JPS6195065A - Resin composition with high stress crack and impact resistance - Google Patents

Abstract

PURPOSE:To provide the titled composition comprising polyphenylene ether resin, hydrogenated product from A1-B-A2 type elastomeric block copolymer and trans-polybutadiene with specified trans bond content. CONSTITUTION:The objective composition can be obtained by blending (A) 20-90pts. by wt. of a polyphenylene ether resin, (B) >=0.5pt. by wt. of a hydro genated product from A1-B-A2 type elastomeric block copolymer (A1 and A2 are each vinyl aromatic hydrocarbon block; B is conjugated diene block) with the molecular weight of B higher than that of A1 plus A2 and an average molec ular weight pref. 4,000-115,000 for A1 and A2 whereas 20,000-450,000 for B especially the average unsaturation degree for B falling <=20% of the original value, and (C) >=0.5pt. by wt. of a resinous trans-polybutadiene with a trans bond content falling between 70-95 (pref. >=85) % so as to total 100pts. by wt. with the amount of the components (B) plus (C) dropping <=40pts. by wt.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides a resin composition with good stress click properties and impact resistance, more specifically, polyphenylene ether! This invention relates to a thermoplastic resin composition comprising a hydrogenation product of an Aney B-type elastomeric block copolymer, a trans-polybutadiene (with a specified trans bond content), and optionally a styrene resin. be.

Conventional technology Polyphenylene ether resin has attracted much attention in recent years because it has excellent mechanical properties, electrical properties, and heat resistance), as well as low water absorption and good dimensional stability. There is. However, this polyphenylene ether resin alone generally has poor processability and impact strength, so in many industrial applications, it is used as a blend with polystyrene or rubber-reinforced polystyrene, such as mechanical parts, electrical parts, office equipment housings, etc. It is widely used in automotive parts, precision parts, etc. 'On the other hand, in recent years,
The shapes of mechanical and electrical parts tend to become more complex, and as a result, the quality of resin compositions has become increasingly demanding, especially impact resistance. Improvements in oil resistance and oil resistance are strongly desired.

Under these circumstances, two efforts have been made to improve the physical properties of polyphenylene ether resins, especially their impact resistance.
Seeds of vinyl aromatic compounds and birds and conjugated diene compounds B
A mixture of AI-B-A2 type elastomer block copolymer with styrene homopolymer or random copolymer resin as an optional component (JP-A-48-62851, JP-A-51-129450) , a homogeneous blend of a styrene resin, a radial teleblock copolymer obtained from a vinyl aromatic compound, a conjugated diene compound, and a coupling agent (Japanese Unexamined Patent Publication No. 125560/1982), styrene resin, A-B- A compound containing an A' type elastomer block copolymer and its hydride (Japanese Unexamined Patent Application Publication No. 1979-79943) has been proposed. However, these compositions have improved impact resistance to some extent. However, depending on the application, this is not always sufficient, and it is necessary to increase the amount of block copolymer in these compositions to achieve the required impact resistance. In such a case, the excellent properties originally possessed by the polyphenylene ether-based material may be lost, such as the stiffness and heat resistance of the composition being reduced, which is undesirable from a practical standpoint.

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2) Although it was found in the process of achieving the present invention that the rack properties were slightly improved, this is still not sufficient for practical use.

Problems to be Solved by the Invention The purpose of the present invention is to improve the shortcomings of conventional polyphenylene ether resin compositions and to improve stress crack resistance and impact resistance without reducing the excellent performance of polyphenylene ether resins. An object of the present invention is to provide a polyphenylene ether resin composition having good properties.

Means for Solving the Problems As a result of extensive research, the inventors found that polyphenylene ether! Fat 1:l-1At-B-AJ! It has been discovered that the above objective can be achieved by combining and blending a hydrogenated product of an elastomer block copolymer and transpolybutadiene whose trans bond content has been specified, and optionally blending a cystyrene resin. Based on this knowledge, the present invention was completed.

