JPH06234911A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To provide a polyphenylene ether resin compsn. which is excellent in the balance among fluidity, heat resistance, and impact resistance and suitable for a large molding. CONSTITUTION:The compsn. comprises 15-50 pts.wt. polyphenylene ether resin, 15-60 pts.wt. arom. alkenyl compd. polymer, 10-20 pts.wt. resin component comprising at least one hydrogenated A-B-A block copolymer (wherein A is an arom. alkenyl compd. polymer block; and B is a diene hydrocarbon polymer block) having a content of polymer block A higher than 50wt.% and at least one hydrogenated A-B-A block copolymer (wherein A and B are each the same as above-mentioned) having a content of polymer block A of 50wt.% or lower, and 1-20 pts.wt. arom. vinyl-grafted ethylene (co)polymer having a high graft efficiency.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a polyphenylene ether resin which is suitable for large molded articles such as interior panels of automobiles and has a good balance of physical properties such as fluidity, heat resistance and impact resistance (particularly low temperature impact resistance). It relates to a composition.

[0002]

2. Description of the Related Art Polyphenylene ether resins are widely used in industrial fields because of their good heat resistance.
However, due to lack of fluidity, this resin is rarely used alone. To compensate for this drawback, polymer alloys with polystyrene resins are commonly used as modified PPE. This resin lacks impact resistance in practical use, and it has been attempted to improve impact resistance by adding various kinds of elastic bodies (elastomers) without impairing the original properties. ing. A typical example of this elastomer is an ABA type triblock copolymer of an alkenyl aromatic compound A and a conjugated diene compound B or a hydrogenated product thereof. Although a series of elastomers having various molecular weights are commercially available, the addition of these elastomers has not yet led to a good balance of practical physical properties. For the purpose of supplementing this, the above AB
-Adding a polyolefin resin to an A-type elastomer to improve impact resistance is disclosed in U.S. Pat. No. 4,166,05.
5, No. 4,239,673, etc., but the compatibility is still insufficient and is still insufficient.

[0003]

The object of the present invention is to solve the above-mentioned problems, namely, the fluidity, heat resistance and impact resistance required for materials suitable for large molded articles such as automobile interior panels. To achieve a good balance of low temperature impact).

[0004]

[Means for Solving the Problems] In order to solve the above problems, the present inventors extensively studied the compatibility between the added elastomer and the base polymer and the effect of addition on the physical properties. As a result, two types of ABA type triblock copolymers containing the component A in a specific range or hydrogenated products thereof and an ethylene-based (co) polymer having a high graft efficiency obtained by a specific production method described later- By adding the aromatic vinyl graft polymer to the polyphenylene ether-based resin, a material having a good physical property balance suitable for a large-sized molded product was obtained, and the present invention was completed.

That is, the present invention comprises (A) polyphenylene ether resin 15 to 50 parts by weight, (B) alkenyl aromatic compound polymer 15 to 60 parts by weight, (C) (C-1).
A hydrogenated product of an ABA type block copolymer (A is a polymer block of an alkenyl aromatic compound, B is a polymer block of a diene hydrocarbon compound), and the content of A is 50.
(C-2) A- and at least one resin in excess of wt%
At least a resin which is a hydrogenated product of a B-A type block copolymer (A is a polymer block of an alkenyl aromatic compound, B is a polymer block of a diene hydrocarbon compound), and the content of A is 50% by weight or less. 10 kinds in total with one kind
˜20 parts by weight, and (D) a resin composition comprising 1 to 20 parts by weight of an ethylene-based (co) polymer-aromatic vinyl graft polymer having a high grafting efficiency.

The polyphenylene ether resin (A) used in the present invention (hereinafter appropriately abbreviated as PPE) has the general formula

[Chemical 1] (In the formula, R1 is a lower alkyl group having 1 to 3 carbon atoms, R2
R3 is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. ) Is a polymer having a structural unit represented by the formula (1) in the main chain, and may be a homopolymer or a copolymer. For example, poly (2,6-dimethyl-1,4phenylene) ether, poly (2, 6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4)
Examples thereof include phenylene) ether, poly (2-methyl, 6-propyl-1,4phenylene) ether, and particularly, poly (2,6-dimethyl-1,4phenylene) ether, 2,6-dimethylphenol and 2,3, A 6-trimethylphenol copolymer is preferred.

