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    • 专利摘要:
    1520974 Laminates HOHNY CHEMICALS CO Ltd 12 March 1976 [29 Aug 1975] 9256/76 Addition to 1520172 Heading B5N In a process for bonding rubber to a ferrous metal substrate, a copper layer is deposited on the substrate by an electroless or electrolytic process from a solution of a copper salt which does not simultaneously contain cupric and halide ions, an adhesive layer comprising an interpolymer derived from 40 to 99% by weight of at least one conjugated diene, 1 to 45% by weight of at least one vinyl-substituted heterocyclic base and 0 to 40% by weight of at least one additional copolymerizable monomer, contacting the adhesive layer with a curable rubber composition and uniting the assembly by the application of heat and pressure. Many suitable dienes and additional monomers are exemplified, the preferred heterocyclic bases being preferably of the pyridine, quinoline or isoquinoline series and containing only one CH2<C< substituent and -the rubber may be natural rubber, polybutadiene, polyisoprene, acopolymer of butadiene with acrylonitrile or styrene, or polychloroprene. The substrate may be in the form of wire, the process being applicable in the manufacture of steel reinforced tyres, belts and hoses.
    公开号:SU784788A3
    申请号:SU762334809
    申请日:1976-03-12
    公开日:1980-11-30
    发明作者:Ли Эди Деннис；Есида Синичи
    申请人:Хонни Кемикалз Ко, Лтд (Фирма)；
    IPC主号:
    专利说明:

    There is a known method of attaching rubber to metal by degreasing the metal surface, applying latex-based glue to copolymers of vinylpyridine and butadiene, followed by vulcanization. However, this method does not provide sufficient bond between rubber and metal. The purpose of the invention is to increase the bond strength. To achieve this goal, after degreasing, the metal surface is treated with a solution of copper salt selected from the group: sulfate, nitrate, formate, pyrophosphate, bromide chloride and put a layer of glue based on copolymer latex 55-99% by weight of diene with conjugated double bonds mi and 1-45 wt.% of the vinyl-substituted heterocyclic nitrogen-containing base or copolymer of the indicated monomers with an olefin in a ratio L of 50-98: 1-45: 1-40. When a copper coating is applied to an iron surface, it is wiped over the surface with water, then a second coating comprising a rubber-like copolymer of dienes with conjugated double bonds and heterocyclic nitrogenous bases is applied over this coating, such a combination of coatings in contact with compound unsaturated rubber forms a bond of unexpectedly high strength, especially at elevated temperatures, when vulcanizing unsaturated rubber. The said copper coating may contain salts of hydrohalic acid and / or copper or iron oxide or hydroxide. The combination of copper coating and copolymer adhesive reveals a definite and unexpected synergistic effect on strength. Bonds for a range of compounded rubbers. Preferred methods for producing these coatings from copper are the precipitation and electroplating from aqueous solutions of salts containing bivalent copper, especially in the presence of accelerating ions. The copper coating is formed on a metallic substrate of iron or steel by electrocoating or a chemical coating of an aqueous or non-aqueous medium of copper salts. Any of the methods can be used as long as the copper coating thus obtained has the metal and rubber indicated by the synergistic effect after combining VINILPYRIDIN M with the polymer Oss1 Expected. Solutions of copper salts, which can be used in the invention, are salts of divalent copper, selected from the group: copper sulfate (p), copper nitrate (p), copper formate (s), copper pyrophosphate (p), copper bromide { I) and chloride {1). The amount of the copper coating formed on the surface of the metal substrate varies depending on the type of anions present in the copper salt solutions, but, mainly, it is in the range from about 0.1 to 9.5 g / m. On the other hand, the polymers used in this invention are polymers of conjugated dienes with vinyl pyridines or their derivatives and, possibly, containing third polymerizable monomers. Copper coatings according to