JPH01319578A - Bonding between millable urethane elastomer and rubber and laminate thereof - Google Patents

Abstract

PURPOSE:To simply carry out bonding between millable urethane elastomer containing an organic peroxide and unvulcanized rubber in good productivity by making unvulcanized rubber containing specific ethylene-propylene copolymer rubber exist between the elastomer and the unvulcanized rubber. CONSTITUTION:(C) (i) Rubber consisting essentially of ethylene-propylene- nonconjugated diene terpolymer rubber or ethylene-propylene copolymer rubber and (ii) unvulcanized rubber containing an organic peroxide and a (meth)acrylate compound having two carbon-carbon unsaturated bonds are made to exist as adhesion rubber between (A) millable urethane elastomer containing an organic peroxide as a crosslinking agent and (B) unvulcanized rubber and vulcanizing bonding is done to bond the millable urethane elastomer to the rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of industrial applications) The present invention relates to a method of adhering a millable urethane elastomer and rubber.

Materials bonded in this way are generally
It can be used for products that require mechanical strength, especially wear resistance, such as industrial parts such as automobile parts, etc.

(Background of the Prior Art) Generally, urethane elastomers can be broadly classified into two types, liquid system and solid system, depending on the type of processing method. There are two types of solid systems: miraful type and thermoplastic type, and miraful type is −
It is a type that can be processed with +12 rubber processing equipment, and is mainly used for industrial parts and automobile parts by press molding. It is well known that urethane X-mer has particularly excellent mechanical strength and abrasion resistance compared to general-purpose rubber.

Millable urethane elastomers are divided into three types: isocyanate-cured, peroxide-cured, and sulfur-cured. Oxide vulcanization type materials are preferably used.

Urethane elastomers, which have these advantages, are more expensive than general-purpose rubbers for use in industrial parts, etc.
In order to take advantage of this feature and achieve a low cost I-, composites of 1/tan elastomer and other materials have been considered.

Other materials include 1, for example cheaper general purpose rubber. In addition, for compounding, it is necessary to bond with, for example, general-purpose rubber as mentioned above.

(Prior Art) Conventionally, as a method for combining urethane elastomer and other materials, for example, Japanese Patent Publication No. 45064/1983 discloses that a polyurethane layer is applied as a skin on a release paper, and a rubber layer is applied to the skin. A GoJ8/polyurethane composite obtained by simultaneously vulcanizing a composite film coated with a graft polymer and dried and unvulcanized rubber, and a method for producing the same are disclosed.

JP-A-58-185244 discloses that the surface of a molded product of an olefin polymer mixture containing an organic compound having a double bond and containing a hydroxyl group and an organic peroxide]
- A laminate consisting of a polyurethane foam obtained by simultaneously performing a urethane polymer production reaction and foaming and a molded product of an olefin polymer mixture has been proposed.

In the invention described in the former publication, the isocyanate is particularly characterized by the effect of bonding and adhering the polyurethane and the rubber graft polymer. It is considered that the organic compound containing the urethane foam is effective in improving the adhesion with the urethane foam.

(Problems with Prior Art) However, in all of these cases, liquid polyurethane is used.

Therefore, as mentioned above, millable urethane elastomer has the advantage of being able to be processed using general rubber processing equipment.Also, as general adhesive techniques, there are methods of applying adhesive or surface treatment, but these methods require a processing step. This results in an increase in productivity, resulting in lower productivity.

As described above, there is no known method for easily bonding a millable urethane elastomer and a general rubber material.

(Object of the invention) The object of the present invention is to use a millable urethane elastomer that can be processed in a general rubber processing process on one side of the composite, and
In order to solve the above-mentioned problems when bonding this to a general rubber material, we created a bond between the millable urethane elastomer and a general rubber material and a rubber material without applying an adhesive in a normal rubber vulcanization process. It is an object of the present invention to provide a method for bonding together with vulcanization, that is, for bonding easily and with high productivity.