The polymer of the alkenyl aromatic compound (B) used in the present invention is a resin containing at least 25% by weight or more of the structural unit represented by the following general formula in the polymer.

[Chemical 2] (In the formula, R1 represents a hydrogen atom or a lower alkyl group, Z represents a halogen atom or a lower alkyl group, and p is 0 or an integer of 1 to 3.) Specific examples include polystyrene and impact-resistant polystyrene. , Styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-α
-Methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene-methylmethacrylate copolymer, ethylene-styrene copolymer, ethylene-propylene-butadiene-styrene copolymer and the like. Of these, impact-resistant polystyrene is particularly preferable,
The impact-resistant polystyrene includes polybutadiene, butadiene-styrene copolymer rubber, or rubber-modified polystyrene modified with a rubber component such as EPDM.

The (C) ABA type block copolymer used in the present invention means a polymer block A of an alkenyl aromatic compound and a polymer block B of a conjugated diene hydrocarbon compound.
Or a hydrogenated product thereof, in which at least two kinds having different A content ratios are added. That is, the content of the component (C-1) A is more than 50% by weight, and at least 1 is selected from ABA type block copolymers, preferably 60 to 80% by weight of ABA type block copolymers. Seed, an ABA type block copolymer having a content of the (C-2) A component of less than 50% by weight, and preferably 20 to 40% by weight of an ABA type block copolymer. The seed is selected. The molecular weight of these ABA type block copolymers is not particularly limited, but in terms of physical property balance, the former is 70,000 to 200,000,
The latter is preferably 100,000 to 300,000. Specific examples of these include hydrogenated products of styrene-butadiene-styrene copolymer (hereinafter abbreviated as SEBS),
Examples thereof include hydrogenated products of styrene-isoprene-styrene copolymer (hereinafter abbreviated as SEPS). (C-1)
Are commercially available under the trade names of Septon 2104 and (C-2) such as Clayton G1651 and Septon 4055.

The ethylene-based (co) polymer-aromatic vinyl graft polymer (D) having a high grafting efficiency used in the present invention is a resin obtained by grafting an aromatic vinyl compound onto an ethylene-based (co) polymer. The composition is obtained, for example, by kneading a graft precursor with an addition polymer at a high temperature. The graft precursor is prepared by suspending 100 parts by weight of an ethylene-based (co) polymer in water and separately adding 5 to 400 parts by weight of an aromatic vinyl monomer to a radical (co) polymerizable organic peroxide. One or a mixture of two or more of the above compounds is added to 100 parts by weight of the aromatic vinyl monomer.
1 to 10 parts by weight, and the total amount of the radical initiator of the aromatic vinyl monomer and the radical (co) polymerizable organic peroxide is 10
A solution in which 0.01 to 5 parts by weight with respect to 0 parts by weight is dissolved is added, and the mixture is heated to preferably 60 to 65 ° C. under the condition that the decomposition of the radical initiator does not substantially occur. Ethylene (co) polymer is impregnated with radical (co) polymerizable organic peroxide and radical initiator, and vinyl monomer, radical (co) polymerizable organic peroxide and radical initiator are used in the respective amounts. The temperature of this aqueous suspension is raised when it is impregnated with more than 50% of
It is a resin composition obtained by graft-copolymerizing an aromatic vinyl monomer and a radical (co) polymerizable organic peroxide in an ethylene (co) polymer at 0 to 85 ° C.