the proposed method are preferably applied using a chemical reduction or substitution reaction using an aqueous solution of divalent copper ion containing strongly accelerating halide chloride ions and bromide. Obviously, the presence of halide ions accelerates the rate of formation of the copper coating. There are many ways to apply copper to a metal surface. For example, using a chemical reduction or substitution reaction, the coating can be carried out from aqueous or organic solutions of copper salts. Also known is the method of electro-self-formation for the formation of a copper coating on a metal surface from solutions of copper salts. In the practice of the present invention, any of these methods can be used since o gives copper coatings similar to those obtained, for example, using a chemical reduction or replacement reaction from an aqueous solution of bivalent copper chloride. The processing time for obtaining the mentioned copper coating is preferably 0.5 - 60 s, but may be up to OD with or less. Depending on the type of anion in the aqueous solution of the salt of divalent copper, as well as the concentration, temperature and degree of stirring of the solution. As noted above, the preferred method of forming the copper coating is to apply the coating by chemical reaction to form or substitute a solution of chloride or bromide. Bivalent copper. Other salts, such as formic acid salts, acetates, nitrates, phosphates, sulfates, tartrates, borates, and the like. can be used in solution with the addition of haloscale ions accelerating deposition. As indicated above, coating with a chemical reaction can be carried out by dipping a l (iron product into a solution of two valence copper for a period of time from 0.1 to about 60 s.) Other conditions of this dipping stage, i.e. salts of divalent copper, solution temperature and the degree of mixing of the solution can vary widely to find the best results for any particular system. Usually a concentration of from about 1 to 10% can be used at temperatures from 15 to 40 ° C with stirring or without it. The time may be more than 60 s, but this is undesirable. The rubber-like copolymers of the diene with con is used as the adhesive are HL-S-IH double bonds with vinyl substituted, heterocyclic ocHOBaHHeEvi or the indicated copolymers with one additional copolymerizable with 1m monomer. These polymers used contain about 55-99% by weight of conjugated diene, 1-45% of vinyl-substituted heterocyclic base in the preferred embodiment 5-15 8es,% and from 1 to 4 About wt.% At least one to copolymerizable monomer. The amount of vinyl-substituted heterocyclic base in the copolymers is preferably maintained at 1-25% by weight. The conjugated dienes used in the present invention preferably contain from 4 to 6 carbon atoms in the molecule, inclusive, but dienes can also be used with a high content of carbon atoms in the molecule, for example 8. These compounds BK: hydrocarbons, such as 1,3-butadiene, isoprene, piperylene, methyl pentadiene, 2,3 dimethyl-1,3-butadiene, halohydrocarbons, such as haloprene: chloroprene, methylchloroprene and other alkoxycarbons, such as metoxy and ethoxy derivatives of these dienes with sopr nnym double bonds, in particular 2-and Z-metoksibutadien-ethoxy-1, 3-butadiene. The polymerized vinyl-substituted heterocyclic bases used in the process according to the invention are bases from the pyridine, quinoline and isoquinoline series. which are copolymerized with dienes, contain Aa1 1IMI conjugated double bonds, and contain one and only one CH2 C substituent, and preferably this group is CHj ,. Q. where Fs2 is either hydrogen or a methyl group. In other words, the substituent is either a vinyl, lib-methylvinyl (isopropenyl) group. Preferred of these compounds are pyridine derivatives. Various other substituted derivatives can also be used, but the total number of carbon atoms in the nucleus of substituted groups, for example alkyl groups, should not exceed 15, since the polymerization rate decreases slightly with an increase in the value of the alkyl group. Compounds in which the substituents of alkyl are methyl and / or ethyl are available in bulk and are preferred; in the present