JP3487211B2 - Olefin-based thermoplastic elastomer molded product - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is provided with a sealant abutting portion that abuts a urethane sealant, and is substantially TPO.
The present invention relates to a TPO molded product formed of a material.

Here, as a TPO molded product, a window glass peripheral molding (hereinafter simply referred to as "mold") 26 as shown in FIG. 1 will be described as an example, but if a sealant contact portion is provided. The present invention is not particularly limited, and the present invention can be applied to the roof molding 27 as shown in FIG. 4, the sealant dam 20 (see FIG. 1), and the like.

[0003]

2. Description of the Related Art A windshield (window glass) 12 is attached to a window frame recess 14 formed of sheet metal as described below as follows. The window frame recess 14 is formed of a flange portion 16 on the bottom side (inside the vehicle) and a standing wall 24 on the rising side.

First, after the sealant 22 is loaded on the flange portion 16 of the window frame recess 14, the double-sided adhesive tape 1 is applied to the inside surface of the vehicle.
The window glass 12 having the sealant dam 20 attached to the periphery thereof via 8 is fitted into the window frame recess 14 and is pushed toward the inside of the vehicle to extend the sealant 22 to move the window glass 12 into the window frame recess 1
Fix at 4. Subsequently, the molding 26 is mounted in the gap formed between the window glass 12 and the rising wall 24 of the window frame recess 14.

At this time, the molding 26 basically has a molding main body 28 located outside the vehicle and the molding main body 28.
It has a leg portion 30 projecting inward from the vehicle and a sealant contact portion 32 formed at the tip of the leg portion 30. The molding body 28 includes the outer peripheral edge of the window frame recess 14 on the outer side of the vehicle and the window glass 1.
2 includes a window glass outer surface engaging portion 34 and a seal lip portion 36 which are respectively locked to the outer peripheral edges of the vehicle outer side. Further, the sealant abutting portion 32 includes a window glass inner surface engaging portion 38 and a rising wall friction locking portion 40.

The molding of the molding 26 is carried out, for example, by extruding a polyvinyl chloride (PVC) material, cutting the extruded product, setting the extruded product in a mold, and injection-molding a corner portion of the molding. I was going to form.

As the sealant 22, a urethane type sealant which is excellent in adhesiveness to the window glass 12 and further excellent in vibration absorption, durability and sealing property is usually used. On the other hand, a strong heat-resistant adhesive property is required between the sealant 22 and the molding 26. For this reason, normally, an isocyanate-based primer is applied to the sealant contact side surface 32a of the sealant contact portion 32 of the PVC molding 26 to ensure adhesiveness.

[0008]

However, in view of recent problems of environmental pollution and resource saving, replacement of PVC material with other material has been demanded also in the molding.

[0009] Therefore, the inventors of the present invention, as a molding material for molding, have little environmental pollution, are easy to recycle, and have the smallest density of the thermoplastic thermoplastic elastomer (TPE) among the thermoplastic elastomer (TPE).
Focused on (PO) and made an effort for development.

However, it has been found that the urethane sealant cannot secure practical adhesive strength (especially after heat resistance test) with TPO. Naturally, urethane sealant and TPO
A suitable primer capable of adhering to and has not been developed yet.

In view of the above, the present invention is substantially T-type.
It is an object of the present invention to make it possible to obtain a practical adhesive strength between a urethane sealant and a sealant contact portion in a TPO molded product formed of a PO material.

[0012]

The TPO molded article of the present invention solves the above problems by the following constitution.

A T having a sealant abutting portion that abuts the urethane sealant and is substantially formed of a TPO material.
In the PO molded product, the sealant contacting side of the sealant contacting portion is a PVC layer or a TPU layer, and at least a portion of the molded product main body adjacent to the PVC layer or the TPU layer contains all or part of the TPO soft phase. It is characterized in that it is formed of chlorinated TPO which can be heat-bonded to the PVC layer by substituting it with chlorinated PE.

