JP2000119615A - Aqueous adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous adhesive composition which is suitable as an adhesive for vulcanizing adhesion of a rubber on a metal, has a high solid content and a high drying rate and exerts a high adhesion against both rubbers and metals. SOLUTION: This aqueous adhesive composition contains (A) a halogen- containing polyolefin latex, (B) a liquid polymer having a diene and a functional group other than dienes, (C) carbon black, (D) an oxime compound and (E) a polymaleimide compound. Preferably, (B) the liquid polymer and (C) carbon black are previously mixed before use. Based on 100 pts.wt. solid component of the latex (A), preferably from 10 to 60 pts.wt. liquid polymer (B) and from 10 to 60 pts.wt. carbon black (C) are contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinked aqueous adhesive composition suitable as an adhesive for vulcanizing and bonding rubber to metal.

[0002]

2. Description of the Related Art In general, a vulcanized (cross-linked) adhesive is used in the production of a rubber laminate. Is vulcanized. In recent years, in such adhesives, it has been desired to minimize the use of organic solvents from the viewpoint of work hygiene and environmental hygiene, and a shift from a solvent type to an aqueous type is desired.

On the other hand, a latex adhesive has been known as a water-based vulcanizable adhesive. For example, Patent 266
No. 7555 proposes an adhesive composition containing a butadiene-styrene-vinylpyridine terpolymer latex and a thermosetting resin as an adhesive for vulcanizing and bonding a fiber material and rubber. . A water-based vulcanizing adhesive containing a halogenated rubber latex for bonding rubber and metal has also been proposed.
No. 3 discloses an adhesive composition containing a halogenated diene rubber (such as butadiene rubber) latex, and Japanese Patent Publication No. 8-509520 discloses an adhesive composition containing a chlorosulfonated polyethylene latex. Have been. It is disclosed that each of the above compositions contains a nitroso compound, a polymaleimide compound or a metal oxide as a vulcanizing agent (crosslinking agent), and may contain carbon black or the like.

[0004] The use of the above-mentioned water-based (aqueous) adhesive can reduce the amount of solvent volatilized during the operation, which is preferable for environmental hygiene. However, the water-based adhesive has a problem that drying is slower than that of the solvent type. There is a point, and an increase in the solid content, that is, a reduction in the water content has been desired. In particular, in applications such as laminated rubber bearings for seismic isolation devices, as the solid content increases, a metal-to-metal and rubber-to-rubber bond strength comparable to that of the solvent type is required. In particular, improvement in rubber-to-rubber bond strength is desired. Was.

[0005] When increasing the solid content of the aqueous adhesive, there is a limit to the increase in the solid content of the latex. Therefore, a method of adding a filler may be considered. At this time, when a rubber reinforced with carbon black, such as a laminated rubber bearing for a seismic isolation device, is used as the adherend, it is preferable to add carbon black as a filler for the adhesive. When the carbon black is contained in the aqueous adhesive, usually, the carbon black is dispersed in water containing a surfactant in advance and then mixed with the latex.

[0006] However, when the amount of carbon black added increases, it becomes difficult to uniformly disperse it in a mixture with latex, and the stability of the latex decreases, and precipitation tends to occur. For this reason, conventionally, the amount of carbon black added to the aqueous adhesive has been limited to a relatively small amount. For example, as shown in the above-mentioned Japanese Patent Application Laid-Open No. 8-509520, 100 parts by weight of a latex solid content is 1%.
It is about 5 to 25 parts by weight. In addition, when the present inventor studied latex containing carbon black, the conventional aqueous adhesive, even if carbon black was added, after vulcanization, carbon black and the vulcanized rubber component in the latex were independent. It has been found that it does not exhibit the reinforcing effect of carbon black compounded in general vulcanized rubber.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is an aqueous vulcanization type adhesive suitable as an adhesive for vulcanizing and bonding rubber to metal. It is an object of the present invention to provide an aqueous adhesive composition which has a high solid content and a high drying rate and exhibits excellent adhesiveness to both rubber and metal.