invention. These heterocyclic nitrogen bases have the formula a KB. R r ... r 4x r lu. R and where R is selected from the group consisting of hydrogen, alkylvinyl, cC-methylvinyl, alkoxy, halo, oxycyano, aryloxy, aryl groups, and combinations of these groups, for example, haloalkyl, alkylaryl, oxyaryl, and the like. one and only one of the mentioned groups is a group of type CH2 C, which in the preferred embodiment is a vinyl or ci-methylvinyl group, and the total number of carbon atoms in the cores of the replacement groups does not exceed 15. As noted preferred groups are those in which The x R groups, in addition to the vinyl or cC-methylvinyl group, are hydrogen or alkyl with 1-4 carbon atoms. Examples of such compounds are; 2-vinylpyridine; 2-vinyl-5-ethylpyridine; 2-methyl-5-vinylpyridine; 4-vinyl pyridine; 2,3,4-trimethyl-5-vinylpyridine; 3,4,5, b-tetramethyl-2-vinylpyridine; 3-ethyl-5-vinylpyridine; 2, 6-diethyl-4-vinylpyridine; 2-isopropyl-4 "-ionyl-5-vinylpyridine; 2-methyl-5-unde cycl-3-; vinylpyridine; 2-decyl-5- (methylmethyl) pyridine; 2-vinyl-3-methyl-5-ethylpyridine; 2-methoxy-4-chloro-6-vinylpyridine; 3-wines Ja1-5-ethoxypyridine 2-VINIL-4,5-dibromopyridine; 2-vinyl-4-chloro-5-bromopyridine; 2- (ob-methyl VINIL -) - 4-hydroxy-b-dianopyridine; 2-vinyl-4-phenoxy-5-methylpyridine; 2-cyano-5- (oL-methylvinyl) pyridine; 3-vinyl-5-phenylpyridine; 2- (p-methylphenyl 3-vinyl-4-methylpyridine; 3-vinyl-5 (hydroxyphenyl) pyridine; 2-vinylquinoline 2-VINYL-4-ETHILHINOLIN; 3-vinylb, 7-di-n-propylquinoline; 2 -methyl-4-nonyl-b-wikylquinoline; 4 (o-methylvinyl) -8-dodecylquinoline; 3-vinylisoquinoline; 1,6-dimethyl-3-vinylNisoquinoline; 2-vinyl-4-benzylquinoli, n 3 "gchininyl- 5-chloroethylquinoline; 5-vinyl-5, b-dichloroisoquinoline; 2-vinyl-b-ethoxy-7-methylquinoline; 3-vinyl-b-hydroxymethyl isoquinoline; and so on. Copolymers can be prepared from a mixture of two previously mentioned dienes with conjugated double bonds and vinyl-substituted heterocyclic or from a conjugated diene and two different vinyl-substituted heterocyclic bases. However, it is more common practice to prepare copolymers from a single diene with conjugated double bonds, one vinyl-substituted heterocyclic base and at least one polymerizable monomer (olefin The last monomers include organic compounds containing at least one polymerized ethylene group of type C C C. These compounds are well known in the art and include, for example, alkenes, alkadienes, and styrene such as, for example, ethylene, propylene, 1-butylene, 2-butylene, isobutylene, 2-octene, 1,4 pentadiene, 1, b -geksadien, octa 1,7-diene, vinyl toluene, zinilksilol, ethylvinylbenzene, vinilkumol, 1, 5-tsikloaktgschien, cyclohexene, cyclooctene, benzilstiren, chlorostyrene, bromstiren, ftorstiren, triftormetilstiren, iodostiren, tsianostiren, nitrostyryl, N, N-dimethylaminostyryl , 3-phenyl 3 butene-1-ol, p-methoxystyrene, vinylnaphthalene, acentoxystyrene, methyl 4 vinyl benzoate, phenoxystyrene, p vinylphenylethyl ether and the like; acrylic and substituted acrylic monomers, for example methyl acrylate, ethyl acrylate, methyl methacrylate, methacrylic anhydride-. reed, acryl phenyl tetracrylate, - chloroacrylonitrile, ethyl methacrylate, butyl methacrylate, metal etacrylate, methacrylamide, M, M-dimethyl-acrylag. id, N, N-dibenzylacrylamide, N-butyl acrylamide, methacryl-formamyl, acylamine, methacrylamide, etc. Vinyls, Vinyls, Vintages 1-fluoroethylene, vinylidene fluoride, vinyl methyl ether, vinyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxy 3 ethyl ether, B4P |. } :: loai ether, 3,4-ditpch draw i. . 2 - darkness; 2 -Butoxy 2 -butoxyethyl efnrg vinyl 2- these / shlerkaptoe silov th: ether ,. WC-Vincel ethyl ketone, vnilFeNILKeTONG VINILZ: GI; TSU, m & gT): U (. Ii l
    Egilsulphoy, M - zin1, U1G1CHO; h about / liapp. ;; - - fii-methyl I M - ziil 11, vgam.1ts. ij-ti: nn, r
    Rolidon BHHHJ HMtiri; a3O, 7I;. DIVINIASU: 1: FFEDG DIVIISH; SULFOXID,. DIVINL-1RG:; -; - 77Bon, natrniv-kilkulsulfoia1 .; IU; with g ..: ii-. nylsulfonat.N vinylpyrrol to CHP.,; dimeRi.psut zhrat, vinyl isocyanate, tatratratrarchttt-zlen, chlorotrnfluoroethnl.en, kitroelkh-Lzy: vinylfuran, Binilcarbazol. nniadetilen etc.
