JPS625457B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to aqueous organic compositions. More particularly, this invention relates to water-based, organic polymer-containing compositions particularly suitable for use as adhesives for bonding natural and synthetic elastomers to rigid or non-rigid substrates. Historically, it has been used to bond natural and synthetic elastomers to the same or different elastomers and other rigid or non-rigid substrates, including metals, wood, ceramics, natural and synthetic organic and inorganic fibers, etc. Adhesives are organic solvent-based adhesives, i.e., the adhesive components, including active ingredients such as film-forming substances and adhesion-promoting additives, as well as inactive ingredients such as fillers and extenders, are made of toluene, xylene or trichloroethane. Volatile, like
The adhesive was dissolved or dispersed in an inert organic solvent. Concerns about the negative effects on the environment and the human body due to the volatilization of organic solvents into the atmosphere have increased, and as a result, efforts have been made to develop adhesives that can replace organic solvent adhesives. Proposed alternatives to currently used organic solvent-based rubber-metal adhesives include those using organic solvents that do not violate various government regulations, and those with a solids content of 70% or more. There are high solids adhesives that minimize the amount of inert organic solvents used, 100% solids compositions that contain almost no inert organic solvents, film adhesives, and water-based adhesives. Water-based adhesives, ie, those in which the adhesive components are soluble or dispersible in water, are particularly attractive. This is because it is less likely to violate environmental regulations than adhesives containing organic solvents and is suitable for use with adhesive machines. A particular challenge for the development of water-based adhesives is finding film-forming polymers or other materials in aqueous solvents that are comparable to the film-forming materials currently used in organic solvent-based adhesives. be. Generally, the materials used as the basis for organic solvent-based adhesives are insoluble in water. Efforts to create satisfactory emulsions from these materials have generally been unsuccessful.
Of these, particularly promising is the development of copolymer emulsions of halogenated conjugated dienes and halogenated vinyl monomers, typified by copolymers of 2,3-dichloro-1,3-butadiene and α-acrylonitrile. Ta. Water-based adhesives were made from these emulsion copolymers, and their rubber-to-metal adhesion was comparable to that of currently used organic solvent-based adhesives. However, these newly developed water-based adhesives
Its environmental durability and pre-heat tolerance (the adhesive applied on the substrate, during the production process, under the bonding temperature before being brought into contact with the elastomer to be bonded)
They are inferior to organic solvent-based adhesives in terms of their ability to maintain their adhesive strength even after being left for a certain period of time. The present invention provides a storage-stable, heat-activated, single-package, water-based adhesive particularly suitable for bonding natural and synthetic rubbers to rigid or non-rigid substrates, An adhesive has been provided that has adhesive strength comparable to that of solvent-based adhesives, and has improved preheat tolerance and environmental durability. In another aspect, the present invention provides a method for bonding natural and synthetic elastomers to the same or different elastomers or rigid or non-rigid substrates. More specifically, the adhesive composition of the invention comprises the presence of at least one anionic surfactant or a mixture of at least one anionic surfactant and at least one nonionic surfactant. (a) 2-halo-1,3-
By emulsion copolymerization of a mixture of at least one conjugated diene selected from the group consisting of butadiene and 2,3-dihalo-1,3-butadiene and (b) at least one monoalkenyl aromatic alkyl halide. It consists of a latex of elastomer copolymer made. The latex adhesive of this invention also includes 100% elastomer copolymer solids.