[0008]

The aqueous adhesive composition according to the present invention comprises (A) a halogen-containing polyolefin latex, (B) a liquid polymer having a diene and a functional group other than a diene, and (C) carbon black. , (D) an oxime compound, and (E) a polymaleimide compound. When preparing an aqueous adhesive composition from (A) to (E), it is desirable to use (B) a liquid polymer and (C) carbon black in a premixed state.

The aqueous adhesive composition preferably contains 10 to 60 parts by weight of the liquid polymer (B) based on 100 parts by weight of the solid content of the latex (A). Carbon black (C) Of the oxime compound (D).
To 60 parts by weight and the polymaleimide compound (E)
It is preferred to contain 40 parts by weight. In the present invention,
50-70% by weight of the total solid content in the aqueous adhesive composition
It can be.

As the latex (A), chlorosulfonated polyethylene latex is specifically mentioned. The liquid polymer having the diene is polybutadiene, styrene-butadiene copolymer, polyisoprene,
Those selected from the group consisting of nitrile rubber, polyisobutylene and butyl rubber are preferred. Liquid polymer (B)
The functional group other than the diene is preferably selected from the group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group, and a silyl group. The liquid polymer (B) desirably contains a functional group other than the diene in an amount of 1 to 20% by weight.
The aqueous adhesive composition according to the present invention is suitable for bonding rubber and metal.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present specification, vulcanization is used in substantially the same meaning as crosslinking. The aqueous adhesive composition according to the present invention,
(A) halogen-containing polyolefin latex, (B)
It contains a liquid polymer (B) having a diene and a functional group other than a diene, (C) carbon black, (D) an oxime compound, and (E) a polymaleimide compound. First, each of these components will be described.

<(A) Halogen-Containing Polyolefin Latex> In the present specification, the latex refers to a colloidal aqueous dispersion of rubber (crosslinkable polymer), and usually contains no organic solvent or a small amount of an organic solvent. It is. In the present invention, a latex whose rubber component is a halogen-containing polyolefin is used. The halogen-containing polyolefin is obtained by replacing a hydrogen atom in a polyolefin molecule such as polyethylene, polypropylene, and polybutene with a halogen or a halogen-containing group. Halogen is
Chlorine and bromine are preferred. Examples of the halogen-containing group include a chlorosulfone group. Halogen-containing polyolefins exhibit rubber elasticity because crystallization of polyolefins is inhibited by bulky groups such as halogens or halogen-containing groups.

As the above-mentioned halogen-containing polyolefin, specifically, chlorosulfonated polyethylene (C
SM), chlorinated polyethylene (CM), polychloroprene, chlorinated polybutadiene, chlorinated ethylene propylene copolymer and the like. Chlorosulfonated polyethylene (CSM) generally has a Cl group and a chlorosulfone group (—SO ₂ Cl) in the polyethylene main chain as shown by the following structure.

[0014]

Embedded image

The halogen or halogen-containing group in such a halogen-containing polyolefin can also function as a crosslinking point. The content of halogen or halogen-containing group varies depending on the type of element or group.
The chlorine content of SM is usually about 20 to 50% by weight, preferably about 25 to 45% by weight, and the sulfur content is about 0.1 to 2% by weight, preferably about 0.5 to 1.5% by weight. , CM should usually be about 30 to 40% by weight. The molecular weight of CSM is usually 50,000 to
It is about 150,000. The latex may include two or more halogen-containing polyolefins.

The method for producing the above-mentioned halogen-containing polyolefin latex is not particularly limited. For example, a latex directly produced by emulsion polymerization or a latex in which a previously produced halogen-containing polyolefin is dispersed in water. You may. The halogen-containing polyolefin latex is generally composed of a halogen-containing polyolefin (solid) previously produced by solution polymerization or the like,
It is obtained by emulsifying water with high shear in the presence of a surfactant. Chlorinated polyethylene (CM) latex used for emulsification is usually obtained by a reaction between polyethylene and chlorine, and chlorosulfonated polyethylene (CSM) is usually obtained by a reaction between polyethylene, chlorine and sulfur dioxide. .

