JPH107849A - Rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber composition having excellent adhesivity to a thermoplastic polyolefin resin (TPO). SOLUTION: This rubber composition is produced by compounding (A) 100 pts.wt. of an ethylene-α-olefin-nonconjugated diene copolymer and/or a rubber composed mainly of an ethylene-α-olefinnonconjugated diene copolymer with (B) 5-50 pts.wt. of a slightly crystalline propylene copolymer and (C) 1-30 pts.wt. of at least one kind of substance selected from a compound and/or polymer containing at least one kind of group selected from a group having an alkoxysilane, hydroxyl group, amino group and epoxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition having excellent adhesion to a thermoplastic polyolefin resin (hereinafter "TPO").

[0002]

2. Description of the Related Art In the production of vulcanized rubber products such as glass run channels, a straight section is formed by an extruder, vulcanization is performed in a vulcanizing tank, and the obtained product is molded and molded. The method of connecting the corner portions by vulcanization adhesion was common. In recent years, attempts have been made to convert corner portions to resin for the purpose of cost reduction and product recycling. However, when resinizing the corners,
In the conventional rubber composition, the interface between the vulcanized rubber and the resin is peeled off at the interface, or even if the material is broken, the adhesive strength is low, and it is not practically satisfactory.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a rubber composition in which the above-mentioned adhesion between the vulcanized rubber and the resin causes material destruction and high adhesive strength.

[0004]

SUMMARY OF THE INVENTION The present invention provides an ethylene-α
In a rubber composition for vulcanization using an olefin-non-conjugated diene copolymer, (A) ethylene-α-olefin-
With respect to 100 parts by weight of a rubber mainly containing a non-conjugated diene copolymer and / or an ethylene-α-olefin-non-conjugated diene copolymer (hereinafter, ethylene-α-olefin-non-conjugated copolymer and the like), B) 5 to 50 parts by weight of a microcrystalline propylene polymer, and (C) a compound and / or polymer containing at least one selected from a group having an alkoxysilane, a hydroxyl group, an amino group and an epoxy group. An object of the present invention is to provide a rubber composition comprising 1 to 30 parts by weight of at least one selected from the group (hereinafter referred to as a functional component).

(A) Ethylene-α- used in the present invention
Examples of the α-olefin of the olefin-non-conjugated diene copolymer include propylene, butene-1, hexene-1, octene-1, decene-1, and dodecene-1, and the like.
Preferred are propylene, butene-1, hexene-1, and octene-1. Further, as the non-conjugated diene, 5-ethylidene-2-norbornene, dicyclopentadiene,
Examples include norbornadiene, 1,7-octadiene, 1,9-decadiene, 7-methyl-1,6-octadiene and the like, preferably 5-ethylidene-2-norbornene, dicyclopentadiene, 7-methyl-1,6-diene. Octadiene. (A) Ethylene used in the present invention
The Mooney viscosity of the α-olefin-non-conjugated diene copolymer (ML1 + 4, 100 ° C., the same applies hereinafter) is preferably 5
It is 0-150, more preferably 80-120. Here, if the Mooney viscosity is less than 50, the mechanical strength tends to decrease, and the compression set tends to be impaired.
If it exceeds, the Mooney viscosity of the rubber composition becomes too high,
Extruder productivity tends to decrease. The ethylene / α-olefin-non-conjugated diene copolymer (A) used in the present invention preferably has a molar ratio of ethylene / α-olefin of 50/50 to 80/20, more preferably 55/45 to 75. / 25. Here, when the molar ratio of ethylene / α-olefin is less than 50/50,
The vulcanization properties may decrease, and if it exceeds 80/20, the cold resistance may deteriorate. Further, the non-conjugated diene content of the (A) ethylene-α-olefin-non-conjugated diene copolymer used in the present invention is preferably 10 to 10 in terms of iodine value.
30, more preferably 20 to 30. Incidentally, two or more non-conjugated diene compounds can be used in combination.
Here, if the iodine value is less than 10, the vulcanization rate becomes slow, and the balance between vulcanization and foaming may be insufficient.
If it exceeds 0, the elongation and tear strength of the rubber product may decrease. Further, in the present invention, the rubber containing ethylene-α-olefin-non-conjugated diene copolymer as a main component includes natural rubber, styrene-butadiene rubber, polybutadiene rubber, diene rubber such as acrylonitrile-butadiene rubber, chlorinated rubber. One or more selected from chlorinated rubbers such as polyethylene, chlorsulfonated polyethylene, and chloroprene rubber, and hydrogenated polymers of the above-mentioned diene rubbers can also be blended.

