JP2001270042A - Rubber/thermoplastic elastomer composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber/thermoplastic elastomer(TPE) composite material having a difficulty in occurrence of discoloring such as yellowing at a TPE part by directly adhering an olefin TPE by forming a rubber part of an EPDM rubber blend containing a crystalline PE. SOLUTION: The rubber/TPE composite material is obtained by directly adhering the rubber part 14 made of a vulcanized material of a rubber blend containing the EPDM as a rubber polymer to the TPE part 20 made of a TPE blend. In this case, the rubber blend contains the crystalline PE as a modified resin polymer, and contains an tackifying agent (tackifier). The TPE blend contains the olefin TPE as a base polymer. As the tackifier satisfying various characteristic values of an SP value of 6.0 to 10.0, a softening point of 90 to 110 deg.C, and an aniline point of 80 deg.C or higher, a hydrogenated 9C hydrocarbon resin is, for example, used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
A rubber part made of a vulcanized product of a rubber compound to be OR, and TP
The present invention relates to a rubber / TPE composite obtained by directly bonding a TPE portion made of an E compound. In particular, the present invention is suitable for a weatherstrip for automobiles and the like in which a decorative layer (TPE portion) made of a TPE compound is directly bonded to a weatherstrip body (rubber portion) made of a vulcanized product of a rubber compound.

Here, an automobile weather strip (door weather strip 12) as shown in FIG. 1 will be mainly described as an example, but another type of weather strip (roof side weather strip 12) as shown in FIG.
A: The rubber portion 14A, the TPE portion 20A), and further, other rubber / TPE composites, for example, a door (lip) molding can be applied.

[0003] The main abbreviations used in this specification are as follows.

TPE: thermoplastic elastomer TPO: olefin-based TPE EODM: ethylene-α-olefin-non-conjugated diene copolymer rubber EOR: ethylene-α-olefin-based rubber EPDM: ethylene-propylene-non-conjugated diene copolymer rubber SP value: Solubility Parameter

[0005]

BACKGROUND ART A door weather strip 12 shown in FIG.
A U-shaped mounting base 14, a hollow seal portion 16 formed on the entire outer surface of the U-shaped cross section of the mounting base 14, and a concealing lip portion 18 extending from the top of the U-shaped mounting base 14.
And A decorative layer 20 is continuously formed on the design surface side of the U-shaped mounting base 14 and the concealing lip 18.

The mounting base 14 has a sheet metal insert 22 embedded therein to secure a gripping force for the flange, and a plurality of (three in the illustrated example) receiving lips on one of the inner facing surfaces of the U-shaped cross section. Part 24, holding lip part 26 on the other side
It has.

Conventionally, the weatherstrip 12 provided with the decorative layer 20 having the above-mentioned structure is a weatherstrip made of a vulcanized rubber compound containing ethylene-propylene-non-conjugated diene copolymer rubber (EPDM) as a rubber polymer. A decorative layer was formed by bonding a strip prepared by cutting a polyvinyl chloride (PVC) sheet to the main body (rubber portion) with an adhesive. However, this technique requires a PVC sheet cutting step, an adhesive application, a pressure bonding step, and the like, and the number of manufacturing steps is increased. In addition, EPDM is used as a rubber polymer because
This is because, compared to other rubber polymers, the polymer density is low and the weather resistance is good (because double bonds are not substantially contained in the polymer).

In order to reduce the number of man-hours for manufacturing the weatherstrip, a decorative layer (TPE) of the same type of TPO is extruded into the weatherstrip body (rubber) immediately after vulcanization of the EPDM compound. It is conceivable to adopt a method of manufacturing a weatherstrip by directly bonding by heat fusion. As a known publication describing this technique, there is JP-A-8-174620-8-230013.

On the other hand, from the viewpoint of improving various physical properties in the rubber part, crystalline PE is contained as a modified resin polymer (usually,
The inventors considered using an EPDM formulation at 5 to 35 phr). Known publications describing this EPDM blend include JP-A-11-193335.