That is, the present invention comprises (D) 20 to 90 parts by weight of a polyphenylene ether resin, (B) an A, -B-- type entomerge rock copolymer (wherein 4 is a polymer block of a vinyl aromatic hydrocarbon, B is a polymerized block of conjugated diene, and the molecular weight of B is larger than the combined molecular weight of A□ and A2). ~95% transpolybutadiene 0.5 parts by weight or more and as desired (up to)
A resin composition comprising 79 parts by weight or less of a styrene resin in a total amount of 100 parts by weight and such that the total amount of components (B) and (C) does not exceed 40 parts by weight. It provides:

The polyphenylene ether resin of component (A) used in the present invention has the general formula (I) or (1) (R1, R2, R
3, R4, R8 and R6 are the same or different alkyl groups having 1 to 4 carbon atoms excluding tart-butyl groups, aryl groups,
It is a homopolymer or copolymer having a repeating unit represented by a halogen atom or a hydrogen atom (R3 and R3 are not hydrogen atoms at the same time), and there are no particular restrictions on the manufacturing method, but for example copper , can be obtained by reacting two raw phenols with oxygen (in the presence of a complex of manganese).

Specific examples of the vine poly 2-enylene ether resin used in the present invention include poly(2,6-dimethyl-1°4-]diunine) ether, poly(2,6-ethyl-1,4-)
unilene) ether, poly(2,6-dichloro-1,4
-phenylene)ether, poly(2,6-dipromu 1)
．． 4-phenylene)ether, 'poly(2-methyl-6)
-ethyl-1,4-phenylene) ether, po+J (
2-chloro-6-methyl-1,4-phenylene) ether, poIJ (2-methyl-6-inglobyl-1.4
-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-chloro-6-promo-1,4-phenylene) ether, poly(2-chloro-6-ethyl) -1,4-phenylene) ether, poly(2-bromo-6-nityl-1,4-phenyl) ether, poly(2-methyl-1,4-7-dinilene) ether, poly(2-phenyl) -1,4-phenylene)ether, poly(2-methyl-6-phenyl-1)
,4-7 enylene) ether, ho1J(2-bromo-6
-phenyl-1,4-phenylene)ether and 2,3
．． (5-) Polyphenylene ether obtained by copolymerizing an alkyl-substituted phenol such as dimethylphenol with, for example, 0-cresol.

Examples include polyphenylene ether copolymers mainly having a layered structure. Furthermore, these may be grafted with a monomer having styrene as the main component.

In the composition of the present invention, when the total amount of each component is 100 parts by weight, the polyphenylene ether resin contains 2 parts by weight.
Used in the range of 0 to 90 parts by weight. If this amount is less than 20 parts by weight, the composition loses the good heat resistance inherent to the boliph 1-enylene ether-based material, while if it exceeds 90 parts by weight, The I addability is markedly reduced, making it unsuitable as a molding material.

In the composition of the present invention, A1 used as the CB) component
-B-' The hydrogenation product of the type 2 elastomeric block copolymer is A, in which the central block and the end blocks are changed,
-B-A2W. In this case, B in the central block is a conjugated diene compound, such as butadiene, isoprene, 1
, 3-pentadiene, 2,3-dimethylbutadiene, etc., and the terminal blocks A1 and A2 are derived from vinyl aromatic compounds, such as styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, etc. (=the block copolymer obtained by hydrogenation and reduced so that the average degree of unsaturation of the central block B is 20 times lower than its initial value, in which the molecular weight of B is between A1 and ... Any molecular weight greater than the combined molecular weight may be used, but from about 4,000 to about 1
Terminal blocks A and A2 having an average molecular weight of 15,000 S and about 20,000 to about 450,000
Preference is given to those forming a central block B having an average molecular weight of up to .

The hydrogenation product of such a block copolymer is 1. Organometallic initiation method using e.g. sodium or lithium metal or their organic derivatives 1: The block copolymer thus obtained is treated with a hydrogenation catalyst, e.g. nickel, Raney nickel, copper chromate, molybdenum sulfide, fine platinum powder,
It can be obtained by hydrogenation using bis(cyclopentagenyl)titanium dichloride, an alkyllithium compound, etc. (see US Pat. No. 5,451,323).

