JPH0532881A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To provide a molded article formed by bonding polyurethane to a PPE resin, which has a good adhesiveness in the absence of a primer intercoated, and in which the PPE resin is not separated from the polyurethane foam even after a thermal cycle test or a moisture resistance test and no delamination occurs in the PPE resin section or no deterioration is caused in its mechanical properties. CONSTITUTION:A molded article formed by bonding polyurethane to a polyphenylene ether resin or a resin composition comprising the resin and a polystyrene resin, wherein the polyphenylene ether resin or the resin composition comprising the resin and a polystyrene resin contains 0.5-30 pts.wt. aliphatic or aromatic phosphoric acid ester and/or 0.1-5 pts.wt. fatty acid bisamide compound for each 100 pts.wt. poly-phenylene ether resin or the sum of the resin and the polystyrene resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article obtained by adhering a polyphenylene ether resin composition containing or not containing a polystyrene resin and polyurethane, and in particular, a device requiring adhesiveness with urethane, For example, the present invention relates to a molded product used for an instrument panel, a door side panel, a center console or the like of an automobile.

[0002]

2. Description of the Related Art Polyphenylene ether resin has excellent mechanical properties and is used as a molding product as an engineering resin. A polyphenylene ether (hereinafter sometimes abbreviated as PPE) resin is often used by blending a vinyl aromatic resin such as polystyrene or rubber reinforced polystyrene (HIPS) resin in order to improve its moldability. However, a molded product obtained from a resin composition comprising a polyphenylene ether resin or a polystyrene resin has a disadvantage that it does not adhere to a polyurethane foam. Therefore, when a molded article in which a PPE resin and a polyurethane foam are adhered to each other is required, such as an instrument panel of an automobile, the above-mentioned inconvenience is avoided by intermediate coating of a primer.

As a method for improving the adhesiveness between a polyurethane foam and a molded article based on a resin composition comprising a polyphenylene ether resin and a vinyl aromatic resin, there is disclosed in Japanese Patent Laid-Open No.
In JP-A-60-36554 and JP-A-63-118366, it is proposed to add a polar resin such as ABS or SMA (styrene-maleic anhydride) to this resin composition. However, since these polar resins have poor compatibility with the polyphenylene ether / polystyrene resin composition, they were obtained when a sufficient amount of polar resin was added to the polyurethane foam to obtain sufficient adhesive strength without using a primer. Molded products have problems such as delamination and deterioration of mechanical properties. In order to solve this problem, it has been proposed in JP-A-2-991164 to mix a terpene phenol resin. According to this technique, the resin molded product obtained does not cause delamination and does not exhibit deterioration in mechanical properties. Also, the adhesion with the urethane foam is improved.
However, a molded article obtained by adhering this resin composition and urethane foam peels off at the interface between the resin and the foam when it is forcibly peeled off. Further, after a heat cycle or a humidity resistance test suitable for an actual use environment such as an instrument panel of an automobile, peeling easily occurs. In the molded article obtained by adhering the resin composition in which the terpene phenol resin is mixed with the polyurethane as described above, the adhesion between the PPE resin and the urethane foam is improved, but sufficient adhesive strength is not achieved. Therefore, the present invention is a molded article obtained by adhering a PPE resin and a polyurethane, which has good adhesiveness without intermediate coating of a primer, and can be used for a PPE resin and a polyurethane foam even after a thermal cycle and a humidity resistance test. It is an object of the present invention to provide a molded product which does not peel off and does not cause delamination in the PPE resin portion or deterioration of mechanical properties.

[0004]

The present invention provides a polyphenylene ether-based resin or a resin composition based on this and a polystyrene-based resin, and a molded article obtained by adhering the same to a polyphenylene ether-based resin or a polystyrene-based resin. Based on 100 parts by weight of the polyphenylene ether-based resin or the polystyrene-based resin in total, 0.5 to 30 parts by weight of one or more compounds selected from the group consisting of a) aliphatic and aromatic phosphate esters, And / or b) a molded article comprising 0.1 to 5 parts by weight of one or more fatty acid bisamide compounds.

It is an important requirement of the present invention that the PPE resin composition contains a phosphate ester and / or an aliphatic bisamide compound as a component. As a result, the adhesiveness of both resin parts in the molded product obtained by adhering the PPE resin composition and polyurethane to PP
It is possible to improve without deteriorating the characteristics of the E-based resin portion. This is totally unexpected.

In the present invention, the polyphenylene ether resin is known per se, and for example, the following general formula can be used.