However, it has been found that the weather strip having the above-described structure causes discoloration such as yellowing with the passage of time. As a countermeasure against discoloration, it is conceivable to increase the amount of the pigment (colorant) to cope with the concealing effect. It is difficult to cope with the recent tendency of the decorative layer to become lighter and lighter.

In view of the above, the present invention provides a crystalline PE
The purpose of the present invention is to provide a rubber / TPE composite in which a rubber part is formed with an EOR-based rubber compound containing a non-polar TPE and a discoloration such as yellowing does not easily occur in the TPE part. I do.

[0012]

Means for Solving the Problems In order to solve the above problems, the present inventors have analyzed the cause of yellowing and found that TP
E alone did not discolor, and no yellowing of the stabilizers (antiaging agent, ultraviolet absorber, etc.) in the TPE formulation was observed.

For this reason, it is presumed that one of the secondary materials in the vulcanized rubber (rubber compound) migrated to the TPE part and became a causative substance of yellowing. Assuming that the discoloration-causing substance is a tackifier (tackifier) and finding that a specific tackifier has a discoloration preventing action, the present invention (rubber / TPE composite) having the following structure I got it.

A rubber part comprising a vulcanized product of a rubber compound having EOR as a rubber polymer, and a TPE comprising a TPE compound
And a rubber / TPE composite in which the rubber compound is directly adhered to the rubber composition, wherein the rubber compound is a crystalline PE as a modified resin polymer.
And contains a tackifier,
In the case where the TPE compound contains a non-polar TPE as a base polymer, the tackifier has an SP value: 6.
0 to 10.0, softening point: 90 to 110 ° C, aniline point:
It is characterized by satisfying the requirement of 80 ° C. or higher.

The above tackifier has a SP value of 7.0.
To 9.0, softening point: 95 to 104 ° C, aniline point: 10
When the requirement of 5 ° C. or more is satisfied, the compatibility with EPDM and the drug dispersing ability are further increased, and the discoloration preventing ability is easily exerted.

When the tackifier is entirely or mainly selected from hydrogenated petroleum hydrocarbon resins or hydrogenated rosin esters, the ability to prevent discoloration can be more reliably achieved.

Of the above hydrogenated petroleum hydrocarbon resins,
The hydrogenated C9 petroleum hydrocarbon resin has an even more reliable discoloration preventing ability.

In the above structure, the rubber compound is usually
The sulfur vulcanization system is used, the rubber polymer is EODM, the amount of the crystalline PE is 5 to 35 phr, and the amount of the tackifier is 2.5 to 10 phr.

When the rubber polymer is EODM, the nonpolar TPE is usually an olefinic TPE.

The effect of the rubber / TPE composite of the present invention becomes more remarkable when applied to an automobile weatherstrip having a rubber portion as a weatherstrip body and a TPE portion as a decorative layer.

[0021]

DETAILED DESCRIPTION OF THE STRUCTURE Each component (solution means) of the present invention will be described in detail below. In addition, the blending unit is a weight unit unless otherwise specified.

For a part of the names and properties of the tackifier, see the section "8. Tackifiers" of "Rubber / Plastic Compounding Chemicals" (1974), edited and published by Rubber Digest. did.

(1) Rubber compound: The rubber compound forming the rubber portion such as the mounting base of the present invention is based on the premise that the rubber polymer is an ethylene-α-olefin rubber (EOR) and the modified resin It contains crystalline polyethylene (crystalline PE) as a polymer and also contains a tackifier.

The EOR may be an ethylene-α-olefin copolymer rubber, for example, an ethylene-propylene copolymer rubber, but is usually an ethylene-α-olefin non-polymer which is sulfur vulcanizable and has good handleability. A conjugated diene copolymer rubber (EODM) is used.

In the EODM, the α-olefin is propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-octene.
Decene and the like are mentioned, and among them, propylene is preferred.
Examples of the non-conjugated diene include 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-
Norbornene and the like can be mentioned.

Preferred EODMs include ethylene-propylene-ethylidene norbornene copolymer rubber and ethylene-propylene-dicyclopentadiene copolymer rubber.

The above crystalline PE usually has an MFR value of from 0.5 to 0.5, which is obtained by polymerization by a low-pressure method or a medium-pressure method.
3.0, preferably 1.0 to 2.0.