The transpolybutadiene used as component (C) in the present invention has a trans bond content in the range of 70 to 95%, and if the trans bond content is less than 70%, the impact resistance is insufficiently improved. , and disadvantages such as a large decrease in flexural modulus are undesirable. In the present invention, the trans bond content is expressed as a value calculated by the Moléguchi method using an infrared spectrometer.

Preferred trans polybutadienes in the present invention include resinous trans polybutadienes having a trans bond content of about 85 or more. What is resinous here?
It is used as a comparison with rubber-like, and has a Young's modulus of 105 to i
Rubber is defined as a rubber having an o'dyne/C1112 range, and refers to a polymer having a ratio of 1o9 dyne/c1!12 or higher. Furthermore, in order to maintain the bending modulus (strength) of the resulting composition at a high level, the transpolybutadiene used in the present invention has a molecular weight (Mw) of 20,000 to 50.
0,000. In particular, it is in the range of 30,000 to 300,000, and the molecular weight distribution (10,000/node) is 1.2 to 5.
o, particularly preferably in the range of 1.5 to 3. Here, the molecular weight and molecular weight distribution are expressed as values measured using a gel permeation chromatograph (GPC) according to a conventional method.

The above specified transpolybutadiene may contain a small amount of a copolymer component, for example, 30% by weight or less of a monomer unit such as styrene or isoprene in a random or block form in its molecular chain. .

Transpolybutadiene, which has a specific structure, can be produced by, for example, adding butadiene to barium, strontium, or calcium compounds in accordance with conventionally known methods (Japanese Unexamined Patent Publication Nos. 55-38827 and 1982-112916). It can be easily obtained using a homogeneous composite catalyst consisting of a lithium compound, an organomagnesium compound, or optionally an organoaluminium compound, and its bonding mode, molecular weight distribution, Mooney viscosity, etc. , composition, polymerization temperature, and other conditions.

, in the present invention, the hydrogenation product of the □-B-~ type elastomer block copolymer of the component (B) and (C
) It is essential to use trans-polybutadiene in the trans-binding stage t70-95 of the components, and each
．． It is necessary to use 5 parts by weight or more.

In addition, there are no particular restrictions on the ratio of these usages, but
Usually in the range of 1:5 to 5:1 on a weight basis
Used in 3゛.

Furthermore, the total amount of these two types of components is the total amount of the above-mentioned (D) component, (B) component, and (C) component, or the (A) component, (■) component, and (C) component, and the following ( It is necessary that the amount is 40 parts by weight or less with respect to 100 parts by weight of the total amount of component D) including the styrene resin. If this amount exceeds 40 parts by weight, the composition loses the good rigidity and heat resistance inherent to the polyphenylene ether material, which is not preferable.

In the composition of the present invention, a styrene resin is further used as the DJ acid component (if desired). This styrenic resin has the following general formula (II[) (where R is a hydrogen atom,
A polymer derived from a compound represented by a halogen atom or a lower alkyl group, where 2 is selected from a hydrogen atom, a chlorine atom, a vinyl group, and a lower alkyl group, and p is an integer from 1 to 5. One unit has a molar ratio of at least 60. Examples of such materials include homopolymers such as polystyrene, poly-α-methylstyrene, and polychlorostyrene; modified polystyrenes such as rubber-modified polystyrene; or styrene-acrylonitrile copolymers (SAN), styrene-butadiene copolymers, and styrene- Acrylonitrile-butadiene copolymer (ABS), ethylvinylbenzene-divinylbenzene copolymer, styrene-α.

β-unsaturated dicarboxylic anhydride copolymer, styrene-
Examples include styrene-containing copolymers such as imidide copolymers of α,β-unsaturated dicarboxylic acids.