From 1 to 200, preferably from 10 to 150 parts by weight, based on parts by weight, of at least one aromatic nitroso compound can be dispersed therein. The adhesive composition of this invention also optionally includes an additional water-soluble or water-dispersible film-forming material selected from the group consisting of halogenated rubbers, halogenated resins, and phenolic resins in combination with the elastomeric copolymer solids. It may contain from 20 to 90% by weight based on the total weight of the additional film-forming material. As the halogenated conjugated diene monomer, 2,3-dihalo-1,3-butadiene is currently preferred, with 2,3-dichloro-1,3-butadiene being currently selected. Bromine and iodine substituted monomers of 1,3-butadiene are also
It can be used to form the elastomeric copolymer latices of this invention. With reference to comonomers, the term "monoalkenyl aromatic alkyl halide" means that the alkenyl group is bonded directly to an aromatic nucleus of 6 to 14 carbon atoms and that at least one halogen-substituted alkyl group substituted with a halogen on the alpha carbon is also aromatic. is intended to refer to monomers directly attached to the group nucleus. The terms "halo,""halogen,""halogenated," or "halide" are intended to refer to chlorine, bromine, and iodine substituents, with chlorine currently being the substituent of choice. More specifically, the monoalkenyl aromatic alkyl halide is represented by the following general formula. Or Here, X is hydrogen, chlorine, bromine or iodine, and R is an alkyl group having 1 to 4 carbon atoms, and chlorine, bromine or Substituted with 1 to 3 halogen atoms selected from the group consisting of iodine, a is 1 or 2, b is 0,
1, or 2, but at least one b must be at least 1. At present,
X is hydrogen, R is 1, halogen group is 1, a is 1, b
is 1. Monoalkenyl aromatic alkyl halides of the general formula () are currently the comonomers of choice. Representative monoalkenyl aromatic alkyl halides include vinylbenzyl chloride (p-chloromethyl-vinylbenzene), p-trichloromethyl-vinylbenzene,
p-(α-chloroethyl)-vinylbenzene, p-
(α-chlorobutyl)-vinylbenzene, α-chlorovinyl-benzyl chloride, o,m-di(α-
(chloroethyl)-vinylbenzene, 4-chloromethylvinylnaphthalene, and their corresponding bromine and iodine analogs. The monoalkenyl aromatic alkyl halide of current choice is vinylbenzyl chloride. The elastomeric copolymer latex of this invention can be conjugated with halogenated conjugates in an aqueous medium in the presence of an ionic surfactant or an ionic-nonionic surfactant system (ionic surfactants are currently preferred). It is made by emulsion polymerization of a diene and a monoalkenyl aromatic alkyl halide comonomer. The elastomeric copolymers of this invention most suitable for practical use are 67 to 97, preferably 75 to 97, most preferably 93 to 97
% by weight of halogenated conjugated diene and thus
It contains from 3 to 33, preferably from 3 to 25, most preferably from 3 to 7% by weight of monoalkenyl aromatic alkyl halide. However, the amount of each comonomer may be outside this limit. However, the reason for doing so is currently unknown. The emulsion polymerization is carried out in a vessel, and the space within the vessel not occupied by the reaction mixture is preferably oxygen-free by a blanket of an inert gas such as nitrogen. The induction period of the polymerization reaction is lengthened by the presence of oxygen, and therefore it is preferable to carry out the reaction in an environment substantially free of oxygen. Broadly speaking, emulsion polymerization is carried out by mixing and emulsifying the monomer components and subjecting the emulsion to mild polymerization conditions until substantially all of the monomers have polymerized. However, for various practical reasons (not discussed here)
The emulsion polymerization of the halogenated conjugated diene and the monoalkenyl aromatic alkyl halide comonomer is carried out by adding the halogenated conjugated diene and the monoalkenyl aromatic alkyl halide at a constant rate to the polymerization region containing the aqueous solution or aqueous dispersion before starting the polymerization. It can be carried out more effectively by a semi-continuous operation consisting of adding an emulsion with monomers. In the absence of such semi-continuous operation, the polymerization conditions are essentially the same as in conventional batch polymerization operations and need not be discussed here. Since the polymerization reaction is an exothermic reaction, the reaction temperature should be kept at about 75°C or lower, preferably at about 60°C or lower. To start the reaction faster and ensure better reproducibility of the results, ammonium persulfate/sodium pyrosulfite, benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide,
Almost any free radical generating catalyst or initiator can be used, including well-known redox catalyst systems such as azo-bis(isobutyrlonitrile), alkali metal persulfates, alkali metal perborate and ammonium perborate. can. After polymerization, unreacted volatile components can be removed by reduced pressure treatment at elevated temperature or steam distillation, and any method may be used. Most important to obtaining a latex that provides acceptable adhesiveness is the selection of surfactant. It has been discovered that it is necessary to use anionic surfactants or mixtures of anionic and nonionic surfactants, and the latter is currently preferred. Although cationic surfactants are effective emulsifiers, their use alone or in conjunction with anionic surfactants degrades adhesive performance.