The amount of the crystalline PE is 5 to 35 phr, preferably 15 to 25 phr. If the amount of crystalline PE is too small, the effect of modifying the vulcanizate (improving various physical properties)
However, when the amount is too large, the rubber-like physical properties (softness, elongation) of the vulcanized product are reduced.

The tackifier used in the present invention has an SP value:
6.0 to 10.0 (preferably 7.0 to 9.0), softening point: 90 to 110 ° C (preferably 95 to 104 ° C), aniline point: 85 ° C or higher (preferably 105 ° C or higher) It shall satisfy the characteristics. The boiling point of aniline is 1
84 ° C. (see “Chemical Dictionary” edited by Shoji Shida (1981-3-9), Morikita Publishing, page 3).

If the SP value is too low or too high, the miscibility with the rubber polymer is lacking, and the effect of the tackifier is not sufficiently exhibited. As a result, the roll processability and the PE dispersibility are improved. It is difficult to obtain the effect. By the way, the SP value of EPDM is 7.9 (Source: Tomotake Kimura, “<Case Study> Troubleshooting on-site trouble at rubber factory” Taiseisha, S58.11.15, p.19).

If the softening point is too low or too high, the temperature does not fall within the temperature range during kneading and the effect of the tackifier is not sufficiently exhibited. It is hard to get.

The higher the aniline point, the higher the degree of saturation (non-unsaturation), the stronger the paraffinic tendency, the higher the discoloration prevention effect, the better the miscibility with PE, and the better the PE dispersibility. improves.

Here, the compounding amount of the tackifier is crystalline P
It is necessary to increase the amount of E in accordance with an increase in the blending amount. When the amount of the crystalline PE is 5 to 35 phr, the tackifier is 2.5 to 10 phr, preferably 4 to 8 phr.
The compounding ratio of the latter to the former is: tackifier / crystalline PE
= 1/2 to 1/6, preferably 1 / 2.5 to 1/4. If the amount of the tackifier is too small, it is difficult to obtain the roll adhesiveness required for roll processing during kneading. Excessive tackifier may cause the roll tackiness to become too high and adversely affect the roll processability, and increase the low molecular weight component in the vulcanized rubber composition, adversely affecting the vulcanized rubber physical properties. Bleeding may occur.

The tackifier can be appropriately selected from a coumarone resin type, a phenol terpene type, a petroleum hydrocarbon resin type, a rosin type and the like, as long as the above properties are satisfied. Among these, those having all or mainly hydrogenated (hydrogenated) petroleum hydrocarbon resins or hydrogenated rosin esters are easy to obtain the above characteristic values and are light-colored (including white) to colorless and transparent. Is preferred because it is easy to obtain.

The hydrogenated petroleum hydrocarbon resin has an unsaturated bond such as a synthetic polyterpene resin, an aromatic hydrocarbon resin, an aliphatic hydrocarbon resin, a polymer of unsaturated hydrocarbon, or an isoprene resin. Hydrogenated petroleum hydrocarbon resins can be mentioned. Among them, the hydrogenated C9 petroleum hydrocarbon resin is desirable because it is easy to obtain well-balanced properties as a whole, is colorless and transparent, and has a high discoloration preventing ability. Here, the C9 petroleum hydrocarbon resin is
C such as propenylbenzene, methylstyrene and indene
It refers to a copolymer obtained by copolymerizing only 9 (carbon number 9) components or a main component.

More specifically, those marketed by Arakawa Forestry Chemical Co., Ltd. under the trade name of "ALCON P90, P100" can be suitably used.

By the way, each characteristic value of "Alcon P100" has an average SP value: 8.0, a softening point: 100 ° C., and an aniline point: 110 to 115 ° C.
It is a colorless, transparent, tasteless and odorless resin.

Examples of the hydrogenated rosin esters include hydrogenated products such as rosin methyl ester, trimethylene glycol ester and pentaerythritol ester.

More specifically, those marketed under the trade name "Fine Crystal CE-100" by Arakawa Hayashi San Kagaku Co., Ltd. can be suitably used.