The above chlorinated TPO has a chlorine content of 1
~ 20 wt% of PVC layer or TP
It is desirable because the heat fusion property with the U layer can be easily secured.

[0015]

[Detailed Description of Configuration] The configuration (means) of the present invention will be described in detail below. In the following description, “part” indicating a compounding unit means “part by weight” unless otherwise specified.
Further, the same parts as those in the above-described example are designated by the same reference numerals, and the whole or part of the description thereof will be omitted.

The molding (TPO molded product) 26 of the present invention is
Sealant contact portion 3 that contacts the urethane sealant 22
2 and is essentially formed of a TPO material.

The sealant contact side 32a of the sealant contact portion 32 is formed of a PVC layer (or TPU layer) 42,
In the molded article body (mole body portion 28 and leg portion 30), at least a portion adjacent to the PVC layer (or TPU layer) 42 replaces all or part of the TPO soft phase with chlorinated PE to form a PVC layer ( Or TPU layer) and chlorinated TPO capable of heat fusion.

At this time, as the chlorinated TPO, one having a chlorine content of 1 to 20% by weight, preferably 2 to 15% by weight is used.

The mall will be described as an example in more detail.

As described above, the molding 26 shown in FIG. 2 has the molding main body portion 28, the leg portion 30, and the sealant contact portion 32. The molding main body portion 28 includes a window glass outer surface engaging portion 34 and a seal lip portion 36 that engage with the vehicle outer peripheral edge of the window frame recess 14 and the vehicle outer peripheral edge of the window glass 12, respectively. Further, the sealant abutting portion 32 includes a window glass inner surface engaging portion 38 and a rising wall friction locking portion 40.

The sealant contact side surface 32a of the sealant contact part 32 is formed of a PVC layer (or TPU layer) 42, and the other part, that is, the molded product body (the molding body 28 and the leg 30) is chlorinated. It is made of TPO.

Here, chlorinated TPO means that the hard phase component is an olefin resin and the soft phase component is ethylene-α-
This is a chlorinated product of TPO, which is an olefin-based copolymer rubber, in which some or all of the ethylene-α-olefin-based copolymer rubber is replaced with chlorinated PE rubber. The ratio of the hard phase component and the soft quality-phase component varies depending hardness required for chlorinated TPO, usually, the former / the latter = 30/7
The range is 0 to 70/30. The hardness can be adjusted to some extent depending on the blending amount of the process oil.

Examples of the olefin resin include polyethylene (PE), polypropylene (PP), polybutene (PB) and copolymers thereof,
Particularly, the block type PP is desirable.

Specific examples of the ethylene-α-olefin copolymer rubber include ethylene-α-olefin copolymer rubber and ethylene-α-olefin-non-conjugated diene copolymer rubber, and α- Propylene is preferably used as the olefin, and ethylidene norbornene is preferably used as the non-conjugated diene.

The ethylene-α-olefin copolymer rubber in TPO can be present in a crosslinked state such as uncrosslinked, partially crosslinked or totally crosslinked, but from the viewpoint of compression set, partially crosslinked or totally crosslinked ( Dynamic vulcanization) is preferred.

The chlorinated PE rubber has a chlorine content of 25.
-60 wt%, preferably 40-50 wt% can be used. If the chlorine content is outside the above range, the following problems are likely to occur.

If the chlorine content is too high, block type PP
Or the ethylene-α-olefin-based copolymer rubber becomes less compatible, and when the amount is too small, it is necessary to relatively increase the amount of the chlorinated PE rubber compounded. The amount of coalesced rubber added is relatively small,
It becomes difficult to adjust the hardness of the molded product.

The total chlorine content of the chlorinated TPO is usually adjusted to 1 to 20% by weight, preferably 3 to 15% by weight by adjusting the compounding amount of the chlorinated PE rubber. If the chlorine content is too low, fusion (co-extrusion) with the PVC layer 42 will be difficult, while if too high, the reduction of chlorine content, which is the object of the present invention, is expected to reduce environmental pollution. Can not. That is, from the viewpoint of environmental pollution reduction, if heat fusion between the chlorinated TPO and the PVC layer 42 is possible,
Smaller chlorine content is desirable.

