, the present invention will be described in detail.

[0005] [1] (A) block segments (b) Description of the hydrogenated block copolymer of component (B) component of the present invention consists of a vinyl aromatic compound polymer, 37 to at (b) component 70 weight
%, Preferably in the range of 38 to 60% by weight. (A) block is poor molding appearance is less than 37% by weight, also unfavorably poor effect of improving impact resistance of the more than 70 wt%.

(A) The vinyl aromatic compound constituting the block includes styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene,
Examples thereof include 1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, and vinylpyridine, and styrene and α-methylstyrene are particularly preferable.

The weight average molecular weight of the block (A) is not particularly limited, but is preferably from 1.5 to 300,000.
If it is less than 15,000, the molded appearance is inferior.

The (B) block segment of the component (B) comprises a polymer mainly composed of a conjugated diene compound.
It is desirable that the amount is in the range of 15 to 60% by weight, preferably 20 to 60% by weight, particularly preferably 25 to 55% by weight in the component. When the content of the block (B) is less than 15% by weight, the effect of improving the impact resistance is poor.

(B) The conjugated diene compound constituting the block includes 1,3-butadiene, isoprene, 2,3
-Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene,
Examples include 3-butyl-1,3-octadiene, chloroprene, and the like, but 1,3-butadiene, isoprene,
1,3-pentadiene is preferred, and particularly preferred is 1,3-pentadiene.
3-butadiene. These conjugated diene compounds include 1
Species or two or more species may be used.

It is desirable that the conjugated diene compound constituting the block (B) has a 1,2-vinyl bond content of 30% or more, and if it is less than 30%, the effect of improving impact resistance is inferior. Further, the conjugated diene compound in the block component (B) is desirably in the range of 65 to 100% by weight, and if it is less than 65% by weight, the effect of improving impact resistance is poor, which is not preferable. (B) Examples of the other monomer constituting the block include a vinyl aromatic compound and an acrylic monomer, and styrene, isoprene, butyl acrylate and the like are preferable. (B) The other monomer in the block component is 3
The content is desirably in the range of 5 to 0% by weight. In the case of a vinyl aromatic compound, if it exceeds 35% by weight, the effect of improving impact resistance is poor, which is not preferable. (B) The weight average molecular weight of the block is not particularly limited, but is preferably from 10,000 to 300,000.

[0011] (ii) component (C) block segment is a polybutadiene block segment (b)
5 to 30% by weight of the component, preferably 5 to 20% by weight,
Particularly preferably, it is 10 to 20% by weight. If it is less than 5% by weight or more than 30% by weight, the impact resistance is inferior.

(C) The block segment is a polybutadiene block segment having a 1,2-vinyl bond content of less than 30% by weight, preferably less than 20% by weight,
Particularly preferably, it is less than 15% by weight. If the content is 30% by weight or more, the impact resistance is poor, which is not preferable.

The weight average molecular weight of the block (C) is not particularly limited, but is preferably from 150,000 to 150,000. If it is less than 10,000, the effect of improving the impact resistance is inferior, and if it exceeds 150,000, the molded appearance is inferior, which is not preferable.

The component (b) comprises the components (A), (B),
(C) block is ABC or (CBA)
n-Z (Z is a residue of a coupling agent, n is an integer of 2 or more)
Is a hydrogenated block copolymer in which a block is formed in a linear or branched form and a double bond of a conjugated diene portion is hydrogenated. The degree of hydrogenation is usually 80% or more, preferably 90% or more, and particularly preferably 95% or more. If it is less than 80%, the effects of improving heat resistance, weather resistance, molded appearance, and impact resistance are not preferred.

The coupling agent is not limited, but may be divinylbenzene, tetrachlorosilane, methyldichlorosilane, butyltrichlorosilane, (dichloromethyl) trichlorosilane, (dichlorophenyl) trichlorosilane, 1,2-bis (trichlorosilane). Silyl) ethane, hexachlorodisilane, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, 1,2
-Dibromoethane, tolylene diisocyanate, diethyl adipate, epoxidized linseed oil and the like.