Of these, CSM latex is particularly preferably used. Chlorosulfonated polyethylene (CSM) has high cross-linking properties and its polarity is particularly close to the polarity of natural rubber, so that it exhibits excellent adhesiveness when natural rubber is used as an adherend. The solid content (rubber component) of the latex used in the present invention is usually 10 to 60% by weight, preferably 25 to 50% by weight.

<(B) Liquid Polymer> In the present invention, a liquid polymer (B) having a diene and a functional group other than the diene is used. This liquid polymer is a crosslinkable polymer containing a diene in its main chain or side chain, and exhibits rubber elasticity after crosslinking.If it is liquid at normal temperature, it is only a liquid itself. Instead, a solid dissolved in a solvent, a plasticizer, or the like may be used, but a liquid itself is preferable.

Examples of such a crosslinkable liquid polymer include liquid diene rubbers such as polybutadiene, styrene-butadiene copolymer, polyisoprene, and nitrile rubber, polyisobutylene having a diene in a side chain, isobutylene and isoprene, for example. And a liquid olefin rubber such as butyl rubber which is a copolymer with a diene monomer.

The liquid polymer preferably has a molecular weight capable of maintaining a liquid state, and although it varies depending on the type of the polymer, the weight average molecular weight is usually about 1,000 to 20,000. More specifically, the weight average molecular weight of the liquid diene rubber is usually about 3000 to 5000. The weight average molecular weight of a liquid olefin-based rubber such as polyisobutylene is usually about 5,000 to 20,000. These are liquid at normal temperature. Such a crosslinkable polymer that is liquid at normal temperature is known as a liquid rubber.

The liquid polymer used in the present invention has a functional group other than a diene, and specifically includes an acid anhydride group,
It has a group selected from the group consisting of a carboxyl group, a hydroxyl group, and a silyl group. The liquid polymer may have two or more of these groups. The liquid polymer (B) has only to have one functional group other than the above-mentioned diene in the molecule, and usually contains the functional group in an amount of 1 to 20% by weight. The liquid polymer having such a functional group exhibits fine dispersibility when mixed with latex.

The liquid polymer (B) may have the above functional group at the molecular terminal of the main chain polymer, or may have the functional group at the inner chain of the molecule. These functional groups can be introduced by a known method. For example, a liquid polymer having these functional groups at the molecular terminals can be produced using a living polymerization method, a bifunctional radical polymerization method, or the like. . In introducing these functional groups into the inner chain of the molecule, a usual modification method or the like can be used.

As the liquid polymer (B) as described above,
Specific examples include maleic anhydride-modified polybutadiene, hydroxyl-terminated polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polyisoprene, carboxyl-terminated polyisoprene, carboxyl-terminated nitrile rubber, silyl-terminated polyisobutylene, and the like.

In the present invention, as the above liquid polymer (B), for example, Ricon130 MA13 (Ricon Resi
n inc.), R-45HT (made by Idemitsu Petrochemical Co., Ltd.),
Poly ip. (Idemitsu Petrochemical Co., Ltd.), Epion EP-10
3s, 303s, 505s (Kanebuchi Chemical Industry Co., Ltd.)
Manufactured), Hycar CTB, CTBN (Ube Industries, Ltd.)
And LIR-410 (manufactured by Kuraray Co., Ltd.). In the present invention, two or more liquid polymers may be used in combination. If necessary, the liquid polymer may be diluted with a solvent or a plasticizer before use.

<Preliminary mixture> In the present invention, when preparing the aqueous adhesive composition, the liquid polymer (B) as described above is used.
And carbon black (C) are preferably mixed and used in advance. The pre-mixing (kneading) is performed using the liquid polymer (B).
And carbon black (C) are stirred so that they can be evenly dispersed. The stirring may be performed at room temperature, or may be performed as necessary. Normally, at 20 to 35 ° C using a ball mill or the like, 3
It is desirable to stir for ~ 8 hours. The mixing ratio of the liquid polymer (B) and the carbon black (C) at the time of the pre-mixing is used based on the amount of each component used per 100 parts by weight of the solid content of the halogen-containing polyolefin latex (A) as described later.