The surfactant is used in an amount of 0.01 to 15% by weight, preferably 1 to 10% by weight, based on the weight of the monomer. It is currently preferred to use mixed anionic-nonionic surfactant systems, the ratio of anionic to nonionic surfactant being between 1.2:1 and 2.1:1, preferably The ratio is 1.3:1 to 2.0:1. Typical anionic surfactants include carboxylates such as fatty acids derived from lauric, stearic, and oleic acids, and acyl derivatives of salosine such as methylglycine; ); sulfated natural oils and esters such as turkey red oil; alkylaryl polyether sulfates such as Triton X-301; Triton X-200 and Ultra Wet DS, K, 35K and 42K. alkylaryl polyether sulfonates such as; isopropyl naphthalene sulfonate such as Aerosol 05 and Aerosols OT, MA, TR, 102 and 18
sulfosuccinic acid esters and sulfosuccinamic acid esters such as; phosphoric acid esters such as short chain fatty alcohol partial esters of complex phosphoric acids (Victawet); included. Typical nonionic surfactants include ethoxylated (ethylene oxide derivatives) monohydric and polyhydric alcohols such as the Tritonoctyl- and nonyl-phenol series; ethylene oxide/propylene oxide block copolymers such as the Pluronic series. esters such as glyceryl monostearate; dehydration products of sorbitol such as sorbitan monostearate and polyethylene oxide sorbitan monolaurate (Span and Tween series); and amides such as lauric acid isopropanolamide (Lauridate LP) is included. Currently preferred are sodium dodecyl diphenyl ether disulfonate (Daufuax 2A1) anionic surfactant and nonylphenol polyethylene glycol (Triton
100) 1.8:1 mixture with nonionic surfactant. Regarding the anionic surfactant and anionic-nonionic surfactant system to be used in this invention, please refer to "Emulsion: Theory and Practice"
(“Emulsions: Theory and Practice” Paul
Becker, Chapter 6, Reinhold Publishing Co., New York, 1965) and “Detergents and Emulsifiers”
1972Annual). The elastomer copolymer latex obtained by emulsion copolymerization of a halogenated conjugated diene and a monoalkenyl aromatic alkyl halide according to the invention always has a pH of 2 to 3. Although such acidic compositions exhibit excellent adhesion performance, acid scavengers or buffers such as zinc oxide, dibasic lead phosphate, and sodium acetate-acetic acid mixtures can be used to reduce the pH to about 4.
It is desirable to adjust the number to between 6 and 11, preferably between 6 and 11, and dibasic lead phosphate is currently preferred and used. Such stabilizers are, of course, used in sufficient amounts to achieve the desired PH. Aromatic nitroso compounds suitable for use in the practice of this invention contain at least two nitroso groups bonded directly to non-adjacent ring carbon atoms. Includes all aromatic hydrocarbons such as benzene, naphthalene, anthriacune and biphenyl. More specifically, such nitroso compounds have 1 to 3 aromatic nuclei (including fused aromatic nuclei), and carbon atoms constituting the nucleus can be directly contacted with non-adjacent atoms. Poly-C with 2 to 6 nitroso groups attached
It can be called a (carbon)-nitroso aromatic compound. Presently preferred poly-C-nitroso compounds are dinitroso aromatic compounds, particularly dinitrosobenzenes and dinitrosonaphthalenes, such as meta- or paradinitrosobenzene and meta- or paradinitrosonaphthalene. The hydrogen atom of the aromatic nucleus is an alkyl group, an alkoxyl group, a cycloalkyl group, an aryl group, an arykyl group, an alkaryl group, an arylamine group, an arylnitroso group,