Among these styrenic resins, preferred are rubber-modified impact-resistant styrene resins, such as poly(4-styrene) modified with natural rubber or synthetic rubber. Specific examples of the synthetic rubber for modification include polybutadiene, polyisoprene, etc. , or a copolymer of a diene compound and another monomer, such as a copolymer of a diene compound and styrene, acrylonitrile, acrylic ester, etc.
-A and A-B types (A is a vinyl aromatic compound such as styrene, B is a diene compound such as butadiene)
Examples include rubbery copolymers including block copolymers of ethylene-propylene-diene terpolymer (EPDM) rubber, and the like.

Such styrene resin is used in an amount of 79 parts by weight or less. If it exceeds 79 parts by weight, the heat resistance of the composition decreases, which is not preferable.

The composition of the present invention (= indicates conventionally known additives, such as aluminum hydroxide, phosphate esters, melamine flame retardants, etc.), rogen flame retardants, and flame retardants such as red phosphorus, depending on the purpose of use; Polybutene, low molecular weight polyethylene, mineral oil, epoxidized soybean oil, polyethylene glycol, plasticizers such as fatty acid esters, phosphite esters, hindered phenols, alkanolamines, acid amides, dithiocarbamate metal salts, inorganic One or more stabilizers such as sulfides and metal oxides, various ultraviolet absorbers, colorants, and mold release agents may be added.

Furthermore, various reinforcing photonic agents such as glass fibers, carbon fibers, various metal fibers, various metal flators, asbestos, ura stonite, calcium carbonate, talc, mica, zinc oxide, potassium titanate, etc. can be added to the composition of the present invention. , titanium oxide, glass beads, etc. can be added to obtain a filler-containing resin composition that has even higher rigidity and heat resistance. Furthermore, if a conductive filler such as carbon fiber is selected as the filler, functions such as conductivity and electromagnetic shielding properties can be imparted to the composition of the present invention.

As a method for obtaining the composition of the present invention, for example, a method of melt-mixing using an extruder, kneader, roll mixer, Banbury mixer, etc. is used. In the case of melt mixing, all the components may be mixed at the same time, or some components may be mixed in advance, and then the remaining components may be added and mixed.

The resin composition of the present invention thus obtained is
Sheets, foams,
It can be easily molded into a wide variety of practically useful products such as films, injection molded products of various shapes, blow molded products, pressure molded products, and vacuum molded products.

Effects of the Invention The resin composition of the present invention, in addition to the properties inherent to polyphenylene ether materials, has excellent stress crack resistance and impact resistance, and is suitable for use in mechanical parts, for example.
It is advantageously used in electrical machinery parts, office equipment housings, automobile parts, precision parts, etc., and has an extremely wide range of applications compared to conventional products.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited in any way by the following Examples.

In addition, the physical properties in Examples and Comparative Examples (=) were measured according to the following methods.

(1) Using an injection molded test piece with a heat-resistant thickness of 1/4',
The heat deformation temperature (hereinafter abbreviated as H0D, T) was measured at a load of 18.6 kg/d according to 7207.

(2) Impact strength 1) Using an injection molded test piece with a thickness of 7V, ASTM-
Notched Izot impact strength was measured according to D-638 (measurement temperature 23°C).

(II) Using a test piece with a thickness of 3 mm, DuPont darting was performed using a 71a'R missile, and the following evaluations were made.

◎Near 5kQ-α or more ○: 55 to 9-α or more, less than 75kg-α △: 35&g
- less than 55 x less than 9-α: less than 55 kQ-α (3) molding the resin composition at 250 ° C. using a stress cracking compression molding machine,
A test piece sample with a thickness of 3 sheaths, a width of 12.71 ff, and a length of 120 birds is prepared. This test piece is annealed in a hot air dryer at 80° C. for 24 hours to remove residual strain. Next, one end of this test piece was held in a creep rupture measuring machine manufactured by Ashikaga Riko, a load of 1 kq was set on the other end, and 0.2 g of shaft grease D (manufactured by Sawara Special Oil Co., Ltd.) was applied at a position 2 oarx from the load setting side. After coating, it is kept in a constant temperature room at 23° C. and 50° humidity, and the time until breakage is measured. The longer the time until breakage, the better the stress cracking property.