The weight average molecular weight of the hydrogenated block copolymer as the component (b) is not particularly limited, but may be from 4 to 4.
750,000 is preferred. If it is less than 40,000, the effect of improving impact resistance is inferior, and if it exceeds 750,000, molding processability is inferior, which is not preferable. The component (b) is obtained by converting the above component (b) to an acid anhydride group,
A modified hydrogenated block copolymer modified with an unsaturated compound having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, an oxazoline group, and an epoxy group may be used.

[2] Description of Component (A) Polyphenylene Ether Resin of the Present Invention As the component (a) polyphenylene ether-based resin (PPE) used in the present invention, known ones can be used. The polyphenylene ether-based resin has, for example, the general formula:

[0018]

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(Wherein Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and at least two carbon atoms between the halogen atom and the phenyl ring) A haloalkyl or haloalkoxy group having an atom and a monovalent substituent selected from those containing no tertiary α-carbon, and q is an integer representing the degree of polymerization.) Thus, the polymer represented by the above general formula may be a single polymer or a copolymer of two or more polymers.

The method for producing PPE is not particularly limited. For example, US Pat. No. 3,306,874 and US Pat. Nos. 3,257,357 and 3,25.
It can be produced by the reaction of phenols according to the procedure described in US Pat. No. 7,358.

These phenols include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dimethylphenol,
Dibutylphenol, 2,6-dilaurylphenol,
2,6-dipropylphenol, 2,6-diphenylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-cyclohexylphenol, 2-methyl-6
-Tolylphenol, 2-methyl-6-methoxyphenol, 2-methyl-6-butylphenol, 2,6-dimethoxyphenol, 2,3,6-trimethylphenol, 2,3,5,6-tetramethylphenol and 2 , 6-diethoxyphenol, but is not limited thereto. Each of these may be reacted alone to the corresponding homopolymer, or reacted with another phenol to the corresponding copolymer having different units encompassed by the above formula.

Specific examples include poly (2,6-dimethylphenylene-1,4-ether), poly (2,6-diethylphenylene-1,4-ether) and poly (2,6-dimethylphenylene-1,4-ether).
Dibromophenylene-1,4-ether), poly (2-
Methyl-6-ethylphenylene-1,4-ether),
Poly (2-chloro-6-methylphenylene-1,4-ether), poly (2-methyl-6-isopropylphenylene-1,4-ether), poly (2,6-di-n-propylphenylene-1) , 4-ether), poly (2-chloro-6-bromophenylene-1,4-ether), poly (2-chloro-6-ethylphenylene-1,4-ether), poly (2-methylphenylene-1) , 4-ether), poly (2-chlorophenylene-1,4-ether), poly (2-phenylphenylene-1,4-ether), poly (2-methyl-6-phenylphenylene-
1,4-ether), poly (2-bromo-6-phenylphenylene-1,4-ether), poly (2,6-methylphenylphenylene-1,4-ether), poly (2,3,6- Trimethylphenylene-1,4-ether) and the like.

In a preferred embodiment, Q ¹ and Q ² are an alkyl group having 1 to 4 carbon atoms, and Q ^{3 and} Q ⁴ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. For example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-)
1,4-phenylene) ether, poly (2-methyl-6)
-Propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether and the like.

As the PPE copolymer, there may be mentioned a copolymer in which the above-mentioned polyphenylene ether repeating unit partially contains an alkyl trisubstituted phenol, for example, 2,3,6-trimethylphenol. Further, a copolymer in which a styrene compound is grafted to these PPEs may be used. The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing, for example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, or the like as the styrene-based compound on the PPE.

The component (c) polystyrene resin (PS) used in the present invention is known per se and has a general formula:

[0026]

Embedded image

Wherein R 'is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z is a halogen atom or a substituent having 1 to 4 carbon atoms,
Is an integer of 0 to 5. ) The polymer must have at least 25% by weight or more of the repeating structural unit derived from the aromatic vinyl compound represented by the formula (1).

Examples of such a styrene polymer include styrene or a derivative thereof, for example, p-methylstyrene, α
-Methylstyrene, α- methyl -p - methylstyrene,
Homopolymers and copolymers such as chlorostyrene and bromostyrene are exemplified.