    The function of the additional monomer (olefin) is to improve the technological properties of 1 {le .. An example may be used as such;:; et1 - ms; ipt:; oo ::, for example, nitriles esters amide
    and ToP., which will be knotted for 1: 1 for: the relevance of a class, business from more than a year ;;.); mastess with; DejHHaMsi) r-pg Onost,
    Koglpauk, zirovayng 1a to l; /; :: and, s; // 1z :: vyavie uiaeannetli sog ol / eagchi. include natural :: c: -i: getically rubbers to MX cm €: si, i-: yvia o; iiHe sufficiently high csviavib 1: .e; ac; ta; asn -1ost1-; :; .. viHai-; VsyM about 70 mol. Prialeramk a -; -, synthetic rubber rub; la ;; chg:, polybuta yen, polyisoprene, aor: c: ia measures butadiene with dtireyy kl1; ap: - lonitrilom polychloroprene and x. ,
    These rubbers are usually compted-unnilialit (filled) alone or near KanojiHia t &amp; le -, layer ;;; shI ator; -E to /:; ; oats
    ditch and aat -; - uska:;. p ;; l. -gley, Sgbsche -.- a :: :: ische; ;: - Auemo:: h r-: an: -; a; U-j,;, ir ..;
    OUT OF IT IS S O6 L 1 SL::: 3 A.OS weight. h. ia 100 carried „h. Ca.uch .... ilano :; Ngtel gli rgazlipada lal-Chs be,. llyn; Kpr5o; a.1 calcium .t calcium;. titanium bluokhgs and samsa. In order to obtain 1;: o; u1oundcroa -.kogo raw materials, used in the production of WKSI, preferably f h / gobk, at least part of the filler was sanna. i.I.r; ac-. snnnkator ac use c: ;; o-.: icheotve::. and 1 to 100, plasti-KH-iaTopa on 100 rubber. 1l:, - 1, amount of plastic ;; az .; h:; ia Sudet depend on the required a irjeKTa softening; Examples of irnssiOn, :: platyfnkatorov are aromatic Essential oils, petroleum rasters; -an1ie asfalgen, nitrogen bases, coal tar products, coumarone. smokhsh and ethers, and-Apr; er dibutyl phthalate and
    It is clear that n-type mixtures of these plasticizers can be used. The substances used in the system of vulcanizers insert a zero: a substance is a substance and usually one head
    Not only are vulcanization accelerators combined with caustic or a number of accelerator activators. The number used in this case is that HPPK materials usually fall into the following ranges: 0.5--5.0 ec. .u.a, :: -:;: for: ora, 0.5-3.0 f ----; c, 4. accelerate tel: -;,. 0, weight, h, akTMHciiijpa ycKOjpiiT; :: l h to the calculation of the JUS h, - kauchuks :, Gr-i; .-:;: DJuviM is suitable for Zulka.niators of sulfur, Her society. ; vdell; o1; -1e sulfur B in a free state; Naprchchmer Tytra11etnltiuramudsulf: hell, pE: 1; -tzs ltiurg1 /: full sulfide or,: KH); fao.; 1s: y: a1: feed; t - ;; jw peroxide, naprimar l aaa;: l: G1 tsyk / tach or re;; -; ls D1-T;:;: -::; pla When using as:; peroxidation improvers, accelerator and accelerator; ;:: Often, they are unnecessary., E ;; aches 7ve of the Vulcacizacite-g accelerators; v - o / vr: -; use dithiocarbacatil; atraststiltiuramsulfyd V mercapts on estisol, Examples of chopsg; -. :: aea of ikky- fitsin; Katsaazm - ;;.:; .. Lch a :; ; - -. A /:. vulcanization to it, ppl; : .a .a.: 3ta, pdithiocarbamate, N.N aiuiavii a-; - o.pei- - butalsulfenyldithiocoamam:, l aarah -atil uramdrsulfide,.,. , c: aan: .10thiaz1-: 7 ansulfide, butyral .cyagada :: ijHH.i merx.ptobenzothiazole.
    1J- -aj; a: -; - Э7 a, :: 5; u: Zanzothiazols lfi - cuv ,, H; a;:. ./- a.ajai -. ;;;;; :: - ;:; - 2-ben zotiazlsulf; aa: hell i Cha.cai :. ; / a, eaibi9 npL-; kompau .aispoi-aHvL-i n -.a ai ..; a ;; tviB iTopa accelerator .-; -.-; teria.1, .1 ;;:, tt; och from oxides of metal,. pag: .rm; a; p Osis zinc, oxide 1gni and glt, which are as follows; tani: with acid and acid, eg de; / avipHKiiviH kis; lots - stearic acid, oleic acid 1i-c; / oy, myristic acid t. ji. B k.chestaa about: l; ole -; mate; al ;:. so; ka can P1 ;; And;.; en resins; i: i acid, an antioxidant in compounding i; e ;; i, er: T usually but in amounts varying from about 0, 5 to 3 ,, About weight.h, ka 100 weight.h. rubber Examples for; suitable 1-oxidizing agents in the form of fekyl-E-naphthylamine, di-tert-buty-Hydroquinone, 2,2,4-Tg) Hmethyl 6-phenyl 1,2-dihydroquinoline, a physical mixture from the co-E-product of the reaction of diarylamine ketone, I and I and I and I and I and I and I. ;; phenylenediamine and m, p. All of this is inevitable to limit the image, but not a recipe, but as a result::., And :: it is widely applicable to iici: anan-diene with conjugation t-iu, ;;:. connection &amp; Shg sggolg-gmernyk vT-afV :::; -; a / -; l :: ameshte; heterogeneous heterocyclic ;: oga; cHODaH5j i for fastening ШКpOiavaTi, - and alazon are co-hounded: to: y: vinegar; E cast iron or steel povarnosg m.,,