By premixing (kneading) the carbon black with the liquid polymer in advance as described above, the carbon black is kneaded into the liquid polymer and becomes coated. By forming such a premix, the carbon black does not come into direct contact with the latex when mixed with the latex to destabilize the latex. For this reason, even if a large amount of carbon black is added, it is difficult for latex precipitation to occur in the aqueous adhesive composition. In addition, the fine dispersibility of the functional group of the liquid polymer allows fine dispersion of carbon black evenly in the aqueous adhesive composition.

According to such a method, even a large amount of carbon black can be easily dispersed, and the solid content of the aqueous adhesive composition, which has been difficult in the past, can be reduced with the carbon black and the liquid polymer. Can be increased. Further, carbon black is added by being coated on the rubbery polymer, and the adhesive strength can be effectively improved as compared with the case where carbon black is added alone. In the present invention, the carbon black (C) is premixed as described above, so that the latex (A) can be added to the latex (A) in an amount of 10 to 60 parts by weight based on 100 parts by weight of the solid content. It can be mixed with good dispersibility.

<Crosslinking Agent> The aqueous adhesive composition according to the present invention contains an oxime compound (D) and a polymaleimide compound (E) as a crosslinking agent component. These crosslinking agents suitably act particularly as a crosslinking agent for the halogen-containing polyolefin (A). In the present invention, among oxime compounds known as the oxime compound (D), those having a structure in which at least two = N-OH atomic groups are directly connected to an aromatic ring are used. Examples of the aromatic ring include benzene, naphthalene, anthracene, biphenyl and the like. Of these, a benzene ring is preferred. The aromatic ring may have a substituent such as a hydrocarbon group such as an alkyl group, an alkoxy group, or a cycloalkyl group aryl group, or an amino group or a halogen group. Among these substituents, an alkyl group having 1 to 8 carbon atoms is preferable.

Specific examples of such oxime compounds include p-quinone dioxime, p, p'-dibenzoquinone dioxime, 1,2,4,5-tetrachlorobenzoquinone, 2-methyl-
Examples include 1,4-benzoquinone dioxime, 1,4-naphthoquinone dioxime, 1,2-naphthoquinone dioxime, and 2,6-naphthoquinone dioxime. Among these, m- or p-dioxime aromatic compounds are preferred, and p-quinone dioxime is particularly preferred because of its high dispersibility and excellent adhesiveness.

The polymaleimide compound (E) used in the present invention may be an aliphatic compound or an aromatic compound as long as it contains at least two maleimide groups. preferable. Of these, 1
An aromatic polymaleimide having about 2 to 100 aromatic rings to which maleimide groups are directly connected is preferable, and the aromatic ring may have a substituent such as an alkyl group. As such an aromatic polymaleimide, for example, N, N'- (4,4'-
Diphenylmethane) bismaleimide, bis (3-ethyl-5
-Methyl-4-maleimidophenyl) methane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane and the like. Among these, N, N '-(4,4'-diphenylmethane) bismaleimide is preferable because it has excellent dispersibility and can improve the metal adhesive strength of the aqueous adhesive composition.

<Aqueous adhesive composition> The aqueous adhesive composition according to the present invention comprises (A) a halogen-containing polyolefin latex (also referred to simply as latex) as described above,
(B) The liquid polymer, (C) carbon black, (preferably a pre-mixture of (B) and (C)), (D) an oxime compound, and (E) a polymaleimide compound. This water-based adhesive composition comprises a latex (A)
The liquid polymer (B) was added to 100 parts by weight of the solid content of
It is desirable to contain it in an amount of 10 to 60 parts by weight, preferably 25 to 50 parts by weight. The carbon black (C) can be contained in an amount of 10 to 60 parts by weight, preferably 25 to 50 parts by weight, based on 100 parts by weight of the solid content of the latex (A).

The crosslinking agent may be contained in such an amount that the halogen-containing polyolefin can be sufficiently crosslinked. Usually, the crosslinking agent is used based on 100 parts by weight of the solid content of the latex (A).
The oxime compound (D) is used in an amount of 5 to 60 parts by weight, preferably 2 to 60 parts by weight.
In an amount of 0 to 40 parts by weight, the maleimide compound (E)
It is desirable to use it in an amount of from 40 to 40 parts by weight, preferably from 10 to 30 parts by weight. In the aqueous adhesive composition containing the oxime compound (D) and the maleimide compound (E) in the amounts described above, the crosslinking reaction can proceed sufficiently,
Shows excellent adhesion to both metal and rubber. If the amount of the oxime compound (D) exceeds 60 parts by weight, precipitation tends to occur in the composition.