(Means to solve the problem) (1) Millable urethane elastomer and Go+6 of the present invention
The method of adhesion is as follows: When adhering (8) and (B) below, use (C) below as adhesive rubber, and place (C) between these (8) and (13).
It is characterized in that it is vulcanized and bonded by interposing.

(A) Millable urethane elastomer containing organic peroxide as a crosslinking agent (B) Unvulcanized rubber (C) Ethylene-propylene-nonconjugated diene terpolymer rubber (hereinafter referred to as +4 P D M) or ethylene-
An unvulcanized rubber containing an organic peroxide and a hydrogen (meth)acrylate compound having two or more carbon-carbon unsaturated bonds in a rubber mainly composed of propylene copolymer rubber (hereinafter referred to as EPM) The present invention In this method, the (Δ) millable urethane elastomer must be crosslinked with an organic peroxide. Examples include polyester urethanes modified with 4,4'-diphenylmethane diisocyanate.

Other chemicals used in organic peroxide vulcanization of mirasol urethane elastomer can be added.

Any conventionally known organic peroxide can be used, such as di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, u, +y'-bis (1-butylperoxy>
-p-diisopropylhenzen, 2,5-dinotyl-2
,5-di(t-butylperoxy)hexano,2,5-
Dimethyl-cy(t-butylperoxy)hexano 3.2
．． 5-dimethyl-2,5-di(benzoylperoxy)
hexano, t-butylperoxyisopropyl carbonate, 1,1-bis(t-butylperoxy)-3,5
, 5-)limethylcyclohexane and the like are preferably used.

The adhesive rubber (C) in the method of the present invention is l'iPDM.
Alternatively, it is a rubber composition containing an organic peroxide and a (meth)acrylate compound having two or more carbon-carbon unsaturated bonds in a rubber mainly composed of EPM.

In addition to EPDM or EPM, natural rubber (
It is also possible to add rubbers such as NR), isoprene rubber (IR), and chloropropane rubber (CR), or if strong adhesion with the Miraflu urethane elastomer is required, the addition of these rubbers. is not preferable because it reduces adhesive strength. In addition, styrene-butadiene rubber (SBR) and butadiene rubber (BR) have particularly high crosslinking efficiency in organic peroxide vulcanization compared to ethylene-propylene rubber.
) is not preferred.

Any conventionally known organic peroxide can be used. For example, the organic peroxide used in the Miraflu urethane elastomer (A) mentioned above may be mentioned.

Next, it has two or more carbon-carbon unsaturated bonds (meta)
Examples of acrylate-1-compounds include trimethylol-opane-1-(F) and 2.2"-bis(4), which are commonly used as co-crosslinking agents in organic peroxide vulcanization.
-Acryloxydie I xyphenyl)propane (D)
, 2.2'-bis(4-methaclokididijetoxyphenyl)propane (E). The amounts of the organic peroxide and co-crosslinking agent added are generally 0.01 mol each per 100 parts by weight of rubber.

According to the present invention, the adhesive can be bonded to the millable urethane elastomer with the same amount of use. Note that when the amount of co-crosslinking agent is much smaller than the amount of organic peroxide, the above-mentioned adhesion is not achieved.

Furthermore, for adhesion with millable urethane elastomer,
The main effect is thought to be the chemical bonding of the co-crosslinking agent with the millable urethane. Therefore, the amount of organic peroxide added in adhesion with millable urethane elastomer can be achieved with a very small amount or no addition, but this will lead to a decrease in adhesive strength due to insufficient vulcanization of the adhesive rubber itself. The amount necessary to vulcanize the adhesive rubber should be added.

Other chemicals that are generally used in the organic peroxide vulcanization of ethylene-propylene rubber can be added, but additives that release sulfur and sulfur, such as rubber vulcanization accelerators, etc. Undesirable. If you are worried,
In organic peroxide vulcanization of millable urethane elastomer, sulfur is known to inhibit this vulcanization, and even with the adhesive method of the present invention, the force 11 at the adhesive interface with millable urethane elastomer is inhibited by sulfur. This is because the elastomer may foam. If this foaming occurs uncontrollably, the adhesive strength may decrease or the adhesive may not adhere properly.