It may be substituted with a group such as an amino group or a halogen group. The presence of these substituents on the aromatic nucleus hardly affects the activity of the poly-C-nitroso compound in this invention. At present, there are no known restrictions on the nature of these substituents, and they may be inorganic or organic. Thus, when referring to poly-C-nitroso "aromatics,""benzene," or "naphthalene," these terms include the substituted versions, unless explicitly stated otherwise. A particularly preferred poly-C-nitroso compound is represented by the general formula ( ^R3 ) _-pAr (-NO) ₂ . Here, Ar is phenylene or naphthalene; R ³ is an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an alkylaryl group, an arylamine group, an alkoxyl group having 1 to 20 carbon atoms, an amino group, and a halogen. a monovalent organic group selected from the group consisting of, preferably an alkyl group having 1 to 8 carbon atoms; and p is 0, 1, 2, 3 or 4, preferably 0. Poly-C-
A non-limiting list of some nitroso compounds is:
Metadinitrosobenzene, Paradinitrosobenzene, Metadinitrosonaphthalene, Paradinitrosonaphthaline, 2,5-dinitroso-paracymene,
2-Methyl-1,4-dinitrosobenzene, 2-
Methyl-5-chloro-1,4-dinitrosobenzene, 2-fluoro-1,4-dinitrosobenzene, 2-methoxy-1,3-dinitrosobenzene, 5-chloro-1,3-dinitrosobenzene,
Mention may be made of 2-benzyl-1,4-dinitrosobenzene and 2-dichlorohexyl-1,4-dinitrosobenzene. Almost any polymer conventionally used as a film-forming material in adhesives can be used as an auxiliary film-forming material in the practice of this invention. Such film-forming substances include, but are not limited to,
Thermosetting condensation polymers such as thermosetting phenolic resins, thermosetting epoxy resins, thermosetting polyester resins, thermosetting thiazine resins; polymers and copolymers of polyethylenically unsaturated compounds such as polyvinyl butyral; polyvinyl formal;
Polyvinyl acetate; Chlorinated polyvinyl chloride; Vinyl acid/vinyl chloride copolymer; Chlorinated copolymer of vinyl acetate and vinyl chloride; Polyacrylic acid;
Copolymers of conjugated dienes such as 1,3-butadiene and acrylic acid; 2-chloro-1,3-butadiene; 2,3-dichloro-1,3-butadiene; and halides thereof; polymethacrylic acid; methacrylic Copolymers of acids and conjugated dienes;
Copolymers of vinylpyridine and conjugated dienes, and polyvalent reaction products thereof: cellulosic materials such as cellulose acetate butyrate, etc. are included. Particularly preferred film-forming materials are halogen-containing rubbers, including, without limitation, chlorinated natural rubber; polychloroprene; chlorinated polychloroprene; chlorinated polybutadiene; chlorinated polyethylene; chlorinated ethylene/propylene copolymer; /propylene/non-conjugated diene terpolymer; chlorinated butadiene/styrene copolymer; chlorosulfonated polyethylene; brominated poly(2,3-dichloro-1,3-butadiene); these halogen-containing rubbers and hypohalogenated rubbers and a mixture of halogenated hydrogenated rubber; two or more of such halogen-containing rubbers, and the like. Other suitable film-forming materials include cellulosic esters such as cellulose acetate butyrate; natural rubber; butyl rubber; ethylene/propylene copolymers (EPM).
Rubber; ethylene/propylene/diene terpolymer (EPDM) rubber; polymers and copolymers of dienes having 4 to 12 carbon atoms, such as polybutadiene, and one or more different dienes, such as PBR and butadiene/acrylonitrile rubber. Copolymers with monomers, etc. are included. As indicated, halogenated polymers, especially chlorinated and brominated rubbers, are preferred additional film-forming materials.
If additional film-forming materials are used, the relative proportions of these to the elastomeric copolymer will generally be from 10 to 90% by weight of the elastomeric copolymer and thus from 90 to 10% by weight of the additional film-forming material.