    Processing of C plus glue on the pre; alaeglesmu method gives good performance; aa xalez: stalgnyh and cast iron .iT,.; : a garhnost l;,. which are defatted 1;: free from all adherent films, preferably by etching. The treated glue and the surface of the adhesive are applied in any known manner, for example, dipping, brushing, dusting, etc., followed by rapid drying at room temperature or applying heat to remove solvents and / or water. The compounded raw rubber is then contacted with the surface of the glue and the entire product is vulcanized with heat and pressure to complete the bonding process. It is understood that the invention is not limited to any particular compounding rubber recipe, for it is widely applicable to a wide range of compound rubber formulations giving high bond strength, due to the processing of Cu on a metal surface, followed by a conjugated diene copolymer and vinyl substituted heterocyclic base. The properties of copolymer glue, such as tackiness, hardness and resistance to oxidation, can be modified by adding one or more combinations of plasticizers, fillers and antioxidants before application to the metal surface. Example 1. A. Steel round wires (, 96 mm) were degreased with a solvent, etched for 20 s in concentrated hydrochloric acid at 55 ° C, washed. in water, immersed first, for 5 s in 5% aqueous solution of cupric chloride, washed in water and then dipped in polymer latex from butadiene, styrene, 40 2-vinylpyridine (composition 70: 15: -15 wt.%, 12% solid resin; the adhesive latex 1) and finally dried at 170 s for 60 s. Then, the coated wires thus coated were vulcanized in the H test form under a pressure of 60 kg / cm at the times and temperatures indicated for these rubber formulations. Vulcanized samples were subjected to relaxation (sedation) for 24 hours at room temperature, then they were kept in an oven at 120 ° C for 20 minutes, and then tested at 120 C. The H test used in this and other examples was performed by vulcanization covered wires under pressure of 60 kg / cm in the center of two blocks of rubber with a width and length of 2 cm and a thickness of 1 cm. The distance between the blocks is 2.5 cm; The wire goes Q in each block to a depth of 2 cm, the total length of the wire is 6.5 cm. The blocks were broken by moving along the wire axis with a Speed of 200 mm / min until j on kly would shchi in. on both sides of the cable (with G15, the wires were not pulled from one of the blocks. The sample obtained according to the proposed method was compared with those obtained by scientists who studied under similar conditions, while in one case they were poisoned, in the other, they poisoned and dug copper, but did not use it, and in the third case, the wire was treated and coated with glued latex (1, but did not have first copper coating. Compound No. 1 of rubber, by weight; Natural rubber 100 Soot ON Sulfur 5 Pine tar3 Stearic acid 1 p - Phenylnaphthylamine 1 Zinc oxide 8. 2-Mercaptoben otiazol 1.5 total: 169.5 A TM 330 is highly abrasive to the pelage, vulcanization time, min ZO temperature of vulcanization, C 135 words / h Coupling (adhesion) 1Г / СМ% Etched wire 5 Etched wire and copper coating 12 Etched wire and glued latex № 110 Etched wire and copper coating, and bonding latex No. 1 56 B. Steel round wires were greased in a solvent, electrolytically rubbed through for 5 seconds in 25% sulfuric acid at room temperature and at a density of 0.5 A / cm, washed in water , ruzili in water solution. chloride of compliant meth. and washed with iodine and ryol gluing latex No. 2, becoming: butadiene, 2-vinylpyridine 85: wt.%, 12% solid gums) dried 120 ° С for 45 s and the rubber formulation No. 2 was repeated. Rubber formulation No. 2. wt.h .: Natural rubber 100 Soot NAG50 Sulfur5 Pine tar; 3 stearic acid 1 b - “Phenylnaphthylamine 1 cobalt naphthenate 2.5 Zinc oxide8 2-Mercaptobenzothiazole 1,5 Total: 172, O vulcanization time, min thirty
    Name
    Table 2
    Synthetic Rubbers
    Example 3. Steel round wires were treated as in Example 1A, except that coupling latices were used with varying amounts of vinylpyridine; glue-coated wires, vulcaniiziro-gluing latex, monomer weight,%: 1,3-Butadiene 2-Vinylpyridine
    the rubber tubs of recipe No. 1 were dried for 60 s (Table 3), and the glue-coated wires cured by the rubber of the W 2 recipe were dried for 45 seconds with abl. four),
    Tablea
    100 99 95 90 85 80 75 70 O15 10 15 20 25 30
    Adhesion kg / cm
    Etched wire.