Evaluation rank ○: 100 hours or more Δ: 50 hours or more and less than 100 hours

Polysunilene ether: ηsp/c=0.60 (
Poly(2,6-dimethylphenylene-1,4-ether) in chloroform (5% solution). (hereinafter abbreviated as PPM) Styron QH405: Asahi Kasei Kogyo (replacement high impact polystyrene Styron 685: Asahi Kasei Kogyo (m polystyrene Dylark 532: ARCO Polymer Co., Ltd. styrene-maleic anhydride copolymer (hereinafter abbreviated as 8MA) Styrene -N-phenylmaleimide copolymer di-N-phenyl-maleimide content of 10% was polymerized and used as a prototype (hereinafter abbreviated as SPM) Clayton G1651 manufactured by Nisiel Chemical Co., Ltd., A□-B-
A.

type hydrogenated styrene-butadiene block copolymer (styrene unit content 33% by weight, polymer concentration 20% by weight)
Luene solution viscosity: 2000 CF2 (25°C)) Riniton G1652: Same as above (styrene unit content: 29
(wt%, polymer concentration 20 wt%) Luene solution viscosity 55
0 cps (25℃)) CARIFLEX TR1101
Manufactured by Nijikoru Chemical Co., Ltd., non-hydrogenated A, -B-~
Type styrene-butadiene block copolymer (styrene unit content 30% by weight, polymer concentration 25% by weight, toluene solution viscosity 4000 Qp days (25°C)) carried out, 11~
5゜Comparative Examples 1 to 4゛I PP'B 50 parts by weight, Styron 68535 parts by weight 1
5 parts by weight of Kraton G1651, 10 parts by weight of various polybutadienes shown in Table 1, 0.2 parts by weight of Irganox 1076 (manufactured by Ciba Geigy) as a stabilizer, and 0.5 parts by weight of Sumilizer BHT (manufactured by Sumitomo Chemical) in a blender. The mixture was mixed in a vented twin-screw extruder and extruded and granulated at a maximum cylinder temperature of 290° C. to obtain resin composition pellets.

A test piece was made from this material using an injection molding machine at 290°C.
Each physical property was determined. The results are shown in Table 2.

As is clear from this table, the resin composition containing the polybutadiene specified in the present invention does not have a particularly large decrease in rigidity (flexural modulus) and is excellent in impact resistance and stress cracking resistance.

In addition, the polybutadiene prototypes 1 to 6 shown in Table 1 were produced by a polymerization method using a homogeneous composite catalyst consisting of barium dinonyl phenoxide, butyl lithium, diptyl magnesium, and triethyl aluminum in a hexane solvent.

Comparative Example 5 A test piece was prepared in the same manner as in Example 1, except that the polybutadiene of Prototype-1 was not used and the amount of Kraton G1651 was 15 parts by weight.
Each physical property was determined. The results are shown in Table 2.

From this table, it can be seen that this product does not have sufficiently good stress crack resistance and impact resistance.

Comparative Example 6 A test piece was prepared in the same manner as in Example 1, except that Kraton G1654 was not used and the amount of polybutadiene in Prototype-1 was 15 parts by weight, and each physical property was determined. Ta. The results are shown in Table 2.

From this table, it can be seen that this product does not have sufficiently good stress cracking properties.

Examples 6 to 8, Comparative Examples 7 to 9 Each component was blended in the parts by weight shown in Table 3, test pieces were prepared in the same manner as in Example 1, and each physical property was determined. The results are shown in Table 4.

As is clear from Table 4, the thermoplastic resin composition having the blending ratio specified in the present invention not only has heat resistance and rigidity, which are characteristics of polyphenylene ether-based materials, but also has good impact resistance and stress crack resistance. On the other hand, compositions with blending ratios that deviate from the present invention result in decreased rigidity, decreased heat resistance, etc., and the excellent properties originally possessed by polyphenylene ether materials are lost. I can see that it is closed.