Next, the (B) microcrystalline propylene polymer used in the present invention is a polypropylene obtained by homopolymerizing propylene, propylene containing at least 50% by weight of a propylene component, ethylene, butene-1, and hexene-polymer. 1,
It is a propylene copolymer obtained by copolymerizing octene-1 and the like, and is commercially available, for example, as UBETAC APAO (manufactured by Ube Lexen). The (B) microcrystalline propylene polymer used in the present invention preferably has a softening temperature of 100 to 160 ° C. in a ring and ball method softening point measurement (measured according to ASTM E28).
More preferably, it exists at 5 to 150 ° C. Furthermore,
The (B) microcrystalline polypropylene-based polymer of the present invention has 19
The melt viscosity at 0 ° C. is preferably 30,000 cps or less,
More preferably, it is 3000 to 20000 cps. Here, if the softening temperature is lower than 100 ° C., sufficient adhesion of TPO / vulcanized rubber may not be obtained, and if it exceeds 160 ° C., poor dispersion in the rubber composition may occur. If the melt viscosity exceeds 30,000 cps, poor dispersion in the rubber composition may occur. The amount of the (B) microcrystalline propylene polymer used is 5 parts per 100 parts by weight of the (A) ethylene-α-olefin-nonconjugated diene copolymer or the like.
５０50 parts by weight, preferably 10-40 parts by weight, more preferably 15-30 parts by weight. If the amount is less than 5 parts by weight, the effect of improving the adhesive strength between the vulcanized rubber and TPO is small, and
If the amount is more than the weight part, the compression set of the vulcanized rubber is undesirably increased.

Among the functional components (C) used in the present invention, compounds and / or polymers containing a group having an alkoxysilane (hereinafter referred to as silane functional components) include, for example, silane coupling agents, And alkoxysilane-modified polymers. Specific examples of the silane coupling agent include, for example, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and γ-methacrylic acid. Roxypropyltrimethoxysilane,
γ-methacryloxypropylmethyldimethoxysilane,
γ-methacryloxypropyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β
-Aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, bis- (3-triethoxysilyl-propyl)- Tetrasulfide and the like. Specific examples of the alkoxysilane-modified polymer include low-density polyethylene, high-density polyethylene, ethylene / vinyl acetate copolymer, and polypropylene. These silane functional components can be used alone or in combination of two or more.

[0008] Examples of the compound and / or polymer having a hydroxyl group (hereinafter, hydroxyl-functional component) include a compound and / or a polymer having at least one alcoholic hydroxyl group and / or phenolic hydroxyl group. Specific examples of such hydroxyl functional components include (poly) alkylene glycols such as polyethylene glycol, polypropylene glycol, and poly (oxytetramethylene) glycol; and tri- or higher valents such as glycerin, trimethylolpropane, and pentaerythrol. Polyhydric alcohols: phenol, kyrilenol, bisphenol A
Such as phenols; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and γ-hydroxypropyl (meth) acrylate and their (co) polymers; hydroxyl-modified hydrogen-terminated polybutadiene at both ends, hydroxyl-modified at both ends Polybutadiene, hydroxyl-modified polyisoprene, hydroxyl-modified polypropylene at both ends, hydroxyl-modified hydrogenated styrene / butadiene copolymer at both ends,
Examples include hydroxyl group-containing polymers such as polyvinyl alcohol and ethylene / vinyl alcohol copolymer. Of these, polyethylene glycol, polypropylene glycol, hydroxyl-terminated hydrogen-modified polybutadiene at both ends and hydroxyl-modified polybutadiene at both ends are preferred, and hydrogen-modified polybutadiene at both ends is more preferred. These hydroxyl functional components can be used alone or in combination of two or more.