% by weight, preferably 80 to 10% by weight. The adhesive compositions of this invention may also contain fillers, extenders and colorants such as carbon black and various metal oxides. These fillers are inert in terms of their effect on the adhesive properties of the composition. Generally, the solids content of the adhesive composition is between 5% and 60%. One of the salient features of the aqueous adhesive composition of this invention
Good shelf life, ie good can stability. Another advantageous feature is that the composition of the invention does not lose its adhesive strength when applied to a substrate and left in the air for a period of time. Furthermore, the bond between the rubber and the substrate (with an adhesive between them) does not deteriorate even after prolonged exposure to air. The method of bonding natural and synthetic rubber to rigid or non-rigid substrates using the vulcanizable adhesives of this invention generally involves (1) forming a water-based adhesive composition as described above; Coat the substrate with a thin layer of (3)
Dry the adhesive coating by air drying or with slight heat in an oven; (4) contact the adhesive-coated substrate with a vulcanizable rubber; and (5) simultaneously apply the rubber. Consists of stages of vulcanizing the adhesive. The adhesive compositions of this invention can be made by conventional emulsification techniques, which need not be further explained here. The following examples were provided to illustrate the invention. All parts and percentages relating to compositions are by weight unless otherwise specified. The following examples were conducted using the test method shown in ASTM D-429, Method B, replacing 90° with 45°. That is, the adhesive strength of the adhesive between the rubber and the metal was tested by changing the angle at which the rubber piece was peeled from the metal plate from 90° to 45°. This is because the adhesive of the present invention can be evaluated more accurately in this manner. The adhesion force, ie the force required to peel the rubber from the metal surface, is expressed in kN/m.
The failure mode is indicated by the number indicating the area ratio (%) of the damaged part followed by R, RC, which indicates the type of failure, as stated in "ASTM D429 15. Terminology related to adhesive failure".
It is shown with symbols such as. For example 50R and 25RC
The area of damage at the rubber itself and at the boundary between the rubber and adhesive is approximately 50% of the total area.
and 25%. Also TR and VTR
This is a further classification of the mode of damage R, and indicates that thin rubber and very thin rubber remained on the metal surface from which the rubber was peeled off. The samples were also tested for resistance to boiling water by immersing them in boiling water for 2 hours. The peeling operation was performed by peeling the rubber off the metal with pliers immediately after removing it from the boiling water. The conditions of this test are more severe than those of the standard test in which the sample is peeled off after it has cooled to room temperature. When using a primer, the metal is first coated with the primer, allowed to dry, then coated with adhesive and dried again.
The elastomer was then brought into contact. If no primer was used, the metal was coated with adhesive and allowed to dry before being contacted with the elastomer. Preheat tolerance was performed by holding the adhesive coated substrate at the vulcanization temperature for the same amount of time as in actual commercial practice before contacting the adhesive with the rubber.
Standard adhesion tests were conducted on such adhesively bonded assemblies. Example 1 Preparation of a halogenated conjugated diene-monoalkenyl aromatic alkyl halide copolymer latex In the first reaction zone, 288 g distilled water, 27 g sodium dodecyl phenyl ether disulfonate anionic surfactant, 15 g ethoxylation Octylphenol nonionic surfactant, 0.9 g sodium bicarbonate and 1.8 g sodium pyrosulfite were charged and purged with nitrogen. In this reaction mixture
515 g of 2,3-dichloro-1,3-butadiene (halogenated conjugated diene) and 16 g of vinylbenzyl chloride (monoalkenyl aromatic alkyl halide) were added. The contents of the reaction zone were cooled to below 40°C and stirred well to form a pre-emulsion. The second reaction zone was charged with 72 g of distilled water and 1.8 g of ammonium persulfate, purged with nitrogen, and heated to a temperature of 40-45°C. The pre-emulsion in the first reaction zone is added to the contents of the second reaction zone while maintaining the reaction temperature at 40 to 45°C.
Addition was made at a constant rate over a period of 90 minutes. After adding the pre-emulsion, heat at 40 to 45°C for another 60°C.