Table 4 ((1) Physical property value units are the same as above Example 9 A test piece was prepared in the same manner as in Example 4 except that Kraton G1652 was used in place of Kraton G1651. Then, each physical property was determined.

The results are shown in Table 5.

It can be seen from this table that a composition was obtained that met the objectives of the present invention.

Example 10 In Example 4, Styron 68,520 parts by weight and SPMI 15 were used instead of Styron 68,535 parts by weight.
A test piece was prepared in exactly the same manner as in Example 4, except that parts by weight were used, and each physical property was determined.

The results are shown in Table 5.

It can be seen from this table that a composition that met the purpose of the present invention was obtained.

Example 11 A test piece was prepared in exactly the same manner as in Example 4, except that 68,525 parts by weight of Stylon 68,525 parts by weight and 10 parts by weight of 8MA were used instead of 68,535 parts by weight of Stylon, and each physical property was determined. . The results are shown in Table 5.

It can be seen from this table that a composition that met the purpose of the present invention was obtained.

Example 12 Same as Example 4, but instead of PPK, ηsp/c=0.
Example 4 except that a copolymer of 2.6-dimethylphenol (90 mol%) and 2.3.6-)limethylphenol (10 mol%) of 65 (chloroform 5% solution) was used. Test pieces were prepared in exactly the same manner, and each physical property was determined. The results are shown in Table 5.

It can be seen from this table that a composition was obtained that met the objectives of the present invention.

Comparative Example 10 A test piece was prepared in exactly the same manner as in Example 4, except that Califlex TR1101 was used instead of Kraton G1651, and each physical property was determined. The results are shown in Table 5. Shown below.

From this table, it can be seen that this product does not have sufficiently good stress cracking properties.

Table 5 Physical property value units are the same as above Procedural amendment November 21, 1980 Director General of the Patent Office Manabu Shiga 1, Indication of the case 1982 Patent Application No. 214333 2, Name of the invention Stress crack Resin Composition 3 with Good Strength and Impact Resistance, Relationship with the Amendment Case Patent Applicant: 1-2-6 Dojimahama, Kita-ku, Osaka, Osaka Prefecture (C03) Asahi Kasei Industries, Ltd. Representative Teru Miyazaki 4 , Agent Kawashima Kuninobu Building 8th Floor 5, 2-2-2 Shinbashi, Minato-ku, Tokyo
・Amendment order date 0 Voluntary
・18. Contents of amendment (1) On page 18 of the specification, the second line (1) will be corrected to (1), and the fifth line (ii) will be corrected to (2).

(2) Table 2 on page 24 is corrected as follows.

(3) "Composition (parts by weight)" in Table 3 on page 26 of the same
Correct it to "Amount (parts by weight)".

(4) The following nine corrections have been made to Table 4 on page 27.

Table 4 (5) Table 5 on page 29 has been amended as follows:〇Table 5

Claims (1)

[Scope of Claims] 1 (A) 20 to 90 parts by weight of polyphenylene ether resin, (B) A_1-B-A_2 type elastomer block copolymer (A_1 and A_2 are vinyl aromatic hydrocarbon polymer blocks, B is a polymerized block of a conjugated diene, and the molecular weight of B is larger than the combined molecular weight of A_1 and A_2), and (C) a trans bond content of 70 to 95 % transpolybutadiene 0.5 parts by weight or more, the total amount is 100%
parts by weight, and the total amount of the components (B) and (C) does not exceed 40 parts by weight. 2 (A) 20 to 90 parts by weight of polyphenylene ether resin, (B) A_1-B-A_2 type elastomer block copolymer (A_1 and A_2 are vinyl aromatic hydrocarbon polymer blocks, B is a conjugated diene polymer block and (B's molecular weight is greater than the combined molecular weight of A_1 and A_2) 0.5 parts by weight or more of a hydrogenated product of (C) 0.5 parts by weight of trans polybutadiene with a trans bond content of 70-95% % or more, and 79 parts by weight or less of (D) styrenic resin so that the total amount is 100 parts by weight, and the total amount of components (B) and (C) does not exceed 40 parts by weight. A resin composition consisting of