Further, a compound containing an amino group and / or
Alternatively, specific examples of the polymer (hereinafter, amino-functional component) include pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminooctane, 1,10- Diamines such as diaminodecane, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine; nylon-6, nylon-7, nylon-11, nylon-1
2, polyamides such as nylon-6,10 and the like. Of these, pentamethylenediamine, hexamethylenediamine, and 1,7-diaminoheptane are preferred. These amino group functional components can be used alone or in combination of two or more.

Specific examples of the compound and / or polymer containing an epoxy group (hereinafter referred to as epoxy functional component) include phenylene glycidyl ether, propyl glycidyl ether, lauryl glycidyl ether, myristyl glycidyl ether, and palmityl glycidyl ether. Glycidyl ethers such as stearyl glycidyl ether and oleyl glycidyl ether, glycidyl (meth) acrylate or its linear (co) polymer or graft copolymer (for example, polystyrene obtained by graft copolymerization of glycidyl (meth) acrylate) Allyl glycidyl ether or its (co) polymer; ethylene-glycidyl methacrylate copolymer;
Epoxidized styrene / butadiene copolymer; epoxy resin and the like. Of these, preferably lauryl glycidyl ether, myristyl glycidyl ether,
Palmityl glycidyl ether, stearyl glycidyl ether and oleyl glycidyl ether. These epoxy group functional components can be used alone or in combination of two or more. Furthermore, in the present invention, any two or more of a silane functional component, a hydroxyl functional component, an amino functional component, and an epoxy functional component can be used in combination.

The amount of the functional component (C) used in the present invention is 1 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the ethylene-α-olefin-non-conjugated diene copolymer (A). Parts by weight. If the amount of the functional component is less than 1 part by weight, the effect of improving the adhesive strength between the vulcanized rubber and TPO is small, and if it exceeds 30 parts by weight, the vulcanized rubber has tensile strength, tear strength, compression set, etc. May worsen, which is not preferable.