As described above, the water-based adhesive composition according to the present invention can contain a larger amount of carbon black than the conventional water-based adhesive composition. Does not destabilize. Therefore, by adding the liquid polymer and carbon black, the solid content of the aqueous adhesive composition can be increased, that is, the water content can be reduced, and the drying speed can be increased. Specifically, in the present invention, the solid content of the aqueous adhesive composition is about 50 to 70% by weight, preferably 55 to 70% by weight.
It can be about 65% by weight. Further, the water-based adhesive composition according to the present invention containing the above-described components also has a reinforcing effect by carbon black. Therefore, the water-based adhesive composition according to the present invention exhibits excellent adhesiveness to both rubber and metal, and can exhibit adhesive strength (breaking strength) comparable to that of a solvent-based adhesive.

The aqueous adhesive composition according to the present invention may contain, if necessary, other additives, such as sulfur and metal oxides, in addition to the above components, as long as the object of the present invention is not impaired. Vulcanizing agents, vulcanization accelerators, vulcanization accelerators, plasticizers,
It may contain a coloring agent, a dispersing agent, a wetting agent and the like. Especially liquid polymers (B) such as sulfur, zinc white and stearic acid
It is preferable to contain a vulcanizing agent, a vulcanization accelerator and the like. The method for preparing the aqueous adhesive composition from each of the above components is not particularly limited. For example, the above component (A),
Preliminary mixture of (B) and (C), (D), (E) and, if necessary, other optional components, and water, preferably distilled water, are mixed using a known mixer such as a ball mill. What is necessary is just to knead. At this time, the amount of water may be adjusted so that the solid content of the aqueous adhesive composition finally becomes a desired amount.

The aqueous adhesive composition according to the present invention as described above is suitable as an adhesive for bonding rubber and metal. Specific examples of the adherend rubber material include natural rubber, isoprene rubber, chloroprene rubber, butadiene rubber, neoprene rubber, butyl rubber, brominated butyl rubber, nitrile rubber, olefin rubber, and thermoplastic elastomer. Natural rubber or rubber containing natural rubber is preferred. The adherend rubber may contain additives generally blended with rubber, such as a vulcanizing agent, a vulcanization accelerator, other fillers, and a rubber oil extender according to the rubber material, Further, it may contain resins as required.
The adherend rubber may be unvulcanized rubber or vulcanized rubber.

As the adherend metal, metals commonly used as structural metals such as iron, steel, stainless steel, lead, aluminum, copper, brass, bronze, nickel and zinc can be used without particular limitation. . A rubber / metal composite can be prepared by appropriately selecting from the above rubbers and metals.

In the present invention, among the above-mentioned rubber / metal composites, a laminated rubber bearing, a vibration damping material, a soundproofing material, etc., which are used particularly as a seismic isolation device, can be cited as preferred examples. For example, a laminated rubber support is usually a laminate of a steel plate such as iron and a rubber of a natural rubber type, and the aqueous adhesive composition has a particularly excellent adhesive strength to such a steel plate and a natural rubber. Show.

In the present invention, when producing a rubber / metal composite, an unvulcanized rubber is used as the adherend rubber, and the adhesive and the rubber are simultaneously vulcanized and bonded to the metal. Is preferred. In this preferred embodiment, specifically,
After the aqueous adhesive composition is applied to the metal surface and dried, a rubber substrate is laminated on the coating layer, and vulcanized and bonded under heating and pressure conditions to obtain a rubber / metal composite.

The aqueous adhesive composition can be applied by spraying, dipping, brushing, wiping, or the like. The vulcanization adhesion varies depending on the thickness of the rubber substrate, etc., but is usually 1 to 10 MPa under heating at 130 to 170 ° C.
a can be performed under pressure.