    Etched wire
    and copper coating
    Etched wire
    and bonding latex
    Etched wire
    copper coating and
    bonding latex
    Note.
     Checkpoints.
    In the above experiments, a glueing latex was used to control..., No. 4, which did not contain vinyl pyri, comprised from about 1 to 25% by weight.
    Adhesion, kg / cm D20 ° C
    Etched wire etched wire and copper coated} 1e etched wire and / adhesive latex etched wire, copper coated and glued latex
    Checkpoints.
    As a control, gluing latex No. 10, not containing vinylpyridine, was used. For this range of latexes, the range of optimal contents is about 1 to 35% by weight.
    Example 4. This example excludes the use of different copolymers as glue in the invention.
    Adhesion kg / cm
    74
    39
    Continued table. 3
    -
    7
    6
    12 16
    15 17
    16 15
    12 10
    ten
    44
    50
    44
    32
    15
    dina. Optimal range containing vinylpyridine for this range of latexes
    Table4
    12
    15
    41
    54
    50
    25
    Steel round wires were processed as in Example 1A, except that gluing latexes with varying amounts of butadiene and styrene were used; the glue-coated wires were dried at 120 ° C for 45 s and attached to rubber # 2.
    59
    45
    45
    20
    PRI me R 5. Steel round wires were treated as in Example 1A, except for the fact that in the resin of the bonding coating it was used adhesive, kg / cm 2-120 ° C
    PRI me R b. Carried out the method of example 1 using rubber formulation No. 1 and bonding latex W 2 with varying time of dipping
    Duration of immersion in a 5% CuCI solution, with
    The results of the I-test, kg / cm, at 120 ° C. EXAMPLE 7 Example 6 was repeated, except that the following solutions and times of immersion were used instead of immersion in a 5% CuCl solution. Duration of immersion, min. Concentration of aqueous 5% CuVga solution
    various monomers were cast; the coated wires were dried for 45 seconds and attached to rubber 2.
    Table
    52 55 73 48
    50
    wire in a solution of divalent copper chloride.
    Received the following results, presented in table.7. Table7
    ten
    44
    46
    52 Immersion duration, with Result of the H-test kg / cm at 120 ° C. EXAMPLE 8 Example 7 was repeated using the following solutions of copper salts and immersion times for compounding rubber No. 2 and gluing latex No. 3. Use the same methods. coating and drying as in example 7. The results are presented in Table 8. Table 8 Example In this example, the use of electroplating as a means of depositing copper layers in accordance with this application is illustrated. Steel bead wires were degreased with a solvent etched for 20 s in concentrated hydrochloric acid, washed in water, and purified in water using ultrasound. Electro precipitation is carried out in an aqueous solution of 1% w / v of CuCl, at a pH of up to 10 with ammonia. At a current density of 1 A / dm, a deposition was obtained for 15 s using copper anodes (Component 0.1 g of copper per 1 m of the wire surface. The coated wires were washed in water, dried, and dipped in adhesive latex No. 1 of Example 1 and then dried at 120 ° С for 15 s. The treated wires were vulcanized with rubber mixture No. 1 for 30 min at IBSC. Experimental results: Experimental adhesion force kg / cm 2, 120 Wire etched 7 Wire etched and electrodeposited copper 15 Etched wire and adhesive latex № 117 Prot Avlena wire, electrodeposited copper and adhesive latex 60 Example A. Steel bead wires (sis-SWRH72A, d 0.96 mm) were covered with solvent, etched for 20 s at 55 ° C in concentrated hydrochloric acid and washed in water. Then, to form a copper coating (2 g / m.), On their surfaces the wires were immersed in an aqueous solution of copper nitrate (P) (with a RP value of 1, attained by nitric acid) and washed in water. The thus treated wires were then immersed in 1,3-butadiene, 2-vinylpyridine, styrene polymer. latex (hereinafter referred to as latex No. 1, composition 70: 15: 15, 12% by weight of solid resin) and dried for 45 seconds and vulcanized in Nt test form for a certain time and at a certain temperature under a pressure of 60 kg / cm with the composition of saturated rubber specified in table 1. The samples were aged for 24 hours at room temperature after vulcanization, then they were heated and tested at 120 ° C. 1 filled rubber composition, parts by weight: Natural rubber 100 HA F Black 50 Sulfur 5 Pine resin 3 Stearic acid Phenyl-b-naphthalene Zinc oxide 2-Mercaptobenzthiazole Vulcanization time, min 30 Vulcanization temperature, ° С 135 Composition of polymerization, parts by weight: 1 , 3 Butadiene Stzrol 2-Vinylpyridine Sodium lauryl sulfate Sodium pyrophosphate Dodecyl mercaptan