The rubber composition of the present invention can contain a filler, a process oil, a vulcanizing agent, a vulcanization accelerator, an activator and the like. The filler is preferably FEF, SR
F, GPF grade carbon black, silicates such as clay, talc, wollastonite, wet or dry silica; carbonates such as calcium carbonate, heavy calcium carbonate, magnesium oxide; zinc oxide, aluminum oxide And a white filler such as a metal oxide such as titanium oxide, a coupling agent thereof, or a surface-treated filler with a fatty acid or the like. The compounding amount of carbon black is preferably 50 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-non-conjugated diene copolymer and the like, and a white filler. Is ethylene-α-olefin-
Usually 100 parts by weight of non-conjugated diene copolymer
0 parts by weight or less, preferably 50 parts by weight or less. Specifically, the process oil is preferably a paraffin-based process oil or a naphthene-based process oil. The amount of the process oil is preferably 1 to 100 parts by weight of the ethylene-α-olefin-nonconjugated diene copolymer or the like.
It is at most 00 parts by weight, more preferably at most 80 parts by weight. Specific examples of the vulcanizing agent include powdered sulfur and colloidal sulfur, and the amount of the vulcanizing agent is ethylene-α-
It is at most 5 parts by weight, preferably at most 3 parts by weight, per 100 parts by weight of the olefin-non-conjugated diene copolymer or the like. Specific examples of the vulcanization accelerator include a thiazole vulcanization accelerator, a thiuram vulcanization accelerator, a dithiocarbamic acid vulcanization accelerator, a guanidine vulcanization accelerator, a thiourea vulcanization accelerator, and the like. These are used in combination of one or more. The amount of the vulcanization accelerator is 1 to 100 parts by weight of the ethylene-α-olefin-non-conjugated diene copolymer or the like.
0 parts by weight or less, preferably 8 parts by weight or less. Specific examples of the activator include zinc oxide, activated zinc white, etc., and the amount of the activator is 30 parts by weight or less, preferably 100 parts by weight of the ethylene-α-olefin-nonconjugated diene copolymer or the like. Is 15 parts by weight or less. Further, the present invention can also be a sponge rubber composition using a foaming agent. As the foaming agent, known foaming agents can be used,
p, p'-Oxybis (benzenesulfonyl hydrazide) (hereinafter OBSH) is preferred, and Neocervone N # 1000 (manufactured by Eiwa Kasei), CellMike S (manufactured by Sankyo Kasei), CelogenOT (Uniroyal Che)
m. Is preferred. The compounding amount of the foaming agent in the rubber composition for sponge is 0.1 to 10 parts by weight based on 100 parts by weight of the ethylene-α-olefin-nonconjugated diene copolymer and the like.
Parts by weight, preferably 2 to 7 parts by weight. Furthermore, in the present invention, it is preferable to mix paraffins, liquid paraffin, fatty acid esters, fatty acid amides, and the like for the purpose of improving the fluidity of the composition. Specific examples of processing aids include polyethylene wax, polyethylene glycol,
Fatty acid amide, fatty acid ester, sub (factice),
Special compounding processing aids (Exton K-1, Sun Aid H
P, iodoplast P, TE-80, actiplast, AFLUX 42, Stractol WB-212, etc.), and these are used in combination of one or more.
The compounding amount of the processing aid is 10 parts by weight or less, preferably 5 parts by weight or less based on 100 parts by weight of the ethylene-α-olefin-nonconjugated diene copolymer or the like. In the present invention, an antioxidant can be blended. Specific examples of this antioxidant include n-octadecyl-3- (4′-
(Hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, tetrakis-dimethylene-3
-(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate @ methane. The compounding amount of the antioxidant is 5 parts by weight or less, preferably 3 parts by weight or less based on 100 parts by weight of the ethylene-α-olefin-nonconjugated diene copolymer or the like. Furthermore, in the present invention, a compounding agent used in normal rubber compounding, such as a dehydrating agent such as calcium oxide, a coloring agent, a pigment, an ultraviolet absorber, and a flame retardant, can be added.

The method for preparing the rubber composition of the present invention includes:
Although not particularly limited, for example, a vulcanizing agent, a vulcanization accelerator, a carbon black excluding a foaming agent, a process oil, an activator, an ethylene-α-olefin-nonconjugated diene copolymer or the like.
After kneading the processing aid, release agent, etc. with a closed kneader such as a roll mill, a Banbury mixer, an intermix, a pressure kneader, a continuous kneader, etc., a dehydrating agent,
It can be performed by kneading a vulcanizing agent, a vulcanization accelerator and a foaming agent with a roll mill and a pressure kneader. Mooney viscosity (ML1 +) of the rubber composition of the present invention after adjustment.
4,100 ° C) is usually 30 to 80, preferably 30 to 80
It is desirable to adjust to 65. Next, in the method provided for the production of normal vulcanized rubber, for example, foaming and vulcanization by raising the temperature by placing the rubber composition in a mold,
Or after molding into an arbitrary shape using an extruder,
By heating and foaming and vulcanizing in a vulcanization tank, a vulcanized product is obtained.

[0014]

EXAMPLES Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Examples and parts and percentages in the examples are by weight unless otherwise specified.
The evaluation methods of the physical properties in Examples and Comparative Examples were based on the following measurement methods.