[0007]

[Chemical 1] (In the formula, R ¹ , R ² , R ³ , and R ⁴ are hydrogen, halogen, an alkyl group, an alkoxy group, a haloalkyl group having at least two carbon atoms between a halogen atom and a phenyl ring, and a haloalkoxy group. Represents a monovalent substituent selected from those containing no tertiary α-carbon, and n is an integer representing the degree of polymerization), and is a general term for the polymer represented by the above general formula. The above may be a single type or a copolymer in which two or more types are combined. In a preferred embodiment, R ¹ and R ² are alkyl groups having 1 to 4 carbon atoms, and R ³ and R ⁴ are hydrogen or 1 to ⁴ carbon atoms.
4 is an alkyl group. 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 can be mentioned. A particularly preferred polyphenylene ether resin is poly (2,6-dimethyl-1,4-phenylene) ether. Examples of the polyphenylene ether copolymer include copolymers in which the above-mentioned polyphenylene ether repeating unit partially contains an alkyl trisubstituted phenol such as 2,3,6-trimethylphenol. Further, it may be a copolymer obtained by grafting a styrene compound on these polyphenylene ethers. Styrene-based compound grafted polyphenylene ether to the above polyphenylene ether,
The styrene compound is a copolymer obtained by graft-polymerizing styrene, α-methylstyrene, vinyltoluene, chlorostyrene and the like.

The polystyrene resin used in the present invention has a general formula

[0009]

[Chemical 2] (Wherein R represents hydrogen or an alkyl group having 1 to 4 carbon atoms, Z represents a halogen or a substituent which is an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 5). It must have at least 25% by weight or more in the polymer of repeating structural units derived from the indicated vinyl aromatic compounds.

Examples of such polystyrene-based resins include polymers of styrene or its derivatives (for example, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof) and polybutadiene, polyisoprene, butyl rubber, etc. Included are styrene polymers modified with natural or synthetic elastomeric materials such as EPDM rubber, ethylene-propylene copolymer, natural rubber, polysulfide rubber, polyurethane rubber, epichlorohydrin.

Particularly preferred polystyrene resins in the present invention are polystyrene and rubber-reinforced polystyrene (HI).
PS) or a mixture thereof.

In the molded article of the present invention, it is preferable to use both a polyphenylene ether resin and a polystyrene resin as components of the PPE resin composition. The weight ratio of the polyphenylene ether resin to the polystyrene resin is preferably 10:90 to 90:10, particularly 20:80 to 80:20.

In the present invention, as a component of the PPE resin composition, in addition to the above resin components, a compound selected from the group of aliphatic and aromatic phosphate esters and / or a fatty acid bisamide compound is used. . Here, it is possible to use either one of the phosphoric acid ester and the bisamide compound, or it is possible to use both.
Preferably both are used together. In any case, one or more compounds can be used as the phosphoric acid ester or bisamide compound.

The aliphatic or aromatic phosphoric acid ester used in the present invention is not particularly limited, and various known ones such as monomers and condensation type multimers can be used. Examples of preferred monomeric phosphates include tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate and 2-Ethylhexyl diphenyl phosphate can be mentioned as an example of preferable condensed multimeric phosphoric acid ester such as resorcinol diphosphate and resorcinol triphosphate. These phosphoric acid esters are used in an amount of 0.5 to 30 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the polyphenylene ether resin or a total of 100 parts by weight of the polystyrene resin. If the amount of phosphoric acid ester is less than 0.5 parts by weight, the adhesiveness between the composition and polyurethane will not be sufficiently improved.
If it is more than 30 parts by weight, the heat distortion temperature is significantly lowered, and the problem of contamination of the molding surface or the mold surface due to bleeding occurs. Further, even if the amount of the phosphoric acid ester is higher than 30 parts by weight, the improvement of the adhesiveness beyond the present invention cannot be expected.

There are no particular restrictions on the aliphatic bisamide, but capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide,
N, N'-methylenebisamide synthesized from formalin with behenic acid amide, oleic acid amide, eicosenoic acid amide, erucic acid amide, elaidic acid amide and the like is preferable. These bis-amide compounds are polyphenylene ether resin or polystyrene resin together with 1
0.5-5 parts by weight, preferably 0.5-
3 parts by weight are used. When the amount of the bisamide compound is less than 0.5 parts by weight, the adhesiveness is not sufficiently improved, and when it exceeds 5 parts by weight, problems such as delamination of layers or contamination of the mold surface due to bleeding occur. Further, even if the amount of the bisamide compound is higher than 5 parts by weight, the improvement in the adhesiveness beyond the present invention cannot be expected.

A terpene phenol resin may be added to the above PPE resin composition. Here, the terpene phenol resin is a resin obtained by copolymerizing terpene and phenol, and is known per se. The terpene phenol resin that can be used in the present invention is not particularly limited, but one having a softening point of 100 ° C. or higher and having 1 or more OH groups per molecule is preferable. These terpene phenol resins are preferably 0.5 parts by weight based on 100 parts by weight of the polyphenylene ether resin or a total amount thereof and the polystyrene resin.
~ 50 parts by weight added.