Potassium peroxide water (stretching rate 200 mm / min) to determine their adhesion strength. For control instead of coated bead wires were used: 1) wires that were only pickled; 2) wires, which were coated with copper salt after etching according to the indicated technology; 3) wires that were coated with the specified polymer latex after etching, and then vulcanized with the same saturated rubber. Polymer latex was obtained from the above polymerizable mixture, which was loaded into a 1 liter autoclave under nitrogen atmosphere with stirring at 50 ° C for 30 h (polymerization yield 98%). All polymer latexes that were used in the following examples were prepared in the same way, except for changes in the composition of the monomers. The test results of the communication strength are presented below. B. Steel bead wires (s.isSWRN.-72A, d 0.96 mm) were degreased in a solvent, electrolytically etched for 5 s at room temperature in 25% sulfuric acid (current density 0.5 A / CNT) washed in water and immersed in a 5% aqueous solution of copper sulphate (i), - pH 2 was adjusted with sulfuric acid (to form a 0.2 / m copper layer) on their surfaces. After washing in water, the wires were immersed in 1, 3-butadiene, 2-vinylpyridine polymer latex (composition 85: 15.12% by weight of solid gum, hereinafter referred to as latex No. 2) and dried at 120 s for 45 s. The coated wires were vulcanized in an N-test form for a certain time and at a certain temperature under a pressure of 60 kg / cm with the composition of saturated rubber shown below. Vulcanized samples were aged for 24 hours at room temperature. ExperienceCommunication force, kg / cm. Example 11 A70 Control (1) 5 Same (2) 12 (3) 10 2 composition of filled science, weight. h : Natural rubber100 NA F Black50 Sulfur5 Pine resin3 Stearic acid1 Phenyl-fb-naphthalene-1 Zinc oxide8 2-Mercaptobenethiazole1,5 Cobalt naphthenate2,5 Cure time, min 30 Cure temperature, from 135 then heated and tested n 120s la 200 mm / min) for determination with a bond in them. Dtt control instead of coated combat wires were used: 1) wires that were only pickled; 2) wires that were coated with copper salt after etching according to the technology described above; 3) coated wires, as described above, with polymeric latex after etching, which were then vulcanized with the same composition of saturated caoutchouc. The results of the test force of communication Evaluation Communication strength, kg / cm Example 11 B65 Control (1) 10 Same (2) 17 (3) 19 V. Steel bead wires (s SWRH-72A, 96 mm) were degreased with a solvent, etched for 20 seconds at 55 ° C in concentrated hydrochloric acid and rinsed in water. In order to form a copper coating of 1.0 g / m, the wires on the surfaces of the wires were electrolytically coated (current 1 A / dm in the coating bath ( pH 9.0.25 ° C) with 14 g / l copper pyrophosphate, 120 g / l potassium pyrophosphate and 10 g / l potassium oxalate, after which the coated wires were immersed in latex No. 1 {12 in a resin solids) and drained for 45 seconds at. Covered side
    100 100 100
    Natural Rubber Polybutadiene Isoprene Rubber
    100
    100 100 100
    100 100
    1-00 the wire was vulcanized in the H-test form for a certain time and at a certain temperature under a pressure of 60 kg / cm with a composition of 1 filled rubber. The vulcanized samples were aged for 24 hours at room temperature, then heated and subjected to tests at 120 s (the stretching rate was 200 mm / min) to determine their bonding forces. For control, instead of the coated side wires used above, were used: 1) wires that were only pickled; 2) wires that were electrolytically coated with copper after etching according to the technology described above; 3) wires coated only with the same polymer latex after etching were vulcanized with a composition of 1 saturated rubber. Results of bond strength tests. Experience. Communication strength, kg / cm Example 11 B 67 Control (1) b Same (2) 11 (3) 9 EXAMPLE 11. Steel side wires (sis -, SV; Ril - 72A, d 0.96 .mm) were degreased in a solvent, etched for 20 s at 55 ° C in concentrated hydrochloric acid and washed in water. Then the wires were immersed in a 10% aqueous solution of copper nitrate (li) p 1 was installed by using nitric acid to form layers of copper (2 g / m) on their surfaces and prom. in water. Thus, the treated wires were dipped: 1 - latex K-1 (12% by weight of solid resin) or 2-latex No. 2 (12% by weight of solid resin) and lowered for 45 s at 120 ° C. The coated bead wires were vulcanized in the H-test form for a certain time and at a certain temperature at a pressure of 60 kg / cm from 11 compositions of the nascent rubber presented in Table 9. Vulcanized samples were aged for 24 hours at room