The unvulcanized rubber (B) in the method of the present invention is a general-purpose rubber composition, and is not particularly limited and may be any rubber. For example, NR, SBI? , BR, acrylonitrile-butadiene rubber (NBR), which includes a composition containing sulfur as a vulcanizing agent.

Furthermore, the adhesive rubber (C) can be made into a composition that has structural strength as well as adhesive function, so that the adhesive rubber (C) can also be used as (B).

These (B) unvulcanized rubber J. and the method of the present invention (
C) Adhesive rubber means that when (C) does not also serve as (B), it is bonded using a normal bonding technique of unvulcanized rubber and unvulcanized Cory 2. It is well known.

The vulcanization conditions of the method of the present invention are based on conventionally known methods, but the adhesion between the millable urethane elastomer and IJ is achieved by simultaneously pressurizing and heating, that is, vulcanization. . Therefore, it is desirable to consider and set the properties of the vulcanized adhesive between the millable urethane elastomer and Im.

Furthermore, the method of applying (A) the Mirablue lacquer/tan elastomer, (B) the unvulcanized rubber, and (C) the adhesive rubber according to the method of the present invention can also be obtained by a generally known rubber processing process.

(2) Next, in the laminate of the present invention, in adhering the following (8) and (B), the following (C) is used as an adhesive rubber, and (C) is used between these (A) and (B). It is obtained by vulcanization adhesion with intervening.

(8) Millable urethane elastomer containing organic peroxide as a crosslinking agent (B) Unvulcanized rubber (C) Rubber mainly composed of EPDtl or EPM, containing organic peroxide and two or more carbon-carbon unsaturated bonds (Function) As described above, according to the present invention, (A) Mirablue rubber containing an organic peroxide as a crosslinking agent;
In adhesion between tan elastomer and (II) unvulcanized rubber, (C) EPDM or EPM-based rubber containing an organic peroxide and two or more carbon-carbon unsaturated bonds (
An unvulcanized rubber containing a meth)acrylate-1-compound is used as an adhesive rubber, and (C
) can be bonded by intervening vulcanization adhesive.

That is, a millable urethane elastomer and a general rubber material can be bonded together with the force curing of the rubber material in a normal rubber vulcanization process without applying an adhesive.

Further, the laminate of the present invention obtained by this method can be processed in a general rubber processing process, unlike conventional methods. Therefore, a laminate of millable urethane elastomer and rubber can be obtained easily and with high productivity.

(Example) The present invention will be explained below with reference to Examples.

In the following, parts indicate parts by weight. Moreover, the peel strength of the obtained adhesive is a value measured using an Autograph (Shimadzu Corporation) on a 2.5 cm wide sample at a peel rate of 50 mm/min. In each table, the experimental results are not shown, but are shown as adhesive strength. Further, the state of the adhesive at the peeling limit point was expressed as the limit state.

Experiment 1 Millable urethane elastomer blend Th(A) Millable urethane (Sumipan 640S: manufactured by Tensei Bayer Urethane) 100 parts Carbon blank N330 20 Plasticizer
5 Anti-aging agent PCD (polysulfodiimide) 3-E auxiliary agent 1 Stearic acid
0.5 dicumyl peroxide (0,
01 mol) 2.7 The above Miraflu sewage/tan combination (A
) was kneaded using an internal mixer and a test roll to form an unvulcanized sheet with a thickness of 2 mm, and the adhesive rubber compound (C) shown in Table 1 was kneaded in the same manner to form an unvulcanized sheet with a thickness of 4 mm. Layer Gore's Sea I on top of Go J sheet and heat to temperature 15.
Vulcanization bonding was carried out by heating and pressing at 0° C. and a pressure of 30 kg/cffl for 30 minutes. Table 1 shows the adhesive horns of the obtained adhesive.