Mooney Viscosity Measurement Test The Mooney viscosity (ML1 + 4, 100 ° C.) of the unvulcanized rubber of the compounded rubber obtained according to the compounding recipe was determined according to JIS.
It was measured according to K6300. An L-shaped rotor was used. Mooney scorch test For the compounded rubber obtained according to the compounding recipe, Mooney scorch of unvulcanized rubber was measured in accordance with JIS K6300. The rotor was L-shaped and the test temperature was 125 ° C. Tensile test The compounded rubber obtained according to the compounding formula was subjected to
The vulcanized rubber vulcanized for one minute was measured according to JIS K6301. The compounded rubber obtained according to the compression set formulation was subjected to
The vulcanized rubber vulcanized for one minute was measured according to JIS K6301. Vulcanized rubber / TPO adhesion test 1) Manufacture of vulcanized rubber Compounding and kneading method: Refer to Table 1. Vulcanization conditions: Press vulcanization at 170 ° C × 10 minutes Others: 60 × 50 × 2 mm Use punched test pieces. 2) Injection condition of TPO Using an injection molding machine (N-100 manufactured by Nippon Steel Corporation), 12
A vulcanized rubber sheet was set in a mold of 0 × 100 × 2 mm as follows, and a molded product was collected under the following conditions. 3) Adhesive strength test between vulcanized rubber and TPO Test piece: JIS No. 2 dumbbell (punched out so that the adhesive interface between TPO and vulcanized rubber is at the center of the dumbbell) Tensile speed: 500 mm / min Test temperature: 25゜ C

Tables 1 to 4 show the formulation, Table 5 shows the physical properties of the microcrystalline polypropylene, and Tables 6 to 9 show the results of the physical property tests. (Examples 1 to 10, Comparative Examples 1 to 7)

[0017]

[Table 1] Table 1 Formulation of vulcanized rubber ──────────────────────────────────── Name of manufacturer Remarks ──────────────────────────────────── EPDM 100 Nippon Synthetic Rubber Company (* 1) Microcrystalline Fluoropolymer-based polymer variable Ube Lexen Polymer Seast 116 145 Tokai Carbon Co., Ltd. Reinforcing agent Thaiana Processes PW380 85 Idemitsu Kosan Co., Ltd. Softener Activated Zinc Flower 5 Sakai Chemical Co., Ltd. Schill & seilacher Co., Ltd. Processing aid Hitachil 1501 1 Hitachi Chemical Co., Ltd. Processing aid (Tackifire) PEG4000 1 Sanyo Chemical Co., Ltd. Activator Pesta PP 10 Inoue Lime Co., Ltd. Dehydrating agent Additive Variable ────────────── ────────────────────── (* 1); ethylene Propylene / 5-ethylidene-2-norbornene copolymer Mooney viscosity (ML1 + 4,100 ℃) = 86 Ethylene propylene molar ratio = 60/34 iodine value = 20

[0018]

[Table 2] Table-2 Vulcanization system A ──────────────────────────────────── Suncellar M1 Sanshin Chemical Vulcanization Accelerator MBT Suncellar PX 1 Sanshin Chemical Vulcanization Accelerator ZnEPDC Suncellar TET 0.5 Sanshin Chemical Vulcanization Accelerator TETD Suncellar D 0.5 Sanshin Chemical Vulcanization Accelerator DPG Powder Sulfur 2 Tsurumi Chemical Vulcanizing agent 社

[0019]

[Table 3] Table-3 Vulcanization system B ──────────────────────────────────── Suncellar M1 Sanshin Chemical Vulcanization Accelerator MBT Suncellar TET 0.7 Sanshin Chemical Vulcanization Accelerator TETD Suncellar TRA 0.7 Sanshin Chemical Vulcanization Accelerator DPTT Suncellar TE-G 0.7 Sanshin Chemical Vulcanization Accelerator TeEDC Powdered sulfur 2 Tsurumi Chemical Company Vulcanizing agent 剤 <Method of vulcanized rubber> 1 After setting the temperature at 50 ° C. using a 0.7 LBR type Banbury mixer (manufactured by Kobe Steel Co., Ltd.), the compounding agents (excluding Vesta PP) shown in Table 1 above were charged and kneaded at 70 rpm for 3 minutes. Using a 6-inch roll, Vesta PP and a vulcanizing system shown in Table 2 or 3 were added to the obtained rubber composition to obtain an EPDM composition. Then vulcanized with a vulcanizing press at 170 ° C for 10 minutes,
A vulcanized sheet of mx 150 mm x 2 mm was prepared. (The compression set block was vulcanized for 15 minutes.)