The obtained graft precursor is melt-kneaded with the addition polymer. By the above operation, an ethylene-based (co) polymer-aromatic vinyl graft polymer having high graft efficiency can be obtained. Here, the ethylene-based (co) polymer is a homopolymer of ethylene or a copolymer of ethylene and an olefin such as propylene. A preferable example of the ethylene-based (co) polymer is a low-density ethylene polymer. The density of this low-density ethylene polymer is preferably 0.910 to 0.935 g / cm ³ , specifically, an ethylene homopolymer obtained by a high-pressure polymerization method,
Examples thereof include a copolymer of ethylene and an α-olefin for density adjustment, such as propylene, butene-1, and pentene-1.

The low-density ethylene polymer may be in the form of pellets having a particle size of 1 to 5 mm or powder. It is preferable to properly use these depending on the blending ratio of the low density ethylene polymer in the grafting precursor. For example, when the low density ethylene polymer in the grafting precursor is 50% by weight or more, it is preferably in the pellet form, and when it is less than 50% by weight, the powder form is preferable. The aromatic vinyl compound polymer is a polymer of styrene or styrene substituted with a halogen atom or a lower alkyl group. Specifically, styrene, methyl styrene, ethyl styrene,
Examples thereof include polymers such as dimethyl styrene, isopropyl styrene, chlorostyrene, α-methyl styrene and α-ethyl styrene. The weight average molecular weight of this polymer is preferably 10,000 to 200,000.

The radical (co) polymerizable organic peroxide is a compound represented by the following chemical formula 3 or chemical formula 4. Specifically, t-butylperoxyacryloyloxyethyl carbonate and t-butylperoxyallyl carbonate can be exemplified as preferable ones.

[Chemical 3] (In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R2 is a hydrogen atom or a methyl group, R3 and R4 are each an alkyl group having 1 to 4 carbon atoms, and R5 is an alkyl group having 1 to 12 carbon atoms. , A phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, m is 0, 1 or 2.

[Chemical 4] (In the formula, R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R7 is a hydrogen atom or a methyl group, R8 and R9 are each an alkyl group having 1 to 4 carbon atoms, and R10 is an alkyl group having 1 to 12 carbon atoms.
Represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. n is 0, 1 or 2. As the radical initiator, a known radical initiator such as benzoyl peroxide is used.

The obtained graft precursor is melt-kneaded with an addition polymer to obtain an ethylene (co) polymer-aromatic vinyl graft polymer having a high graft efficiency. Here, the addition polymer is either one or both of a homopolymer of ethylene or a copolymer of ethylene and an olefin such as propylene, or a polymer of styrene substituted with a halogen atom or a lower alkyl group. Is a polymer composed of The weight average molecular weight of the addition polymer is preferably 20,000 to 200,000.

In the graft polymer of the present invention, the ratio of the ethylene (co) polymer and the addition polymer to be used is not particularly limited, but the ratio of the ethylene (co) polymer is the total amount of both. 15 to 85% by weight is preferable,
More preferably, it is 25 to 70% by weight. Considering compatibility, 30 to 50% by weight is most preferable. The graft polymer used in the present invention is characterized by high graft efficiency. When the grafting efficiency is represented by (grafted aromatic vinyl monomer) / (used aromatic vinyl monomer) × 100, the grafting efficiency of the graft polymer of the present invention is 50 to 6
It reaches 0%, which is much higher than the grafting efficiency (about 10%) of the usual graft polymer. Preferred ethylene-based (co) polymer-aromatic vinyl graft polymers include those marketed under the trade name of Modiper.

The resin composition of the present invention can be produced by the equipment and method generally used for producing a thermoplastic resin composition. For example, the components constituting the resin composition can be mixed with a mixer such as a tumbler, kneaded using a uniaxial or biaxial extruder, and extrusion-molded to produce pellets or the like.

The resin composition of the present invention may contain a flame retardant such as a halogen-based or phosphorus-containing flame retardant, various pigments, an ultraviolet absorber, or an inorganic filler material such as glass fiber or carbon fiber.