Further, the above-mentioned aromatic vinyl compound is
Rubber-modified polystyrene (hereinafter, sometimes referred to as HIPS) composed of up to 99% by weight and 1 to 30% by weight of a diene rubber can be used. Examples of the diene rubber constituting HIPS include homopolymers of conjugated diene compounds such as butadiene, isoprene and chloroprene, copolymers of conjugated diene compounds and unsaturated nitrile compounds or aromatic vinyl compounds, and also natural rubber. And one or more of them can be used. Particularly, polybutadiene and butadiene-styrene copolymer are preferred. HIPS is obtained by a method of emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization or a combination thereof.

In the resin composition of the present invention, component (a)
The mixing ratio of PPE and component (c) PS is (a) 1 to 10
(C) 99 to 0 parts by weight with respect to 0 parts by weight.
The usage ratio of (A) or (A) + (C) and the (B) component is usually (A) + (C) / (B) = 1 to 99% by weight /
It is 99 to 1% by weight, and can be applied in a wide range from a hard resin to a soft resin. (A) or (A) + (C) and (B) when the resin composition of the present invention is used as a hard resin.
Is preferably (A) + (C) / (B) = 30 to 99% by weight / 70 to 1% by weight, more preferably 40 to 99% by weight / 60 to 1% by weight. Is within. If (b) is less than 1% by weight, the effect of improving the impact resistance is inferior, which is not preferable. When the content exceeds 99% by weight, the performance of the composition obtained is almost the same as the performance of (b) alone, and there is no meaning as a composition.

Further, the resin composition of the present invention may be mixed with other optional components as long as properties such as good molding appearance and impact resistance are not lost. The mixing ratio is (a) + ( B) +
(C) = 0 to 150 parts by weight with respect to 100 parts by weight.

Examples of the optional component include, for example, SBS, SEBS, SIS, SEP
S, EPM, EPDM, EMB, acrylic rubber, ionomer, thermoplastic polyurethane, polyamide elastomer, polyester elastomer, silicone rubber, silicone rubber copolymer, hydrogenated SBR, and the like. Examples of the thermoplastic resin include 1, 2-polybutadiene, polybutene-1, polyethylene (HDPE, LDPE, LL
DPE), EVA, EVA-modified polymer, ethylene-ethyl acrylate copolymer, polypropylene, ethylene-based copolymer, PPS, polycarbonate, polyamide, polyester, PMMA, crystalline polystyrene, polystyrene, styrene-acrylonitrile copolymer, HIPS, ABS , AES, MBS and other styrene resins, and these may be used alone or in combination of two or more.

Further, in addition to the above, an antioxidant, an ultraviolet absorber, a heat stabilizer,
Stabilizers such as light stabilizers, antistatic agents, lubricants, plasticizers, plasticizers, glass fibers, metal fibers, metal flakes, carbon fibers, calcium carbonate, silica, talc, clay, mica, whisker titanate, zinc oxide , A reinforcing material such as titanium oxide, magnesium carbonate, and carbon black, a filler, a coloring agent, a pigment, a dye, a flame retardant, and the like.

The method for producing the resin composition of the present invention is not particularly limited, and a generally known method can be employed. That is, after the compounds of the component (a) PPE, the component (c) PS, and the component (b) are uniformly mixed in a pellet, powder, or strip state using a high-speed stirrer or the like, a uniaxial having sufficient kneading ability is obtained. Alternatively, various methods such as a method of melt-kneading with a multi-screw extruder or a method of melt-kneading with a Banbury mixer or a rubber roll machine can be adopted.

The resin composition of the present invention thus obtained can be formed into various molded articles by injection molding, sheet extrusion molding, vacuum molding, profile extrusion molding, foam molding, blow molding, stampable molding and the like. . The obtained molded article can be used for exterior and interior members of automobiles, various electric / electronic parts, housings, etc. by utilizing its excellent properties.

[0036]

The present invention will be described more specifically with reference to the following examples. The examples are representative of the invention,
It does not limit the scope of the invention. The hydrogenated block copolymers shown in Tables 1, 2, 3 and 4 were mixed at the compounding ratios shown in the same table using a twin-screw extruder at 270 to 320 ° C.
The mixture was kneaded and pelletized at 00 rpm, and injection molding and performance evaluation were performed by the following methods.