Polymerization was carried out for minutes. The resulting copolymer latex had a ratio of halogenated conjugated diene to monoalkenyl aromatic alkyl halide of 95:5. The pH of the latex was adjusted to 6.8 with dibasic lead phosphate. The total solids content (TSC) of the latex was 43%. Preparation of 2,3-dichloro-butadiene-α-chloroacrylonitrile copolymer latex 6.9 g disodium dodecyl diphenyl ether disulfonate anionic surfactant, 4.6 g ethoxylated octylphenol nonionic surfactant in the reaction zone and 172 g of distilled water. The reaction area was purged with nitrogen and 129 g
2,3-dichloro-1,3-butadiene and
42g of α-chloroacrylonitrile was added. The resulting mixture was stirred well to form an emulsion. Add 0.5g of ammonium persulfate to this emulsion.
0.5g of sodium dithionite was added. The reaction mixture reached a temperature of 45°C due to its own exotherm. After the initial exotherm has ended, heat the contents of the reaction zone to 75°C.
Keep at 55°C for minutes. This reaction mixture was then added at a constant rate for 5 hours to (1) 74 g of disodium dodecyl phenyl ether disulfonate anionic surfactant, emulsified in 1828 g of distilled water; 49.1 g;
of ethoxylated octylphenol nonionic surfactant, 1420 g of 2,3-dichloro-1,3-
An emulsion consisting of butadiene and 465 g of alpha-chloroacrylonitrile and (2) an aqueous activator solution containing 8 g of sodium pyrophosphate, 4 g of ammonium persulfate, and 4 g of sodium pyrosulfite in 334 g of distilled water were prepared separately, but added at the same time. The reaction temperature was maintained at 55-60° C. during the addition of the comonomer emulsion and aqueous activator solution. After the addition was completed, the copolymerization reaction was carried out at 55°C for an additional 90 minutes. Next, 90 g of ethoxylated octylphenol nonionic surfactant containing 3.75 g of disodium dodecyl diphenyl ether disulfonate anionic surfactant and 2.5 g of ethoxylated octylphenol nonionic surfactant was added to the reaction zone at a constant rate for 45 minutes. 100 g of 2,3-dichloro-1,3-butadiene emulsified in distilled water was added. At the same time, at a constant speed,
0.6g sodium pyrophosphate in 25g distilled water,
A solution containing 0.3 g ammonium persulfate and 0.3 g sodium pyrosulfite was added to the copolymerization reaction zone. After the addition was complete, the copolymerization reaction mixture was heated and held at 55°C for 90 minutes. The ratio of 2,3-dichloro-1,3-butadiene to α-chloroacrylonitrile in the obtained copolymer latex is
It was 3.25:1. Example 2 The following adhesive compositions were prepared using a halogenated conjugated diene-monoalkenyl aromatic alkyl halide copolymer latex, a halogenated conjugated diene homopolymer latex, and a monoalkenyl aromatic alkyl halide homopolymer latex. All amounts herein are given in parts by weight based on dry weight.

Table: The adhesive composition was used to bond cold rolled steel to vulcanizable natural rubber and styrene-butadiene rubber, the surface of which had been wiped with organic solvent and grit blasted. Prior to applying the adhesive, the steel was coated with an organic solvent-based heat-reactive phenolic resin primer. The natural rubber assembly was vulcanized at 153°C for 15 minutes and tested for boiling water resistance. The synthetic rubber assemblies were vulcanized for 30 minutes at 153°C, with and without preheating for 10 minutes, and peeled and bonded using a method modified from ASTM D-420, B method at 45°. A force test was conducted. These results are shown in the following table. Natural rubber adhesive failure mode A 22R B 100R C 100RC D 98R

[Table] Example 3 The following adhesive was prepared using the latex of Example 1. All amounts are in parts by weight based on dry weight.

Table Contents This adhesive composition was used to bond cold rolled steel to vulcanizable natural rubber, the surface of which had been wiped with organic solvent and grit blasted. Prior to applying the adhesive, the steel was coated with an organic solvent-based heat-reactive phenolic resin plasmar. This assembly was vulcanized at 153° C. for 15 minutes and tested for boiling water resistance. The results are shown in the table below. Boiling water resistance (soaked for 2 hours at 100°C) Adhesive failure mode E 100R F 86R G 47RC H 20R I 0R Example 4 Monoalkenyl aromatic alkyl from 2,3-dichloro-1,3-butadiene and vinylbenzyl chloride Halide content is 5, 11, and 15, respectively.
and 22% halogenated conjugated diene-monoalkenyl aromatic alkyl halide copolymer latex was prepared according to the procedure of Example 1. Each latex was used to make an adhesive having the following composition. All amounts herein are given in parts by weight based on dry weight.