[0017]

EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. PPE of the present invention
The physical properties of the resin composition were confirmed by the following methods. Molding method: PPE resin compositions having the compounding ratios shown in Tables 1 and 2 were mixed in a tumbler type blender for 10 minutes, and a twin-screw extruder, TEM35 type, with a barrel set temperature of 270 to 2 was used.
Melt kneading was performed at 90 ° C. to form pellets. After drying these pellets at 90 ° C. for 5 hours, a test piece for measuring physical properties was molded at a molding temperature of 290 ° C. by a molding machine with a mold clamping pressure of 50 tons. Physical property measuring methods (The physical properties shown in Tables 3 and 4 were measured by the following measuring methods.) Izod impact value: measured according to ASTM D-256 at a thickness of 1/8 ", a notched temperature of 23 ° C and -30 ° C. (Kg / cm ² ) DTUL: 1 / thickness according to ASTM D-648
4 ", load 18.6 Kg / cm < ² >. (° C) Flow length: J100SA-2 type molding machine manufactured by Japan Steel Works, Ltd., cylinder temperature 290 ° C, injection pressure 1000 Kg.
/ Cm ² , thickness 2 mm, width 20 mm bar flow length (m
m) was measured. Appearance: With respect to the sample piece whose flow length was measured, the layer delamination state of the gate was observed and ranked as follows. ◯: No delamination Δ: Degree of delamination is slight ×: Delamination is remarkable

Example 1 40 parts by weight of PPE (manufactured by Mitsubishi Gas Chemical Co., Inc., limiting viscosity 0.45 in chloroform at 25 ° C.), impact-resistant polystyrene resin (manufactured by Mitsubishi Kasei Polytech Co., Ltd., trade name Dialex) HT478) 49 parts by weight, hydrogenated SEPS-A
(Kuraray Co., Ltd., trade name Septon 2104) 5 parts by weight, hydrogenated SEPS-B (Kuraray Co., Ltd., trade name Septon 4055) 3 parts by weight, LDPE-g-PS (NOF Corporation modiper) A-1101) 3 parts by weight, stabilizer-1 (Sumitomo Chemical Co., Ltd., Sumilizer BHT) 0.2 parts by weight, stabilizer-2 (SANDOZ Co., Ltd., Sandstave P-EPQ) 0.2. Parts by weight were mixed and a test sample was prepared under the above conditions.

Example 2 HT47 was used as the impact-resistant polystyrene resin in Example 1.
Example 1 was repeated except that a 1: 1 mixture of 8 and Mitsubishi Kasei Polytech GPPS, trade name Dialex HF77 was blended.

Example 3 The mixing ratio of the polystyrene resin used in Example 2 was set to 2: 1. Except for this, the same procedure as in Example 1 was performed.

EXAMPLE 4 35 parts by weight of PPE (used in Example 1), 40 parts by weight of impact polystyrene resin (used in Example 1), hydrogenated SEPS-A, 7 parts by weight, hydrogenated SEPS-B,
8 parts by weight, LDPE-g-PS, 10 parts by weight, and others were the same as in Example 1.

Comparative Example 1 Instead of the modeler in Example 1, EPR (EX Co., Ltd.) was used.
XON, trade name Vistalon 878P) was mixed in 3 parts by weight. Others were the same as in Example 1.

Comparative Example 2 40 parts by weight of PPE (used in Example 1), 60 parts by weight of polystyrene resin (used in Example 1) and stabilizers 1 and 2 were blended in the same manner as in Example 1.

Comparative Example 3 40 parts by weight of PPE (used in Example 1), 55 parts by weight of polystyrene resin (used in Example 1), hydrogenated S
EBS (manufactured by SHELL, product name Clayton G16
In the same manner as in Example 1, 51 parts by weight and 5 parts by weight of stabilizers 1 and 2 were blended.