In the present embodiment, although not necessarily, the seal lip portion 36 of the molding body portion 28 is made of a TPO material softer than other portions from the viewpoint of sealing property, and the outer surface of the outer surface engaging portion of the window glass 12 is made. Is a TP that is relatively harder than other parts from the viewpoint of imparting abrasion resistance when wiping the window glass 12.
It is desirable to form the wear resistant layer 44 with an O material. For example, when the molded product body (mall body portion 28, leg portion 30, sealant contact portion 32) has a hardness H _s (JIS A) of 85 °,
The hardness of the seal lip portion 36 is H _s (JIS A) 75 ° and the hardness of the wear resistant layer is H _s (JIS A) 90 °.

At this time, the seal lip portion 36 and the wear resistant layer 44 may be formed of general-purpose non-chlorinated TPO.
It is desirable to use chlorinated TPO for each TPO material from the viewpoint of fusion property and coextrusion property. Table 1 shows an example of the material composition of each hardness that can be used for each part. TPO-
4 is for the seal lip portion 36, and TPO-5 is for the wear resistant layer 44.

The PVC layer (or TPU layer) 42 is
As shown in FIG. 3, the entire sealant contact portion 32 may be used, but in the case of a PVC layer, from the viewpoint of reducing environmental pollution, T
In the case of the PU layer, it is desirable that the PU layer be as thin as possible from the viewpoint of material cost reduction.

The PVC layer (or TPU layer) 42 may be formed by coating with a dispersion paint (including paste sol) or the like, but coextrusion is preferable from the viewpoint of productivity. In that case, the wall thickness is 0.05 to 1 mm. If it is less than 0.05 mm, coextrusion is difficult, and
It is difficult to obtain a practical adhesive strength even when a urethane primer is applied to a urethane sealant.

When the TPU layer is used instead of the PVC layer, since the sealant is a urethane type, it has not been confirmed, but it can be expected that primerless is possible.

As the PVC material for forming the PVC layer 42, usually, 30 to 70 phr of an ester plasticizer such as DOP is added to a vinyl chloride homopolymer or a vinyl chloride-based copolymer. Accordingly, it is desirable to use a soft PVC material (elongation at break of 180% or more) in which the hardness of the molded product body and the tensile elastic modulus are substantially the same. A polymer blend type PVC-based thermoplastic elastomer can also be used.

The TPU forming the TPU layer 42 is
A polymer chain composed of diisocyanate and a short-chain glycol serves as a hard segment, and a polymer chain composed of diisocyanate and a long-chain glycol serves as a soft segment. Here, as the short-chain glycol, ethylene glycol, propylene glycol, 1,4-butanediol, etc. are used, and as the long-chain glycol,
Polyether-based ones such as polyalkylene glycol (particularly PTMG: polytetramethylene glycol) or polyester-based ones such as polycaprolactone and polycarbonate are used. (Polymer Society, “Polymer Material One Poin
t-19 Elastomer "(1989-2-20) Kyoritsu, p.75).

Among these long-chain glycols, water resistance,
A caprolactone-based material is preferable because it is easy to balance heat aging resistance, oil resistance and cold resistance.

As the diisocyanate, 4,
4'-diphenylmethane diisocyanate (hereinafter "MD
I)), crude MDI, liquid MDI, tolylene diisocyanate, phenylene diisocyanate, and the like, and from the viewpoint of handling, dimer, trimer, trimethylolpropane, prepolymer obtained by polymerizing these. Aromatic compounds such as polymers, or isocyanate hexamethylene diisocyanate (HMDI),
Xylene diisocyanate (XDI), hydrogenated xylene diisocyanate (hydrogenated XDI), 4,4'-methylenebisdicyclohexyl diisocyanate (H12MD
I), methylcyclohexyl diisocyanate (hydrogenated T
DI) and isophorone diisocyanate (IPDI)
Further, from the viewpoint of handling, so-called non-yellowing aliphatic (alicyclic) compounds such as dimers, trimers, trimethylolpropane adducts and prepolymers obtained by polymerizing them can be used.