[0040]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. (Examples 1 to 5) The liquid polymer (B) and the carbon black (C) in the amounts shown in Table 1 were mixed at 30 ° C. using a ball mill.
For 4 hours to obtain a premix. The obtained preliminary mixture and the other components shown in Table 1 were mixed in an amount shown in Table 1 using a homogenizer to obtain an aqueous adhesive composition. Adhesiveness of the obtained aqueous adhesive composition (initial adhesiveness,
(Water resistance) was evaluated using a steel sheet / rubber adhesive (test sample) prepared as follows.

<Preparation of Test Samples> Sandblasted steel plates (SS-400, 20 mm × 100 mm ×
2 mm thick), and after applying the aqueous adhesive composition and air-drying, a rubber having the following composition preformed into a 3 mm-thick plate in the form of a 10 mm × 50 mm adhesive area with the coating layer was applied on the coating layer, By holding at 2 MPa and 150 ° C. for 40 minutes, the adherend rubber and the adhesive were simultaneously vulcanized,
A rubber laminate (test sample) was obtained.

<Rubber composition for adherend> Rubber (NR / BR weight ratio = 70/30): 100 parts by weight Carbon black (HAF grade): 70 parts by weight Resin high resin (trade name: QPA): 20 parts by weight Aroma oil: 10 parts by weight Sulfur: 1 part by weight Zinc oxide (zinc white): 5 parts by weight Vulcanization accelerator: 2 parts by weight (CBS: N-cyclohexyl-2-benzothiazole sulfenamide) Stearic acid: 2 parts by weight

<Test Method> 1) Initial Adhesion The test sample obtained above was cured at 25 ° C.
After standing for 27 hours at 90 ° C., a 90 ° peel test was performed in accordance with JIS K6256 “Test for peeling rubber bonded to a metal piece in a 90 ° direction” to measure peel strength and observe the peeled surface. In Table 1, the measured value of the peel strength is shown as the breaking strength (N / cm).

The observation of the peeled surface showed whether the peeling occurred at the interface between the adhesive layer and the rubber layer or the metal layer, or was due to the destruction of the rubber layer. In the table, R / R indicates that the peeling occurred due to the destruction of the rubber layer, and the subscript indicates the ratio (%) of the bonding area of the rubber not peeled from the steel sheet to the total bonding area of the rubber bonded to the steel sheet. Show. Where R / R10
"0" indicates that all peeling was due to the destruction of the rubber layer. The “rubber attached state” indicates the state of the rubber layer remaining on the steel plate side.

2) Water Resistance Adhesion A test sample was immersed in warm water at 80 ° C. for one month, and then the same test as the initial adhesion was performed. In the adhesion test as described above, in the observation of the peeled surface, even if the peeling is all R / R100 due to the destruction of the rubber layer, if the rubber adhesion state of the steel sheet is “thick and uniform”, the adhesive It shows that the adhesive force is much stronger than the adherend rubber strength, and also R / R
Even if it is 100, if it is "thin and uniform", the adhesive strength between the adhesive layer and the rubber layer is weaker than the rubber strength, and peeling has occurred because almost the interface between these layers is broken. Is interpreted as Therefore, when the remaining rubber layer is “thin and uniform”, the breaking strength is generally lower than when the remaining rubber layer is “thick and uniform”, and its value is less scattered.

(Comparative Examples 1 and 2) The procedure of Example 1 was repeated except that only carbon black (C) was used in the amount shown in Table 1 in place of the preliminary mixture of liquid polymer (B) and carbon black (C). In the same manner as in the above, an aqueous adhesive composition was obtained. Using the obtained aqueous adhesive composition, test samples similar to those in the examples were prepared, and the adhesion was evaluated. Table 1 shows the results.

Comparative Example 3 Aqueous adhesion was carried out in the same manner as in Example 4 except that the latex was replaced with that shown in Table 1 and only carbon black (C) was used without using the liquid polymer (B). Agent composition was obtained. Using the obtained aqueous adhesive composition, test samples similar to those in the examples were prepared, and the adhesion was evaluated. Table 1 shows the results.