Table: The respective adhesives were used to bond cold-rolled steel, wiped with organic solvent and grit-blasted, to vulcanizable natural rubber and styrene-butadiene rubber. Prior to application of the adhesive composition, the steel was coated with an organic solvent-based heat-reactive phenolic primer or a water-based novolak phenolic primer. Natural rubber was vulcanized at 153°C for 15 minutes, both without preheating and with preheating at 153°C for 6 minutes. The synthetic rubber assembly was vulcanized at 153° C. for 30 minutes under the same preheating conditions. Both natural rubber assemblies and synthetic rubber assemblies
Peel adhesion tests were conducted using the ASTM D-429B method with a 45° variation. The natural rubber assembly was tested for boiling water resistance by soaking at 100°C for 2 hours. The test results are shown in the table below.

【table】

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[Table] Example 5 The following adhesive was prepared using the halogenated conjugated diene-monoalkenyl aromatic alkyl halide copolymer latex prepared in Example 1. Here, amounts are given in parts by weight based on dry weight.

Table: Cold rolled steel whose surface was wiped with organic solvent and grit blasted was bonded to vulcanizable natural rubber and styrene-butadiene rubber using the adhesive composition. Prior to applying the adhesive, the steel was coated with a water-based primer containing a thermally non-reactive phenolic resin and a resin hardener. The adhesive coated steel was preheated to 153° C. for 9, 12, or 15 minutes before contacting the vulcanizable rubber. The natural rubber assembly was vulcanized at 153°C for 15 minutes, and the synthetic rubber assembly was vulcanized at 153°C for 30 minutes.
These assemblies were tested according to ASTM D-429, Method B with a 45° modification. The results are shown in the table below.

【table】

【table】

[Table] Example 6 According to the method of Example 1, 2,3-dichloro-
A halogenated conjugated diene-monoalkenyl aromatic alkyl halide copolymer latex with a monoalkenyl aromatic alkyl halide content of 22% was prepared from 1,3-butadiene and vinylbenzyl chloride. The following adhesive was made using this latex. All amounts are given in parts by weight based on dry weight. Copolymer latex 100 Dinitrosobenzene 18 Total solids content (%) in water 43 This adhesive is used to coat grid-blasted cold-rolled steel with a variety of vulcanizable materials by wiping the surface with an organic solvent. Adhered to natural rubber and synthetic rubber. Prior to applying the adhesive, the steel was coated with an organic solvent-based heat-reactive phenolic resin primer. The assembly was vulcanized under conventional time, temperature, and pressure conditions. After vulcanization, the assembly
Only primary adhesion was tested according to ASTM D-429, Method B with a 45° variation. The results are shown in the table below.

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Claims (1)

[Scope of Claims] 1 (a) At least one copolymer obtained by emulsion polymerization of (a) at least one halogenated conjugated diene and (b) at least one monoalkenyl aromatic alkyl halide. (b) an anionic surfactant and a mixture of at least one anionic surfactant and at least one nonionic surfactant; 0.01 to 15% by dry weight, based on the total weight of the halogenated conjugated diene and the monoalkenyl aromatic alkyl halide;
a surfactant system, and wherein said copolymer has a monoalkenyl aromatic alkyl halide content of from 3 to 33% by weight, and wherein said copolymer has a monoalkenyl aromatic alkyl halide content of from 3 to 33% by weight, and said copolymer has a total solids content of from 3 to 33% by weight. The composition has a content of 5 to 70% by weight. 2 The monoalkenyl aromatic alkyl halide monomer has the general formula or (However, X is hydrogen, chlorine, bromine, or iodine,
R is an alkyl group having 1 to 4 carbon atoms, and 1 selected from the group consisting of chlorine, bromine, and iodine on the carbon atom directly bonded to the aromatic nucleus;
or those substituted with three halogen atoms,
The composition according to claim 1, wherein a is 1 or 2, b is 0, 1, or 2, and at least one b is at least 1. 3 The halogenated conjugated diene is 2,3-dichloro-
A composition according to claim 1, which is 1,3-butadiene. 4 The monoalkenyl aromatic alkyl halide is vinylbenzyl chloride, Claim 1
Compositions as described in Section. 5. Claim 3, wherein the monoalkenyl aromatic alkyl halide is vinylbenzyl chloride.