Looking at the results shown in Table 1, Compound No. 1, which used EPDM as the rubber in (C), adhered to millable urethane. And as the rubber of (C), EPDM/
When set to NR, 80/20 (composition No. 2),
60/40 (Blend No. 3), the more the amount of Nll increases, the lower the adhesive force becomes. Also, from the results of formulations No. 094 to 7, the rubber of (C) was EPDM/SBR, EPDM/NBR.
When this happens, interfacial abrasion occurs in the limit state.

In addition, in Table 1, dicumyl peroxide and trimedylolpropane 1-remethacrylate-1- are each 0.
The amount added was 0.01 mol.

Experiment 2 In the same manner as in Experiment 1, adhesives of adhesive rubbers shown in Tables 2 and 3 and millable urethane elas 1 to mer compounds were prepared,
The adhesive strength is shown in Tables 2 and 3.

As a result, adhesive rubber (C) formulations No. 081, No. 8,
Samples No. 9, No. 11, No. 12 adhered well to the millable urethane. That is, for either EPDM or EPM, 2,2'-bis(4-acryloxydiethoxyphenyl)propane (D), 2,2'-bis(4-methacryloxydiethoxyphenyl)propane (E
), l-rimethylolpropane trimethacrylate (
The adhesive rubber (C) made by adding F) adheres to the millable urethane elastomer compound.

In addition, in Tables 2 and 3, the amounts of dicumyl peroxite and the crosslinking agent are each 0.01 mol.

Experiment 3 In the same manner as in Experiment 1.2, adhesives of the adhesive rubber (C) shown in Table 4 and the millable urethane elastomer compound were prepared, and the adhesive strength thereof is shown in Table 4.

However, for adhesive rubber No. 27, the adhesive strength between a millable urethane elastomer (referred to as PUR in the figures and tables) and adhesive rubber was measured as a three-layer composite shown below.

*)) Mi〕DM (FP33) Io
Part o carbon flask 60 Paraffin oil 30 Zinc oxide 5 Stearic acid 0.5 Anti-aging agent 2.5 Dicumyl peroxide 3.5 Ethylene dimethacrylate-1-3,0 According to the experimental results, adhesive rubber In (C), when the amount of 1-rimethyI7-propane trino'kukuri L/-t-1 is extremely small compared to the amount of dicumyl peroxide (No.
, 29), no longer adheres to millable urethane elastomer formulations.

Experiment 4 Using adhesive rubber (C) formulation No. 1 (see Table 1) in Experiment 1, a millable urethane elastomer compound was prepared. )(
+1) was prepared. The processing method is Experiments 1 to 3.
Same as , 2mm of millable urethane and 2mm of adhesive rubber.
, bind the adhered rubber to 2 mm and apply 1 stone of force for 30 minutes at 150°C.

Adhesive rubber〉 G) N1190/l11710, S/Prompt CZ/Prompt paste A
System formulation It) N1t50/5BR50, S/Yaku CZ
/Prompt I] system formulation 1) NBimaEIO/5BR20,
S no Yuki TS / Yuki DM type compound J) lmil] Old 00,
Dicumyl peroxyl"/Ethi I/Dimethacrylate 1-based combination proboscis K) UP70/EPDM, Dicumyl peroxyl"/Ethi I/Dimethacrylate-1-based combination promoting agent shows.

Promoted CZ: N-cyclohexyl-2-・\nzothiazi/
l Nosulfenamide-promoted MSA: N-oxydiethylene-2-hendizo1-anino-lsulfenamide-promoted D, Cyphenylquanicine-promoted TS + Latramethylthiura J, Mono→Nolphide-promoted DM - Cybenzothiazyl cisulfite - Measurement results are shown in Table 5.

Table 5 1---□□≧1j! ;□House'fii□;-ni-mu-oki-,1,,,--.