By the way, "Fine Crystal CE-10"
The characteristic values of “0” are as follows. Each characteristic value is an average value, SP value: 8.4, softening point: 100 ° C., aniline point:
It is a very light-colored brittle resin that has a temperature of 100 ° C.

A small amount of a general-purpose aromatic or unsaturated aliphatic tackifier may be used together with the specific tackifier used in the present invention.

The vulcanization system may be a peroxide vulcanization system, but is usually a sulfur vulcanization system. The sulfur vulcanizing agent includes an active sulfur releasing organic vulcanizing agent in addition to sulfur. Examples of the active sulfur releasing type organic vulcanizing agent include morpholine disulfide, alkylphenol disulfide, organic polysulfide polymer, and sulfur-containing vulcanization accelerators such as thiuram type and thiourea type. If necessary, a peroxide vulcanizing agent, a polyamine vulcanizing agent, or the like can be appropriately used in combination.

In the rubber compound, in addition to the vulcanizing agent, carbon black, process oil, lubricant, inorganic filler, antioxidant, and other auxiliary materials are appropriately compounded, kneaded and the like, and weather stripped. It is a rubber material for extrusion molding of the main body.

The preparation of the rubber compound as a molding material is performed, for example, through a kneading step as shown in FIG.

First, Banbury mixer (closed mixer)
The primary kneading of the raw rubber and the auxiliary material containing the vulcanizing agent is carried out by using 28 or the like. The degree of dispersion of the secondary material in the rubber compound is increased while the secondary compound is mixed and kneaded by the kneading roll machine 30 with the rubber compound M1 after the primary kneading. Further, the sheet is rolled out (sheet processing) by a roll-out roll 32, and the tape-shaped molding material M2 is loaded on a carriage 36 through a batch-off step (cooling step) using a cooling tank 34.

In the kneading step, particularly in the secondary kneading, if the added amount of the tackifier is too small, the raw rubber compound M1 floats from the roll 30a, cannot be kneaded again, and cannot be kneaded.

(2) TPE compound: The base polymer of the TPE compound forming the decorative layer of the present invention is rubber part 1
Olefin-based TPE (TPO), styrene-based TPE
A non-polar TPE such as (SBS) can be used. EPD
From the viewpoints of direct adhesion to the M rubber portion and weather resistance, TPO is preferable as the nonpolar TPE.

Here, the ratio of the hard segment to the soft segment of the TPO is the former / the latter = 10/90 to 90 /
10, preferably 70/30 to 20/80.

The hard segment is made of an olefin resin, and is made of polypropylene (PP) or polyethylene (P).
E) or a copolymer of propylene and an α-olefin having 2 or more carbon atoms can be used, and polypropylene is particularly preferable. Examples of the α-olefin having 2 or more carbon atoms include ethylene, 1-butene, 1-pentene, 3
-Methyl-1-butene, 1-hexene, 1-decene, 3
-Methyl-1-pentene, 4-methyl-1-pentene,
1-octene and the like. Olefin resins are
The melt flow rate (MFR; 2.16 kg) is usually in the range of 0.1 to 100 g / 10 min, preferably 0.5 to 50 g / 10 min.

The soft segment is ethylene-α-olefin copolymer rubber (EPR), that is, ethylene-α
-Olefin copolymer rubber (EPM) or ethylene-
α-olefin-non-conjugated diene copolymer rubber (EPD
M) etc. can be used. Here, as the α-olefin, those listed in the above description of the hard segment can be used, and propylene is particularly preferable.

The weight ratio of ethylene / α-olefin is usually 90/10 to 30/70, preferably 85/30.
/ 15 to 45/55. Ethylene α-olefin-
When the non-conjugated diene copolymer rubber is used, the content of the non-conjugated diene is usually from 5 to 40 in iodine value. In addition,
Ethylene α-olefin copolymer rubber and ethylene α-olefin-non-conjugated diene copolymer rubber may be mixed and used. Further, oil-extended rubber may be used.

The Mooney viscosity (ML _{1 + 4} 1
00 ° C) is usually 10 to 350, preferably 3
0 to 300. If the Mooney viscosity is too low, the mechanical strength such as abrasion resistance may be inferior. On the other hand, if the Mooney viscosity is too high, the surface of the decorative layer tends to have irregularities and the appearance may be impaired.