In the PPE resin composition of the present invention, a rubber-like substance is further added, for example, per 100 parts by weight of the polyphenylene ether resin or 100 parts by weight of the polystyrene resin.
It can be included in an amount up to 20 parts by weight. As the rubber-like substance, a styrene-based hydrocarbon polymer block-conjugated diene-based elastomer block copolymer and a styrene-based hydrocarbon polymer block-olefin-based elastomer block copolymer are particularly preferable.

Further, the PPE resin composition may further contain a reinforcing material such as glass fiber in an amount of preferably 50 parts by weight or less per 100 parts by weight of the total of the polyphenylene ether resin or the polyphenylene ether resin and polystyrene resin. Further, other additives such as pigments, dyes, fillers, heat-resistant agents, oxidative deterioration inhibitors, weathering agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, flame retardants, and flow agents, as long as their physical properties are not impaired. It is also possible to add a property improver, an antistatic agent and the like.

PPE used in the present invention from each of the above components
The method for producing the resin composition is not particularly limited, and a usual method can be satisfactorily used. However, melt mixing is generally preferred. There is no particular limitation on the temperature and time required for melt mixing, and they can be appropriately determined by the composition of the materials. The temperature varies somewhat with the mixing ratio of polyphenylene ether to polystyrene, but is generally in the range of 270-350 ° C. A long time and / or a high shear rate are desirable for mixing, but the deterioration of the resin composition proceeds. Therefore, it is desirable to determine the time taking these points into consideration. The components can be added and mixed in any order, and can be melt-mixed continuously or batchwise using, for example, an extruder, a Banbury mixer, a roller, a kneader and the like.

The molded article of the present invention comprises the above PPE resin composition and polyurethane bonded together. Here, the term "polyurethane" includes all polymers having a urethane bond (-NHCOO-), and may be a single polymer having a urethane bond or a copolymer in which two or more polymers are combined. There are no particular restrictions on its characteristics such as molecular structure and molecular weight.
That is, the polyurethane that can be used in the molded article of the present invention is not limited to a particular one, and in the present invention, it is possible to select a polyurethane having properties according to the use of the molded article. Polyurethane is usually urethane foam. The polyurethane may contain conventional additives. Methods of making polyurethanes are well known to those skilled in the art and need not be specifically described here.

The molded product of the present invention can be manufactured by, for example, a method of molding and curing by placing a urethane raw material in a molding frame containing a molded product of a PPE resin composition. In this method, the PPE and the polyurethane only need to be in contact with each other at the stage of curing, and do not have to be in contact with each other from the time of molding. Alternatively, a method of spray-flushing a liquid material of a urethane raw material to a molded product of the PPE resin composition can be used. In this method, the urethane raw material may be sprayed on the hot PPE molded body immediately after molding, or may be sprayed on the PPE molded body while warming the urethane raw material. Alternatively, by spraying the urethane raw material on the PPE molded product and then heating it, a molded product in which the both are adhered can be obtained. The method for producing the molded article of the present invention is not limited to these, and methods other than the above may be adopted. In any of the above methods, the molded product of the PPE-based resin composition may be manufactured by a known method, and it is not necessary to adopt a special manufacturing method. Further, the shape thereof is not particularly limited. In the production of the molded article of the present invention, molding and curing of the PPE resin composition and urethane may be performed by any known method, and sufficiently strong adhesion can be obtained without using any special adhesion means or process. it can.

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

[0023]

EXAMPLES In the following Examples and Comparative Examples, poly (2,6-polyphenylene ether-based resin (PPE-based resin)) having an intrinsic viscosity of 0.48 dl / g (25 ° C. in chloroform) was used.
Dimethyl-1,4-phenylene) ether was used.

As the polystyrene type resin (hereinafter sometimes referred to as PS), Dialex HT644 (trademark, rubber reinforced polystyrene of Mitsubishi Monsanto Kasei Co., Ltd.) or Dick Styrene CR3500 (trademark of Dainippon Ink and Chemicals, Inc.) Polystyrene) was used.

As the phosphoric acid ester, a-1) triphenyl phosphate (T containing 9.5% phosphorus)
PP, Daihachi Chemical Industry Co., Ltd.) a-2) Polyphosphoric acid ester (Phosphirex 574, Akzo Kashima Co., Ltd.) a-3) Tributoxyethyl phosphate (TBP, Daihachi Chemical Industry Co., Ltd.) is used. did.

As the b) bisamide compound, N, N'-methylenestearic acid bisamide (AC200 bis, Nippon Kasei Co., Ltd.) was used.