−−−−−−−−−−−−−1−−−World 2 pair o,
1 , , , , , -1 Ru ■ - wo,?・-G) Adhesive force kg/25mm 25.0 11.0
Limit state Adhesive Z tsum layer destruction Adhesive rubber layer destruction H)
Adhesive force kg/25mm 18.0 1
0.5 limit state Adhesive rubber fracture Adhesive rubber J, layer fracture■) Adhesive force kg/25mm 18.0
8.5 Limit state Adhesive rubber fracture Adhesive rubber layer fracture J) Adhesive force kg/25mm 12.0
11.5 Limit state Adhesive rubber break Adhesive rubber break 1UiK) Adhesive force kg/25mm 12.
0 12.5 Limit state Adhesive rubber fracture From the adhesive rubber fracture experimental results, according to the method of the present invention, a vulcanized adhesive of commonly used sulfur vulcanized rubber (B) and millable urethane elastomer can be obtained. I understand that.

Experiment 5 The adhesive rubber (C) compound was replaced with the adhesive rubber (C) in Experiment 4.
) The composition and formulation elements are the same, but in order to change the structural strength, the type and amount of carbon used and the amount of plasticizer used are changed as shown in Table 6. , (C) itself was used as ni'$, rubber, and mu (B), and an adhesive with a millable urethane elastomer was prepared.

The processing method was the same as in Experiments 1 to 3.
mm, the adhesive rubber and adhesion plate is 4 mm, and the temperature is 150°C.
× Vulcanize for 30 minutes.

Table 6 No, I No, 31 No, 32 No, 33
EPDM (EP33) 100 100 1
00 100GPF N660 car phone 50-1-
−−−−−−−−−−−FEF N550 car phone □
5O------HAF N330 Carbon---11040 Paraffin Oil 2
0 20 10 2F+zinc oxide
5 5 5 5 Stearic acid 1
1 1 1DCP (Park Mill D) 2
．． 7 2.7 2.7 2.7T Gate P (Light Ester 3.4 3., + 3.4 3.
4 Hardness (JIS-Δ) 54 60 6
8 59TB (kg/cm)
125 145 16
3 152EB (%) 390
4.20 350 450 Adhesive strength (kg/25
mm) 10.5 14 15 14.
5 Limit state Adhesive rubber Adhesive rubber Adhesive Go J, Contact 21 Go J.

−−−−−−−−−−Rupture −−−−−−−
--- From Kiri Experimental Yuri, contact 7117, (C) Mixture N0
No. 11, No. 31, No. 32, No. 33 were also in good contact with Miraflu urethane. As in the wood experiment, the type and amount of carbon fiber used and the amount of plasticizer can be varied.

Therefore, the adhesive rubber (C) was designed taking into account the required hardness or strength, and a laminate of Miraflu urethane and lath l-mer was made into a two-layered product. It can be used as a laminate made of

(Articles according to the present invention) Articles (conhair belts, flat belts, etc.) can be made using the method of the present invention. That is, if wear resistance is required, a laminate using Miraflu urethane on the surface can be obtained.

The structure of the laminate is shown in Figures 1-5. The method for making it is as follows.

The millable urethane elastomer (A), the unvulcanized rubber (B), and the adhesive rubber (C) of the laminate of the present invention can all be obtained from ordinary rubber processing steps. For example, kneading is carried out using an internal mixer such as a hand mixer or an open roll, and then a desired thick sheet is obtained by rolling using a calender roll. Then, using a vulcanizer such as a step press or a rotary press, these sheets 1 to 1 are stacked and vulcanized and bonded to produce a laminate.

The vulcanization conditions are determined by considering the properties of the millable urethane elastomer and rubber.

(Materials used) The trade names of materials used in the examples of the present invention are shown in the following format.