[0020]

[Table 4] Table-4 Formulation of TPO ──────────────────────────────────── Manufacturer name Remarks ─ ─────────────────────────────────── EP98A 75 Nippon Synthetic Rubber Company (* 2) MR02R 25 Mitsubishi Chemical Corporation PP Linklon CH750T 10 Mitsubishi Chemical Corporation Alkoxysilane-modified LDPE Thaiana Process PW90 0.5 Idemitsu Kosan Co., Ltd. Process Oil Verhexyne 25B-40 0.3 Nippon Yushi Company Organic Baroxide PM 0.5 PM Ouchi Shinko Co., Ltd. ──────────────────────────── (* 1); ethylene / propylene / 5-ethylidene-2-norbornene copolymer Mooney viscosity ( (ML1 + 4,100 ° C) = 300 Ethylene propylene molar ratio = 78/22 Iodine value = 15 Paraffin Oil 75phr containing <base TPO manufacturing method> 150 preheated pressure kneader to ° C.: Diana Process in the formulation to (Moriyama Seisakusho volume 10L) PW90, Pahekishin 25B
Add compounding ingredients except -40 and Linklon CH750T,
The mixture was kneaded at 40 rpm for 10 minutes until MR02R was melted and the added components were uniformly dispersed. The obtained composition was formed into a sheet with a 10-inch roll, and formed into a square pellet with a square cutting pelletizer. Diana Process PW90 and Perhexin 25B-40 were added to the obtained square pellet composition.
Was mixed with a Henschel mixer for 30 seconds, and the mixture was extruded into a twin-screw extruder (PCM-45, L / D = 33.
5, 230 ° C with same direction complete meshing screw)
, And extruded while dynamically heat-treating so that the residence time was 2 minutes to obtain base TPO pellets. <Method of manufacturing TPO> Base TPO and Wrinklon CH75
After kneading for 10 minutes with a kneader preheated from 0T to 150 ° C., it is passed through a roll at 80 ° C. once to form a sheet-like TPO.
I got As is clear from Tables 6 to 9, each of the examples falling within the scope of the present invention has a high adhesive strength to TPO and shows good mechanical properties.

[0021]

[Table 5]

[0022]

[Table 6]

[0023]

[Table 7]

[0024]

[Table 8]

[0025]

[Table 9]

[0026]

Industrial Applicability The rubber composition of the present invention has a high adhesive strength in an adhesive strength test with TPO, and can provide a rubber composition excellent in processability and mechanical properties. The rubber composition is used for various weather strips such as glass run channels, sponge-solid-metal composite door seal sponges, trunk lids, and sealing materials for civil engineering and construction.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 23/16 LCY C08L 23/16 LCY // (C08L 23/08 101: 02)

Claims (1)

[Claims] 1. A rubber composition for vulcanization using an ethylene-α-olefin-non-conjugated diene copolymer, comprising: (A)
(B) based on 100 parts by weight of a rubber containing an ethylene-α-olefin-non-conjugated diene copolymer and / or an ethylene-α-olefin-non-conjugated diene copolymer as a main component,
5 to 50 parts by weight of a microcrystalline propylene polymer, (C)
At least one selected from the group of compounds and / or polymers containing at least one selected from a group having an alkoxysilane, a hydroxyl group, an amino group, and an epoxy group
A rubber composition comprising 1 to 30 parts by weight of a seed.