C) As the terpene phenol resin, Mighty Ace K125 (trademark, Yasuhara Chemical, softening point 125
C., 2 OH groups / 1 molecule) were used.

Further, d) a rubber-like substance (SEBS) and e) glass fiber as optional components, and f) a styrene-maleic anhydride copolymer (SMA, maleic anhydride) as components used in Comparative Examples. Of 17%) was used.

The above components were uniformly premixed in a weight ratio shown in the following table using a Henschel mixer, which was kneaded and pelletized by a twin-screw extruder set to a cylinder temperature of 290 ° C. and a screw rotation speed of 300 rpm. did. After pre-drying the obtained pellets at 100 ℃ for 2 hours,
Molded articles for evaluation of heat distortion temperature, Izod impact strength, tensile strength, tensile elongation at break and adhesion to polyurethane foam were prepared using an injection molding machine set at 80 ° C and mold temperature of 80 ° C.

The mechanical properties and the like of each PPE-based resin molded product and the adhesiveness with a polyurethane foam were tested. The results are shown in Table 1. The heat distortion temperature is ASTM D648, Izod impact strength (notched) is ASTM D256, tensile strength is ASTM D638, and tensile breaking strength is AST.
The measurement was performed according to M D638.

As the raw material of the urethane for foam molding used for the test piece, the one having the following composition was prepared. Urethane A polyether polyol 64.6% by weight water 2.0% by weight TDA 0.6% by weight polyethanolamine 0.1% by weight methylene diisocyanate 32.4% by weight pigment 0.3% by weight urethane B polyether 58.1% by weight triethanolamine 3.0% by weight water 1.5% by weight triethylamine 0.6 % By weight Crude methylene diisocyanate 36.8% by weight Using these urethane raw materials, test pieces for evaluation of adhesiveness with polyurethane foam were prepared as follows.

A 150 × 150 × 3 mm plate-shaped molded article injection-molded from the PPE resin composition of each Example and Comparative Example was fixed in a molding die, and the urethane raw material at 20 ° C. (15 After stirring for 2 seconds), the mixture was cast and foam-cured at 40 ° C. for 10 minutes. The thickness of the polyurethane layer was about 10 mm, and the foam density was 0.17. A test piece having a width of 20 mm and a length of 150 mm was cut out from the thus-obtained molded article of the PPE resin composition having polyurethane attached thereto.

The test piece thus obtained was subjected to 5 cycles of cooling and heating with α: as it was, β: −30 ° C. for 1 hour and 110 ° C. for 1 hour, and then γ: 60 ° C. × 95 RH% × 40 hours. After being exposed to the high temperature and high humidity aging conditions, the following three tests were performed to test the adhesion between the molded article of each PPE resin composition and the polyurethane foam.

Test 1: The polyurethane layer and the PPE layer were grasped together at one end so that the polyurethane layer was down in the length direction of the test piece, and at the other end only the urethane layer was pulled downwards. , Warped deformation was given.

Test 2: At one end of the test piece, the polyurethane layer and the PPE layer were respectively sandwiched by fingers, and a force was applied to slowly peel them off.

Test 3: After the polyurethane was forcibly removed from the test piece, the surface was rubbed with a scraper and PPE was used.
It was visually observed whether the clean surface of the layer was exposed.

In the columns of tests 1 and 2 in Table 1, ○
Indicates that the polyurethane foam was torn, and x indicates that it was peeled off at the interface between the polyurethane foam and the PPE layer.
Δ indicates that the phenomena of ○ and × occurred.

In the column of Test 3 in Table 1, ◯ means that the surface of the PPE layer did not appear even after rubbing many times.
Indicates that the surface of the PPE layer appeared when rubbed several times.
It is shown that the part that became like and the part that became like x were seen.

[0039]

[Table 1]

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 71/12 LQM 9167-4J

Claims (2)

[Claims] 1. A molded article obtained by adhering a polyphenylene ether-based resin or a resin composition based on the same and a polystyrene-based resin to polyurethane, wherein the polyphenylene ether-based resin or the resin composition based on the polystyrene-based resin is a polyphenylene ether. A) 0.5 to 30 parts by weight of one or more compounds selected from the group of aliphatic and aromatic phosphates, and / or b) one or more, based on 100 parts by weight of the resin or polystyrene resin. A molded article comprising 0.1 to 5 parts by weight of a fatty acid bisamide compound. 2. The polyphenylene ether resin or a resin composition based on the same and a polystyrene resin further contains 0.5 to 50 parts by weight of a terpene phenol resin per 100 parts by weight of the total of the polyphenylene ether resin or the polystyrene resin. The molded article according to claim 1, wherein