[0037] A-1 of component (i) used in Examples and Comparative Examples are 2,6-xylenol, bromide second as catalyst
This is a polyphenylene ether obtained by performing a polymerization reaction using copper and di-n-butylamine in a toluene solution at 30 ° C. while blowing oxygen. ( A ) Component A-
No. 2 is a blend of A-1 / polystyrene [manufactured by Mitsui Toatsu Co., Ltd., Toporex 500-51] = 50/50% by weight. ( A ) Component A-3 is A-1 / HIPS
[Kuflex HF-76, manufactured by Mitsubishi Polytec Corporation]
= 50/50 wt% blend.

Evaluation method of impact resistance 270 to 3 using an injection molding machine (Nissei PS40E5A)
At a molding temperature of 20 ° C., a 3.2 mm-thick test piece was prepared and subjected to a notched Izod impact test in a 23 ° C. environment. When the Izod impact energy exceeds 200 J / m, it can be used practically and is preferable.

Evaluation Method of Mold Appearance Using an injection molding machine (Toshiba IS125CN II), the injection speed was set so that the shear rate when passing through the gate was 10,000 1 / sec. After molding, the appearance of the molded article was visually evaluated. A: The molded appearance is particularly good. ：: Good molded appearance. X: The peeling state near the flow mark and the gate was severe, and the appearance of the molded product was poor.

Method for Evaluating Moldability The melt viscosity greatly affects the moldability. As an index of the melt viscosity, the melt flow rate under a load of 10 kg at 250 ° C. was evaluated. Melt flow rate is 6g / 10m
If it is in or more, it can be said that the moldability is good.

Examples 1 to 9 and Comparative Examples 1 to 14 The performances of the resin compositions having the compositions shown in Tables 1, 2, 3 and 4 were evaluated, and the results are shown in the same table. From the results of Examples 1 to 9 shown in Tables 1 and 2, the resin composition of the present invention has a better balance of impact resistance, molding appearance, and moldability than Comparative Examples 1 to 14 shown in Tables 3 and 4. It turns out that it is excellent. Comparative Example 5
Is obtained by hydrogenating a commercially available ABA (A: polystyrene, B: polybutadiene) type thermoplastic elastomer as the component (b), and is inferior in molding appearance and workability. In Comparative Examples 6 to 14, since the hydrogenated block copolymer is outside the scope of the present invention, the balance between the molded appearance and the workability is poor. Comparative Examples 1 to 4 are inferior in the balance of impact resistance, molding appearance and molding workability since the compounding ratio is out of the range of the present invention.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

As described above, blending of various rubbery polymers has been studied to improve the impact resistance of PPE resins.
It is difficult to obtain a composition having a good balance of impact resistance, molded appearance, and moldability. The present invention, by using a hydrogenated block copolymer having a specific structure,
It is a product obtained from a PPE-based resin composition having excellent balance of impact resistance, molding appearance and molding processability, and is particularly suitable as a material for large molded articles such as exterior and interior parts of automobiles,
The industrial value is great.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshihisa Fujinaga 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Kenichi Sakai 2-2 Kinuigaoka, Moka City, Tochigi Prefecture (56) References JP-A-5-170844 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 53/00-53/02 C08L 25/04- 25/14 C08L 71/12

Claims (2)

(57) [Claims] (1) Polyphenylene ether-based resin 1
(B) (A) 37 to 70 % by weight of a block segment comprising a vinyl aromatic compound polymer;
(B) 65 to 100% by weight of a conjugated diene compound having a 1,2-vinyl bond amount of 30% by weight or more and 35 to 100% of another monomer
Polymer block segment of 15 to 60% by weight
(C) 5 to 30% by weight of a polybutadiene block segment having a 1,2-vinyl bond content of less than 30% by weight
[However, a linear or branched block copolymer consisting of (A) + (B) + (C) = 100% by weight] is hydrogenated, and hydrogen in which the double bond of the conjugated diene portion is saturated by 80% or more. A resin composition comprising 1 to 99% by weight of the added block copolymer. 2. A polyphenylene ether resin
A resin composition comprising a total of 1 to 99% by weight of 100 parts by weight and (C) 99 to 0% by weight of a polystyrene resin, and 99 to 1% by weight of the component (B) of claim 1.