As in the case of the PVC layer, the TPU layer is also made of a soft PVC material (tensile modulus and tensile modulus of the molded article body are adjusted to be substantially the same by adjusting the ratio of the hard segment and the soft segment). It is desirable to use an elongation at break of 180% or more).

In the above description, the windshield molding is taken as an example, but the roof molding 2 as shown in FIG. 4 is used.
Of course, it is applicable to 7. For example, the mall body 28
A is made of chlorinated TPO, the sealant contact side of the molding body portion 28A is formed of a PVC layer (or TPU layer) 42A, and the wear resistant layer 44A on the opposite side surface is slightly harder than that of the molding body portion 28A. It is a structure formed of highly chlorinated TPO.

[0040]

As described above, the TPO molded article of the present invention has a PVC layer (or TPU layer) formed on at least the sealant contacting side of the sealant contacting portion, and at least the above-mentioned PVC in the molded article body. The part adjacent to the layer is made of chlorinated TPO capable of being heat-sealed (heat-bonded) to the PVC layer (or TPU layer) by replacing all or part of the soft phase with chlorinated PE. In a TPO molded product that is molded by TPO, practical adhesive strength with a urethane sealant can be obtained without special measures such as a primer.

[0041]

[Test Example] Next, a test example performed for confirming the effect of the present invention will be described for the combination of the example and the comparative example.

A. PVC layer / TPU used in the test
The layer forming material, the isocyanate-based primer and the urethane sealant will be described below.

(1) PVC layer forming material (soft PVC) Polymer: straight Average degree of polymerization 1100 Plasticizer: di- (2-ethylhexyl) phthalate (DO
P) 55 phr _{Hardness: H S (JIS A) 85} ° (2) TPU layer forming material (TPU) polycaprolactone _{Hardness: H S (JIS A) 85} ° elongation: 600% (3) an isocyanate-based primer "Sunstar Manufacture and sale of Sunstar Giken Co., Ltd. (4) Urethane sealant "Sunstar Penguin seal # 552" Manufacture and sale of Sunstar Giken Co., Ltd. B. The test was performed for each of the following items by the following method.

(1) Adhesiveness Evaluation Test with Urethane Sealant A base material (30 mm × 100 mm × 30 mm × 100 mm × 30 mm) was cut from an extruded product prepared by extruding the side surface materials of TPO-1 to 5 shown in Table 2 in contact with the sealant. The surface of 1 mmt) was coated with the above-mentioned isocyanate-based primer (5 g / 100 cm ² ), left at room temperature (23 ° C.) for 24 hours, and then further urethane sealant (“WS-70” manufactured by Yokohama Rubber Co., Ltd.). ) Was applied with a hand gun to a thickness of 3 to 4 mm and allowed to stand at room temperature (23 ° C.) for 144 hours to cure the sealant layer to give a test piece.

With respect to each test piece, with the interface between the base material and the sealant layer peeled off by a knife for a length of about 20 mm, the base material was pressed by hand and the sealant layer was gripped by the hand.
Peeling test by pulling in the bent direction of more than °,
The interface state was visually observed. The evaluation criteria are as follows.

◯ ... Cohesive failure of sealant layer Χ: The results of the interfacial failure test between the base material or the primer layer and the sealant layer are shown in Table 2. Although the PVC layer or the TPU layer and the sealant layer can be bonded, TPO It is difficult to obtain practical adhesive strength with any of the layers. That is, unchlorinated T
PO-1 or TPO-2 with a low chlorine content of 4.5%
・ In the cases of 4 and 5, practical adhesive strength was not obtained both in the initial stage and after the heat resistance test, and the chlorine content was as high as 13.5%.
In the case of PO-3, practical adhesive strength can be obtained in the initial stage, but practical adhesive strength cannot be obtained after the heat resistance test.