The EOR can be present in the TPE formulation in an uncrosslinked or partially crosslinked, fully crosslinked, or the like state.

The above-mentioned TPE compound is usually mixed with an inorganic filler such as talc and calcium carbonate, a flame retardant,
Additives such as lubricants, antistatic agents, anti-aging agents (heat and light stabilizers), pigments and the like are appropriately added and added.
After extrusion kneading, granulation is performed to obtain an extruded material.

The above-mentioned TPE compound may contain, if necessary, a peroxide non-crosslinked hydrocarbon-based rubbery substance represented by polyisobutylene, butyl rubber and the like and / or a mineral oil-based softener. The amount of the mineral oil-based softener is usually 5 to 100 phr.

The rubber / TPE composite (weather strip) of the present invention is produced by directly bonding a rubber portion and a TPE portion. Here, the direct bonding means that the rubber part and the TP
This means an adhesion state in which a substantial barrier layer does not exist between the rubber layer and the E portion.
E is extruded and pressed into an uncured state, and the compression is performed. The case where the TPE part is extruded or hot-pressed on the rubber part in a state immediately before vulcanization is completed, and the vulcanized adhesive is also included.

The rubber / TPE composite (weather strip) of the present invention can be produced by other conventional methods. For example, when producing the weather strip shown in FIG. 1, the following method is used. It is desirable to manufacture (Fig. 4
reference).

First, a cross-head type two-color extruder 38
After the co-extrusion of the solit rubber part (mounting base part 14) and the sponge rubber part (hollow seal part 16), UH
F (microwave) vulcanizer 40, hot air vulcanizer (HA)
V) Vulcanizing with 42 or the like to obtain a weather strip main body (rubber portion) W which is a vulcanized rubber extrudate.

Next, the decorative film D made of the TPE compound is coated with a predetermined thickness independently of the weatherstrip body W.
After the decorative film is extruded in the width by the decorative film extruder 44, the decorative film D is pressed against the upper surface of the mounting base 14 and the concealing lip 18 of the weatherstrip main body W by the pressing rollers 46 and 48 before curing. The decorative layer 20 is formed on W.

That is, the vulcanizing step end position of the weatherstrip body W (outside the outlet side of the hot air vulcanizing device 42 in the illustrated example).
, A decorative film extrusion device 44 is provided, and first and second pressure rollers 46 and 48 are sequentially contacted near the exit side of the decorative film extrusion die (not shown). In addition,
50 is a take-up roller. The first pressure roller 4
6, a receiving roller 52 may be provided (see FIG. 4).
See dash-double-dot line).

Here, in order to ensure reliable direct adhesion between the weatherstrip body W and the decorative film D, the decorative film D is pressed with the pressure roller 46 at a temperature not lower than the melting temperature of the thermoplastic resin. 48 and between the weatherstrip body (vulcanized rubber extruded product) W and cooled by the pressure rollers 46, 48 to a temperature not higher than the melting temperature of the thermoplastic resin. It is desirable to send out from between the object W.

The control temperature of the pressure rollers 46 and 48 is usually set at 40 to 50 ° C. The decorative film D is extruded at a temperature 10 to 20 ° C. higher than the melting temperature of the thermoplastic resin, and the decorative film is surely extruded at a temperature equal to or higher than the melting temperature with the pressing rollers 46 and 48 and the vulcanized rubber extrudate W. , The weatherstrip body W is also
It is desirable to heat to about 0 ° C.

[0063]

According to the rubber / TPE composite of the present invention, discoloration such as yellowing does not occur due to the above constitution, as supported by the test examples described later. Therefore, when the present invention is applied to an automobile weather strip or the like, a remarkable effect of maintaining the beautiful appearance at the beginning of use forever is exerted.

[0064]

[Test Examples] Next, test examples performed to confirm the effects of the present invention will be described.

The properties of tackifiers other than "Alcon P100" and "hydrogenated rosin" used in each of the examples and comparative examples are as follows.