Compositions as described in Section. 6 The halogenated conjugated diene is 2,3-dichloro-
The composition according to claim 2, which is 1,3-butadiene. 7 Claim 2 in which the monoalkenyl aromatic alkyl halide is vinylbenzyl chloride
Compositions as described in Section. 8. The composition according to claim 1, which has a pH of 4 to 11. 9. The composition according to claim 2, which has a pH of 4 to 11. 10 Claim 5 in which PH is 4 to 11
Compositions as described in Section. 11. The composition of claim 2, wherein the monoalkenyl aromatic alkyl halide content in the copolymer is from 3 to 25% by weight. 12. The composition of claim 5, wherein the monoalkenyl aromatic alkyl halide content in the copolymer is from 3 to 7% by weight. 13 (a) (dry weight) consisting of at least one copolymer obtained by emulsion polymerization of (a) at least one halogenated conjugated diene and (b) at least one monoalkenyl aromatic alkyl halide; 100 parts by weight of an elastomeric latex; (b) an anionic surfactant and a mixture of at least one anionic surfactant and at least one nonionic surfactant; 0.01 to 15% by dry weight based on the total weight of the halogenated conjugated diene and the monoalkenyl aromatic alkyl halide
(c) at least one aromatic nitroso compound dispersed in at least 1 part by weight per 100 parts by weight of said copolymer solids; The copolymer has a monoalkenyl aromatic alkyl halide content of 3 to 33% by weight and a total solids content of the copolymer latex composition of 5 to 70% by weight. 14 The amount of aromatic nitroso compound is 1 to 200
14. The composition of claim 13 in parts by weight. 15 Monoalkenyl aromatic alkyl halide monomers have the general formula or (However, X is hydrogen, chlorine, bromine, or iodine,
R is an alkyl group having 1 to 4 carbon atoms, and 1 selected from the group consisting of chlorine, bromine, and iodine on the carbon atom directly bonded to the aromatic nucleus;
or those substituted with three halogen atoms,
15. The composition according to claim 14, wherein a is 1 or 2, b is 0, 1, or 2, and at least one b is at least 1. 16 Claim 1 in which the halogenated conjugated diene is 2,3-dichloro-1,3-butadiene
Composition according to item 5. 17. The composition of claim 15, wherein the monoalkenyl aromatic alkyl halide is vinylbenzyl chloride. 18. The composition of claim 16, wherein the monoalkenyl aromatic alkyl halide is vinylbenzyl chloride. 19 Claim 1 in which PH is 4 to 11
Composition according to item 4. 20 Claim 1 in which PH is 4 to 11
Composition according to item 5. 21. The composition of claim 15, wherein the monoalkenyl aromatic alkyl halide content in the copolymer is from 3 to 25% by weight. 22 Second claim in which PH is 4 to 11
Composition according to item 1. 23 The second claim in which the halogenated conjugated diene is 2,3-dichloro-1,3-butadiene
Composition according to item 2. 24. The composition of claim 22, wherein the monoalkenyl aromatic alkyl halide is vinylbenzyl chloride. 25. The composition of claim 23, wherein the monoalkenyl aromatic alkyl halide is vinylbenzyl chloride. 26. The composition of claim 18, wherein the monoalkenyl aromatic alkyl halide content in the copolymer is from 3 to 7% by weight. 27 Second claim in which PH is 4 to 11
Composition according to item 6.