(2) Adhesion Evaluation Test between PVC Layer or TPU Layer and TPO Material Each material of TPO-1.2.3 shown in Table 1 and the above PVC
Strip-shaped base material (30 mm × 100 mm × 1 mm) prepared by cutting an extrusion-molded sheet formed from a material or TPU material
t) The pieces were superposed on each other, and half of the pieces were heated and pressure-bonded (180 ° C. × 3 MPa × 10 seconds) with a press molding machine and cooled to obtain a test piece.

The PVC layer and each TPO layer were grasped by both hands and pulled to both sides, and the presence or absence of peeling was visually evaluated. The evaluation criteria are as follows.

◯: No peeling, Χ: Complete peeling.

Between the PVC layer or the TPU layer and the TPO layer, when chlorinated TPO-2.3 is used, practical adhesive strength is obtained, but non-chlorinated TPO-1.
It can be seen that the practical adhesive strength cannot be obtained when the above is used.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a conventional mounting example of a window glass peripheral molding to which the present invention is applied.

FIG. 2 is a cross-sectional view of a window glass peripheral molding showing an embodiment of the present invention.

FIG. 3 is a sectional view of a window glass peripheral molding showing another embodiment of the present invention.

FIG. 4 is a sectional view of a roof molding showing another embodiment of the present invention.

[Explanation of symbols]

12 Windshield (window glass) 14 Window frame depression 26 Window glass peripheral mall 27 Roof Mall 28, 28A Mall body 30 legs 32 Sealant contact part 32a Sealant contact side surface 42, 42A PVC layer (or TPU layer) 44, 44A Wear resistant layer

Front page continued (72) Inventor Hiroshi Iwasaki 1 Ochiai, Nagachiji, Kasuga-cho, Nishi-Kasugai-gun, Aichi Toyoda Gosei Co., Ltd. Within the corporation (56) Reference JP-A-5-77363 (JP, A) JP-A-3-150156 (JP, A) JP-A-8-12788 (JP, A) Actually open flat 4-37011 (JP, A) U) Actual Kaihei 5-32061 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 B60J 1/02

Claims (4)

(57) [Claims] 1. A molding body located outside a vehicle,
The leg protruding from the main body to the inside of the vehicle and the tip of the leg
The formed Rutotomoni a urethane sealant and abuts the sealant contact portion, the sealant abutment windowpane
Comprising a friction engaging portion rising the inner surface engaging portion, and in the window glass periphery mall formed by molding with a substantially olefin-based thermoplastic elastomer (TPO) material, the sealant abutting section may Zealand abutment side Only the polyvinyl chloride layer (PVC layer) or the thermoplastic urethane layer (TPU layer) is formed , and the part adjacent to the PVC layer or the TPU layer is a chlorinated polyethylene (or a part of the TPO soft phase). Chlorinated T) that can be heat-sealed to the PVC layer or TPU layer by substituting it with chlorinated PE) rubber
Periphery window glass characterized by being made of PO
The 2. The PVC layer or the TPU layer has a wall thickness of 0.
The window glass peripheral molding according to claim 1, which is a thin layer of 05 to 1 mm. 3. A molding body located outside the vehicle and the molding
The leg protruding from the main body to the inside of the vehicle and the tip of the leg
The formed Rutotomoni a urethane sealant and abuts the sealant contact portion, the sealant abutment windowpane
In a windowpane peripheral molding that includes an inner surface engaging portion and a rising friction locking portion, and is substantially formed of a TPO material, the sealant contact portion has only a sealant contact side surface. P
A chlorine content of 1 to 20 formed by a VC layer or a TPU layer , and a portion adjacent to the PVC layer or the TPU layer is obtained by replacing all or part of the TPO soft phase with a chlorinated PE rubber.
A window glass peripheral molding characterized by being formed of wt% chlorinated TPO. 4. The PVC layer or the TPU layer has a wall thickness of 0.
The window glass peripheral molding according to claim 3, which is a thin layer having a thickness of 05 to 1 mm.