Rosin: SP value: 8.3, softening point: 106
° C, aniline point: 76 ° C, polyterpene ... SP value: 9.
1. Softening point: 135 ° C, aniline point: 78 ° C, (1) Preparation of EPDM compound: Based on the compounding recipe shown in Tables 1-2, raw rubber and auxiliary materials (drugs) were prepared as shown in FIG. According to the process, kneading was performed to prepare a molding EPDM compound. In the secondary kneading, the roll kneading was performed at a roll rotation speed of 27 rpm by using a roll kneading machine having two rolls each having a mill blender, a roll diameter of 24 inches, and a roll drive motor of 70 kW.

For each rubber compound, the roll kneadability was determined as follows:
The roll processability, kneading dispersion degree, and kneading completion time were evaluated according to the following criteria.

Roll processability (visual judgment of the roll adhesion of the rubber material) 無 し: no lifting from the roll, Δ: floating from the roll, kneading dispersity (existence of agglomerates in the rubber material after completion of kneading) Visual judgment) ... ○: No agglomerate, Δ: Some agglomerate, Δ: Stand out agglomeration Kneading completion time (reference: 2 to 2.5 minutes) And the results are shown in Tables 1 and 2. PE
It can be seen that Comparative Example 1 containing no PE has no problem in kneading property, whereas Comparative Example 2 containing crystalline PE and containing no tackifier has a problem in kneading property. On the other hand, it can be seen that Comparative Examples 3 and 4 in which a general-purpose tackifier is blended have no problem in kneading.

Further, it can be seen that all the examples are good in all items and there is no problem in roll kneading.

For reference, the unvulcanized rubber properties (Mooney viscosity (ML _{1 + 4} 145 ° C.) and Mooney scorch time (ST) of each rubber compound in Comparative Example 1 and Examples 1, 3, and 4 were used. ) Was measured in accordance with JIS K 67300, and the normal physical properties of the rubber vulcanizate were measured in accordance with JIS K 6301. Table 3 showing the results shows the following.

Example 1 containing 10 phr of crystalline PE
Tensile properties (T _B , E _B ) are increased at 10 phr as compared to Comparative Example 1 containing no crystalline PE. Further, in Example 2 containing 20 phr of crystalline PE, the tear strength (T _R ) as well as the tensile properties (T _B , E _B ) were significantly increased as compared with both Comparative Example 1 and Example 1. . In addition, Example 3 containing 30 phr of crystalline PE, compared to Example 2,
Although the tear strength (T _R ) and the 100% modulus increase, the tensile properties (T _B , E _B ) hardly change.

(2) Preparation of TPE blend: PP (230 ° C.
20 parts, MFR = 12 g / 10 min, EPDM (non-conjugated diene: ethylene-propylene-5-ethylidene-2-
Norbornene, ethylene / propylene weight ratio = 79/2
1, iodine value = 12) 80 parts, organic peroxide (2,5-
0.2 parts of dimethyl-2,5-di (tert-butylperoxy) hexane was melt-mixed for 12 minutes using a Banbury mixer and dynamically heat-treated. Then, a paraffin-based process oil (Diana PW manufactured by Idemitsu Kosan Co., Ltd.)
380 ”), 5 parts, 0.6 part of a gray pigment (titanium) were added, mixed for 5 minutes, and further granulated by a single screw extruder to obtain a pellet-like composition for TPE extrusion molding of Example 1. Was prepared.

(3) Discoloration resistance (yellowing) test A rubber substrate (1 mmt) made of each of the rubber compounds prepared above was used.
Vulcanized by extrusion (condition: 170 ° C x 10 minutes)
Immediately after, the decorative layer (1 mmt) made of the TPE compound prepared above was extruded and pressed (hot press at 60 ° C.) to obtain a laminated sheet material, which was cut (40 mm) to prepare each test piece. Did.

For each test piece, the discoloration (discoloration degree) after each of the following tests was evaluated by the color difference before and after the following light resistance test based on JIS D 0205. As a measuring device, "Color Nata (TM type two-path optical glare preventing optical system)" manufactured by Suga Test Instruments Co., Ltd. was used.

