JP2612487B2 - Method for improving adhesion to polyurethane foam - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for improving the adhesion of a resin composition containing a polyphenylene ether-based resin and a polystyrene-based resin to a polyurethane foam.

[Prior Art] Polyphenylene ether resins are frequently used in molded articles as engineering resins because of their excellent mechanical properties. However, since polyphenylene ether resin is inferior in moldability, it is often mixed with polystyrene resin and injection-molded. Particularly in the field where impact resistance is required, rubber-reinforced polystyrene (HIPS) is used by being blended with polyphenylene ether resin.

However, a molded article of such a resin composition comprising a polyphenylene ether resin and a polystyrene resin does not adhere to a polyurethane foam. For example, in an instrument panel of an automobile, it is necessary to adhere to a polyurethane foam.

It has been proposed to mix a polar resin such as ABS and SMA (styrene-maleic anhydride) to improve the adhesiveness (JP-A-60-36554 and JP-A-63-118366). But,
These polar resins have poor compatibility with the polyphenylene ether / polystyrene system, and thus cause problems such as delamination and deterioration of mechanical properties.

[Problems to be Solved by the Invention] The present invention improves the adhesion of a resin composition containing a polyphenylene ether-based resin and a polystyrene-based resin to a polyurethane foam without delamination and mechanical properties as described above. The purpose is to:

[Means for Solving the Problems] The present invention relates to a polyurethane foam of a resin composition containing a polyphenylene ether-based resin and a polystyrene-based resin (but not containing a styrene-grafted propylene polymer) and containing no inorganic filler. And a method for improving the adhesiveness with the terpene phenol resin in an amount of 0.5 to 50 parts by weight per 100 polymerized parts of the polyphenylene ether-based resin and the polystyrene-based resin in total.

The terpene phenolic resin used in the present invention is known. The terpene phenol resin is used in an amount of 0.5 to 50 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the total of the polyphenylene ether resin and the polystyrene resin. If the amount is less than this, the effect of the invention, that is, the effect of improving the adhesiveness is too small, while if it is more than this, the excellent mechanical properties of the polyphenylene ether / polystyrene system cannot be exhibited.

In the present invention, the polyphenylene ether-based resin is known per se, for example, a compound represented by the general formula (A) (Wherein R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen, halogen, alkyl, alkoxy, haloalkyl and haloalkoxy having at least two carbon atoms between the halogen atom and the phenyl ring) Represents a monovalent substituent selected from those not containing a tertiary α-carbon, and n is an integer representing the degree of polymerization. Or a copolymer of two or more. In a preferred embodiment, R ₁
And R ₂ are an alkyl group having 1 to 4 carbon atoms, and R ₃ , R ₄
Is hydrogen 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.
A particularly preferred polyphenylene ether resin is poly (2,6
-Dimethyl-1,4-phenylene) ether. Examples of the polyphenylene ether copolymer include a copolymer in which an alkyl trisubstituted phenol, for example, 2,3,6-trimethylphenol is partially contained in the above polyphenylene ether repeating unit. Further, a copolymer in which a styrene compound is grafted to these polyphenylene ethers 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 to the above-mentioned polyphenylene ether.

The polystyrene resin used in the present invention has a general formula (Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms, Z is a halogen or a substituent which is an alkyl group having 1 to 4 carbon atoms, and p is an integer of 0 to 5). It must have at least 25% by weight or more of the repeating structural units derived from the indicated vinyl aromatic compound in the polymer.

Examples of such polystyrene resins include polymers of styrene or derivatives thereof (eg, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene, and mixtures thereof), such as polybutadiene, polyisoprene, butyl rubber, EPDM rubber, Styrene polymers modified with natural or synthetic elastomeric materials, such as natural rubber, polysulfide rubber, polyurethane rubber, epichlorohydrin. The composition of the present invention does not include a styrene-grafted propylene polymer, where the propylene polymer also includes a propylene copolymer, and also includes a polymer obtained by grafting styrene and other monomers onto the propylene polymer.

Particularly preferred polystyrene resin in the present invention,
Polystyrene, rubber reinforced polystyrene (HIPS), or a mixture thereof.

In the present invention, the weight ratio of the polyphenylene ether-based resin and the polystyrene-based resin is 10:90 to 90:10, preferably 2
0:80 to 80:20.