[0048]

[Table 1]

Each component in the table 1) CSM latex: chlorosulfonated polyethylene latex (trade name: CSM200 manufactured by Sumitomo Seika Co., Ltd.), solid content: 40% by weight 2) SBR latex: styrene-butadiene rubber latex (trade name: Japan) LX430 manufactured by Zeon Co., Ltd., solid content 50% by weight 3) Maleic anhydride-modified polybutadiene (Ricon Resin)
Inc. Ricon130MA13): Maleic anhydride modification rate 13
%, Mn = 3100 4) OH-terminated polybutadiene (R manufactured by Idemitsu Petrochemical Co., Ltd.)
-45HT): OH content 1.2%, Mw = 2800 5) OH-terminated polyisoprene (Pod manufactured by Idemitsu Petrochemical Co., Ltd.)
ly ip.): OH content 1.1%, Mw = 2900 6) Silyl group-terminated polyisobutylene (Epion EP-505s, manufactured by Kaneguchi Chemical Co., Ltd.): Silyl group content 0.8
%, Mw = 20,000, plasticizer 33% by weight 7) Oxime compound: p-quinonedioxime (GM-P manufactured by Ouchi Shinko Chemical Co., Ltd.) 8) Polymaleimide compound: N, N '-(4,4'- Diphenylmethane) bismaleimide, (BMI manufactured by KI Kasei)

[0050]

The water-based adhesive composition according to the present invention does not release volatile solvents during work, so that it is not only favorable for work hygiene and environmental hygiene but also has a fast drying and exhibits excellent adhesive performance. In particular, this aqueous adhesive composition exhibits adhesive strength to rubber comparable to that of the conventional solvent type. Such an aqueous adhesive composition is particularly suitable as an adhesive for a rubber / metal laminate such as a laminated rubber support for a seismic isolation device, a vibration damping material, and a soundproofing material.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J040 CA052 CA072 CA082 CA102 DA021 DA132 DA142 DA181 DA191 DB052 DF082 GA01 GA05 GA07 GA12 GA13 GA30 HA026 HA126 HC17 JA03 JB02 KA16 LA05 LA06 MA02 MA12 NA12

Claims (11)

[Claims] 1. A method comprising: (A) a halogen-containing polyolefin latex, (B) a liquid polymer having a diene and a functional group other than a diene, (C) carbon black, (D) an oxime compound, and (E) a polymaleimide compound. An aqueous adhesive composition containing the composition. 2. A premix of (A) a halogen-containing polyolefin latex, (B) a liquid polymer and (C) carbon black, (D) an oxime compound, and (E)
The aqueous adhesive composition according to claim 1, which is obtained by mixing a polymaleimide compound. 3. The aqueous adhesive composition according to claim 1, wherein the liquid polymer (B) is contained in an amount of 10 to 60 parts by weight based on 100 parts by weight of the solid content of the latex (A). 4. The aqueous adhesive composition according to claim 1, wherein the carbon black (C) is contained in an amount of 10 to 60 parts by weight based on 100 parts by weight of the solid content of the latex (A). 5. The latex (A) contains 5 to 60 parts by weight of the oxime compound (D) and 2 to 40 parts by weight of the polymaleimide compound (E) based on 100 parts by weight of the solid content of the latex (A). The aqueous adhesive composition according to any one of items 1 to 4, wherein 6. The aqueous adhesive composition according to claim 1, wherein the latex (A) is a chlorosulfonated polyethylene latex. 7. The aqueous adhesive composition according to claim 1, wherein the total solid content in the aqueous adhesive composition is 50 to 70% by weight. 8. The method according to claim 1, wherein the diene-containing liquid polymer is selected from the group consisting of polybutadiene, styrene-butadiene copolymer, polyisoprene, nitrile rubber, polyisobutylene, and butyl rubber. Aqueous adhesive composition. 9. The aqueous solution according to claim 1, wherein the functional group other than diene of the liquid polymer (B) is selected from the group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group and a silyl group. Adhesive composition. 10. The aqueous adhesive composition according to claim 9, wherein the liquid polymer (B) contains a functional group other than the diene in an amount of 1 to 20% by weight. 11. An adhesive for bonding rubber and metal.
The aqueous adhesive composition according to any one of items 10 to 10.