The test results are shown in Tables 1 and 2. In each of the examples using the tackifier satisfying the requirements of the present invention, the results were remarkably higher than those in Comparative Examples 3 and 4 in which a general-purpose tackifier was blended. It can be seen that the yellowing degree is low. Conversely, it can be seen that the specific tackifier composition has the ability to prevent discoloration. That is, when a predetermined amount or more of the tackifier exhibiting the characteristics of the present invention is blended, the discoloration resistance can be improved, as compared with Comparative Example 2 in which no tackifier is blended and Comparative Example 5 in which the tackifier is underblended. 3 can be seen from the fact that the degree of discoloration is smaller.

Further, even if the tackifier satisfies the characteristic requirements of the present invention, Comparative Example 5 in which the compounding amount is too small (2 parts) has not only a poor kneading property but also a discoloration degree of each example. It turns out that it is slightly higher than the comparison.

<Light resistance test> Fade meter (ultraviolet carbon arc lamp type light resistance tester) (black panel temperature:
83 ° C) and accelerated exposure test according to JIS D 0205.
00h.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a door weather strip showing an example of a rubber / TPE composite to which the present invention is applied.

FIG. 2 is a sectional view of a roof side weather strip showing another example.

FIG. 3 is an explanatory view showing an example of a kneading process of a rubber compound.

FIG. 4 is a schematic overall process diagram showing a TPE part bonding method when the rubber / TPE composite of the present invention is applied to a weather strip.

[Explanation of symbols]

 12 Door Weather Strip (Rubber / TPE Composite) 14 Weather Strip Attachment Base (Rubber) 20 Decorating Layer (TPE) 30 Kneading Roll Machine 30a Roll of Kneading Roll Machine W Weather Strip Main Body (Rubber) D Decorative Film (TPE section)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23:06 C08L 23:06 57:02) 57:02) F-term (Reference) 3D024 AA00 AB01 AB57 4F071 AA15 AA16 AA39 AA74 AE20 AH09 CD01 CD07 4F100 AK02A AK02H AK03B AK07 AK62A AK62B AK66B AK75 AK75A AL09B AN02A BA02 CA16A GB32 JA04A JA04H JA11A JB16B JN28 JN30 YY00A Y023B01 001003

Claims (8)

[Claims] 1. A rubber portion comprising a vulcanized product of a rubber compound having an ethylene-α-olefin rubber (EOR) as a rubber polymer and a TPE portion comprising a thermoplastic elastomer (TPE) compound are directly bonded. A rubber / TPE composite, wherein the rubber compound contains a crystalline polyethylene (crystalline PE) as a modified resin polymer and a tackifier (tackifier); In the case where the TPE compound contains a nonpolar TPE as a base polymer, the property of the tackifier is SP.
A rubber / TPE composite characterized by satisfying the following requirements: value: 6.0 to 10.0, softening point: 90 to 110 ° C, and aniline point: 80 ° C or higher. 2. The property of the tackifier is SP value: 7.
0-9.0, softening point: 95-104 ° C, aniline point: 1
The rubber / TPE composite according to claim 1, which satisfies a requirement of not less than 05 ° C. 3. The rubber / TPE composite according to claim 2, wherein all or the main component of the tackifier is selected from hydrogenated (hydrogenated) petroleum hydrocarbon resins. 4. The hydrogenated petroleum hydrocarbon resin is hydrogenated C9.
The rubber / TPE composite according to claim 3, which is a petroleum hydrocarbon resin. 5. The rubber / TPE composite according to claim 2, wherein all or the main component of the tackifier is selected from hydrogenated rosin esters. 6. The rubber compound is a sulfur vulcanized system, the rubber polymer is an ethylene-α-olefin-nonconjugated diene copolymer rubber (EODM), and the compounding amount of the crystalline PE. The rubber / TPE composite according to claim 1, 2, 3, 4, or 5, wherein the amount of the tackifier is 2.5 to 10 phr. 7. The non-polar TPE is an olefinic TPE.
The rubber / TPE composite according to claim 6, wherein 8. The rubber / TPE composite according to claim 1, wherein the rubber portion is a weatherstrip body and the TPE portion is a decorative layer. Automotive weather strip.