The resin composition of the present invention can further contain a rubber-like substance in an amount of, for example, 20 parts by weight or less per 100 parts by weight of the total of the polyphenylene ether-based resin and the polystyrene-based resin. As the rubbery 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.

Furthermore, the resin composition of the present invention may contain other additives, for example, pigments, dyes, fillers, as long as the physical properties are not impaired.
Heat-resistant agents, antioxidant deterioration agents, weathering agents, lubricants, release agents, crystal nucleating agents, plasticizers, flame retardants, flow improvers, antistatic agents and the like can be added.

There is no particular limitation on the method for producing the resin composition of the present invention, and ordinary methods can be used satisfactorily. However, the melt mixing method is generally preferred. There is no particular limitation on the temperature and time required for melt mixing, and they can be appropriately determined depending on the composition of the material. The temperature will vary somewhat with the mixing ratio of polyphenylene ether to polystyrene, but typically ranges from 270 to 3
Within the range of 50 ° C. Although a long time and / or a high shear rate is desirable for mixing, the deterioration of the resin composition proceeds. Therefore, it is desirable that the time is determined in consideration of these points. 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, or the like.

EXAMPLES Hereinafter, the present invention will be further described with reference to examples.

The polyphenylene ether resin (PP
O) has an intrinsic viscosity of 0.48dl / g in chloroform at 25 ° C.
Of poly (2,6-dimethyl-1,4-phenylene) ether.

The polystyrene resin is a rubber reinforced polystyrene (Mitsubishi Monsanto Kasei Co., Ltd., trade name Dialex HT64)
4) or Posistyrene (Dainippon Ink and Chemicals, Dick Styrene CR3500).

Terpene phenolic resin is Mighty Ace G-150
(Trademark, Yasuhara Yushi Kogyo Co., Ltd.) with an average molecular weight of 70
0, having a softening point of 150 ° C and 1.7 hydroxyl groups per molecule.

 As an optional ingredient, a rubbery substance (SEBS) was added.

As a comparative example, a terpene phenol resin was not used and a styrene-maleic anhydride copolymer (SMA) was used.
An example using (containing 17% of maleic anhydride) is shown below.

All components were uniformly premixed using a Henschel mixer at the weight ratios shown in the following table, and the mixture was heated at a cylinder temperature of 290.
The mixture was kneaded with a twin-screw extruder set at 300 ° C. and a screw rotation speed of 300 rpm to form pellets. After pre-drying the obtained pellets at 100 ° C for 2 hours, the cylinder temperature was 280 ° C and the mold temperature was 80 ° C.
Izod impact strength using an injection molding machine set at ℃
Test pieces for evaluating tensile strength, tensile elongation at break, heat deformation temperature and adhesion to polyurethane foam were formed.

The mechanical properties of each molded article were tested. The results are shown in the table.

Further, the adhesion between the molded article and the polyurethane foam was tested. The following composition was prepared as a urethane raw material for foam molding.

Injection-molded from the resin compositions of Examples and Comparative Examples 15
A plate-shaped molded product of 0 × 150 × 3 mm was fixed in a mold, and the above-mentioned urethane raw material at 20 ° C. was cast thereon, followed by foaming and curing at 40 ° C. for 10 minutes. The thickness of the polyurethane layer was about 10 mm, and the foam density was 0.17.

Obtained in this way. A test piece having a width of 20 mm and a length of 150 mm was cut out of the plate-like molded product having polyurethane adhered thereto. Next, the resin plate and the polyurethane layer were partially peeled off at the longitudinal end, the urethane layer was sandwiched by the left hand with the urethane layer facing down, and the other end of the test piece was grasped by the right hand and bent upward. At this time, the peeling state between the resin plate and the polyurethane layer was visually observed.

As is evident from the above, according to the present invention, the adhesion between the resin composition containing the polyphenylene ether-based resin and the polystyrene-based resin and the polyurethane foam could be improved without delamination and reduction in mechanical properties.

Claims (1)

(57) [Claims] 1. A method for improving the adhesion of a resin composition containing a polyphenylene ether resin and a polystyrene resin (but not containing a styrene graft propylene polymer) and containing no inorganic filler to a polyurethane foam. A method comprising adding 0.5 to 50 parts by weight of a terpene phenol resin per 100 polymerized parts of a polyphenylene ether-based resin and a polystyrene-based resin in total.