Compound splitting------------Product name------------------PDM Japan Synthetic Rubber rEP 33 ji7 Natural rubber, standard rR5S No. 3" BR Japan Synthetic Rubber rl, 502J BR Japan Synthetic Rubber rN230s JPM 1" This synthetic rubber rcPll" I. Rimethi L7-Lup 2 Pantrimethacrylate Kyoeisha Yushi Kagaku Kogyo "Light Ester TMP J Ethylene Dimethacrylate I. Kyoeisha Oil and Fat Chemical Industry “Rye I. Ester EGJ2, 2
“-Bis(4-acryloxydiethoxyphenyl)propane Kyoeisha Yushi Kagaku Kogyo rBP-4EAJ2, 2゛-bis(4-acryloxydiethoxyphenyl)-diphenyl)propane Shin-Nakamura Chemical Co., Ltd. rNK Ester BPE-200
Jte I ~ Rahi I - Rofurfuryl Methacrylate I/Kyoeisha Yushi Kagaku Kogyo "Light Ester TtlF Jl, 3-
Butylene dimethacrylate-1/Kyoeisha Yushi Kagaku Kogyo ``Light Ester 1.38G''.

1,4-Butylene dimethacryle = I. Kyoeisha Yushi Kagaku Kogyo “Light Ester 1.4BG J1
．． 61 No. 1 diol methacrylate-1-Shin Nakamura Kagakugyo rllk Esral lI 1111.6-\
Kizanshiordimetakuri! 2.-1. Kyoeisha Oil and Fat Chemical 2I], industry '1.611X-Al polyethylene greeni? -) Regimethacrylate-1-Kyoeisha Oil and Fat Chemical Industry [Light Varnish Wall 4F) G-II, Rimethylolp [I Pan I, Reacryl Relay I, Kyoeisha Oil and Fat Chemical T Industry rTMl
)-8" Zinc acrylic I/-t Asada Chemical r[1ss-1 Zinc methacrylate-1 Asada Chemical rR-20SJ Dihinyl Hensen Sankyo Kasei Kogyo "Divinyl\Nsen" N, N'
-Meta-)j, Nylenedimaleimito Ouchi Shinko Chemical Industry
"Harnock PMJ (Effects of the Invention) As described above, according to the present invention, (8) adhesion to a millable urethane elastomer containing an organic peroxide as a crosslinking agent ([1) Ono Jl'l Sulfur/, (C) A wood containing an acrylate-I-compound containing a board peroxide and two or more raw wood-carbon unsaturated bonds in a resin containing EPDM or ljPM as a body. The unvulcanized rubber is used as adhesive rubber, and (C
) can be bonded by using vulcanization adhesive.

7 Therefore, the laminate obtained by the method of the present invention is
For example, it can be used for conveyor belts, flat conveyor belts, etc., and has improved abrasion resistance compared to those in which the material is used as cover rubber for conveyor belts.

[Brief explanation of the drawing]

1 to 5 are partially enlarged views of the laminate of the present invention. 1.1" Millable urethane elastomer 2.2"
Adhesive rubber layer 3 A layer formed from general rubber material 1j.1 (for example, a sulfur-cured natural rubber layer)

Claims (1)

[Claims] 1. In adhesion of the following (A) and (B), the following (C)
is the adhesive rubber, and between these (A) and (B) is (C)
A method of adhering a millable urethane elastomer and rubber, characterized by vulcanization adhesion with the interposition of. (A) Millable urethane elastomer containing organic peroxide as a crosslinking agent (B) Unvulcanized rubber (C) Rubber mainly composed of ethylene-propylene-nonconjugated diene ternary copolymer rubber or ethylene-propylene copolymer rubber , Unvulcanized rubber containing an organic peroxide and a (meth)acrylate compound having two or more carbon-carbon unsaturated bonds 2 As a (meth)acrylate compound having two or more carbon-carbon unsaturated bonds, the following ( The method of bonding a millable urethane elastomer and rubber according to claim 1, using at least one of D) to (F). (D) 2,2'-bis(4-acryloxydiethoxyphenyl)propane, (E) 2,2'-bis(4-methacryloxydiethoxyphenyl)propane, (F) Trimethylolpropane trimethacrylate 3rd 1 layer (surface) is millable urethane elastomer,
A laminate in which the second layer (adhesive layer) is made of the adhesive rubber according to claim 1 or 2, and the third layer is made of rubber. 4. The laminate according to claim 3, wherein the second layer also serves as the third layer. 5. A power transmission belt and a conveyance belt having at least the laminate according to claim 3 or claim 4.