Comparative Example 4 In Comparative Example 3, 52 parts by weight of polystyrene resin and hydrogenated SEBS were used.
8 parts by weight of (Clayton G1651 manufactured by SHELL) was compounded. The above formulation tables are shown in Tables 1 and 2, and the physical property evaluation results are shown in Tables 3 and 4. The symbols representing each component in the table are described below. A-1) PPE resin (Mitsubishi Gas Chemical Co., Ltd., intrinsic viscosity in chloroform at 25 ° C. 0.45) B-1) HIPS (Mitsubishi Kasei Polytech Co., Ltd., Dialex HT478) B-2) HT478 And GPPS (manufactured by Mitsubishi Kasei Polytech Co., Ltd., Dialex HF77) in a 1: 1 mixture. B-3) A mixture of the HIPS and GPPS in a ratio of 2: 1. C-1) Hydrogenated SEPS (Septon 2104) C-2-1) Hydrogenated SEPS (Septon 4055) C-2-2) Hydrogenated SEBS (Clayton G1651) D-1) LDPE-g-PS (Modeper A1101) E-1) EPR (Vistaron 878P) S-1) Sumilizer BHT S-2) Sand Starve P-EPQ

[0026]

Table 1 Component 1 Example 1 Example 2 Example 3 Example 4 A-1 40 40 40 35 B-1 49 0 0 40 B-2 0 50 0 0 B-3 0 0 50 0 C- 1 5 5 5 7 C-2-1 3 3 3 8 D-1 3 2 2 10 S-1 0.2 0.2 0.2 0.2 0.2 S-2 0.2 0.2 0.2 0. Two

[0027]

[Table 2] Table 2 Components Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 A-1 40 40 40 40 B-1 49 60 55 55 52 C-1 5 0 0 0 C-2-1 3 0 0 0 C-2-2 0 0 5 8 E-1 3 0 0 0 S-1 0.2 0.2 0.2 0.2 S-2 0.2 0.2 0.2 0.2

[0028]

Table 3 Items Table 1 Example 1 Example 2 Example 3 Example 4 Izod 35 17 24 50 (23 ° C.) Izod 12 7 10 20 (−30 ° C.) Bar flow 210 235 220 170 DTUL 120 120 120 120 117 Appearance ○ ○ ○ △

[0029]

Table 4 Table 4 Items Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Izod 50 11 17 20 (23 ° C) Izod 20 6 8 10 (-30 ° C) Bar flow 160 220 220 185 170 DTUL 118 119 120 120 Appearance × ○ ○ ×

[0030]

The resin composition obtained by the present invention has a good balance of physical properties such as fluidity, heat resistance and (low temperature) impact resistance, and is found when an incompatible elastomer is added.
It is a material with high practical value that suppresses the delamination phenomenon and is suitable for large moldings such as automobile interior panel materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C08L 53/02 LLY 7308-4J LLZ 7308-4J (72) Inventor Hiroshi Murayama 5 Higashiyawata, Hiratsuka City, Kanagawa Prefecture Inside 6-2 Sanryo Gas Chemical Co., Ltd. Plastics Center (72) Inventor Goro Shimaoka 5-6-2 Higashi-Hachiman, Hiratsuka City, Kanagawa Sanritsu Gas Chemical Co., Ltd. Plastics Center

Claims (2)

[Claims] 1. A polyphenylene ether resin (A) 15 to
50 parts by weight of (B) alkenyl aromatic compound polymer 1
5 to 60 parts by weight, (C) (C-1) A-B-A type block copolymer (A is a polymer block of an alkenyl aromatic compound, B is a polymer block of a diene hydrocarbon compound) or its hydrogenation (C-2) A-B-A type block copolymer (A is a block of an alkenyl aromatic compound, B is a diene-based carbonization) and at least one resin having an A content of more than 50% by weight. Polymerization block of hydrogen compounds)
Or a hydrogenated product thereof having an A content of 50% by weight
10 in total in combination with at least one of the following resins
20 parts by weight, (D) a resin composition comprising 1 to 20 parts by weight of an ethylene-based (co) polymer-aromatic vinyl graft polymer having a high grafting efficiency. 2. An ethylene-based (co) polymer-aromatic vinyl graft polymer (D) comprises a polyolefin, one or a mixture of radically copolymerizable organic peroxides, an aromatic vinyl monomer and The resin composition according to claim 1, which is a polyolefin-aromatic vinyl graft polymer having a high graft efficiency, which is obtained by kneading with a polymer of a vinyl aromatic monomer in the coexistence of a radical polymerization initiator.