temperature, then heated and tested at 120 ° C (stretching rate 200 mm / min) to determine their bond strength. - T a b of l and c 9 Butadiene-styrene rubber Mrs black 50 50 HAF black 2 Silica Hi-Si C 233 Bentonite Activated clay Sulfur Coarse resin Stearic acid Antioxidant D Cobalt naphthalate Zinc oxide Vulcanization accelerator. (11 D control instead of boron The wires used were 1) wires that were only pickled, 2) wires that were processed after pickling salt of copper using the described technology, C) wires that were coated in coated polymeric latex (No. 1) after pickling, and 4) wires, cat were etched after etching with latex No. 2 and were vulcanized with each of the eleven compositions of saturated rubbers, represented by lennuch in Table 17. Example 12 A ". Steel 6opTa wire (-5N4RD-72A ,, 96 mm) was degreased in a solvent , etched for 20 s at 55 ° C in concentrated hydrochloric acid and washed in water. Then they were dipped in a 10% solution of copper (P) nitrate (pH 2 was adjusted with nitric acid) to form a copper coating of 2 g / m on their
    Continued table. 9 70 40 30
    1,3
    155
    thirty
    48
    51
    five
    12
    eleven
    9 0. 5 0 surfaces and washed in water. Ta-, KIM-treated wires were immersed in polymer latexes (see tablo.), Having different compositions and 12 wt. % solid resin and dried in those 1 45 s at 120 C. Coated bortovka wires vulcanized in the H-test form for a certain time and at a certain temperature under pressure of 60 kg / cm with a composition of 2 "filled rubber. The vulcanized images were aged for 24 hours at room temperature, then heated and tested at 120 ° C (cKOpoc-tb stretching was 200 mm / min) to determine their strength. For control, instead of coated side wires, wires were used that were only coated with one of the latexes (Table 10) after etching (without treatment with copper salt) and were vulcanized with a similar composition of saturated rubber. B. The process of Example 10A was repeated, 15 except that the polymer latex was
    PRI me R 13. The process of Example 10A was repeated, except that the composition of the polymer latex was changed in accordance with Table 12.
    The test results of the coupling strength are also given in Table 12.
    Composition, wt.% 1,3-Butadiene Isoprene 2-Vinylpyridine
    Spreadsheet
    PRI m e r14. The same process as in example 10 A was repeated, except that the composition was changed in accordance with the data table. 13.
    Table 13 also shows the results of the test of communication strength.
    Table 12
    T a b l and c a 13
    80 174
    80 15
    80. changed in accordance with the table. 11. In the same table 11 shows the results of tests of strength. t a b l and c a li
    4-Zinylpyridine
    2-Methyl-5-vinylpyridine
    Styrene
    Methyl methacrylate Acrylonitrile Coupling strength, kg / cm Example 14 Control
    5% copper sulphate (11) + sulfuric acid wire (5- (5 -svyW- 72 A, d 0.96 mm; were degreased in a solvent, etched for 20 s at 55 ° C in concentrated hydrochloric acid and washed in water They were then immersed in each of the aqueous solutions of copper salts {Table 14) to form layers of copper on their surfaces. After washing in water, the wires were immersed in latex 2 (12%,
    Continued table. 13
    15 5
    10 16
    66 15
    55 9
    68 10
    61
    Table 14
    45 seconds at 120 ° C. The coated bead wires were vulcanized in H-test form for a certain time and at a certain temperature under a pressure of 60 kg / cm with a composition of 2 filled rubber. The vulcanized samples were aged for 24 hours at room temperature, then heated and tested at a temperature of 120 ° C (tensile rate 120 mm / min) to determine their bond strength.
    Table 14 also shows the relationship between the amount of copper coating and the strength of the bond.
    For control, instead of wires coated in accordance with the present invention, wires were used that were only pickled, treated with a salt of copper and vulcanized with the same composition of filled rubber.
    Example 15 B. Steel bead wires (S i.s-SWRH-727, d 0.96 mm) were degreased in a solvent, washed in those for 30 seconds with concentrated hydrochloric acid and washed in water. Then they were subjected to electrocoating in a bath (pH 9.0–26 ° C) containing 14 g / l pyro () copper osfate, 120 g / l potassium pyrophosphate: and 10 g / l potassium oxalate. After washing in water, the thus-treated wires were immersed in latex 2 (12% w / w solid resin) and dried for 45 s at 120 ° C. Pokytye side wires were vulcanized: in H-test form for a certain time and at a certain temperature under a pressure of 60 kg / cm-2 with a composition of 2 filled rubber. The vulcanized samples were aged for 24 hours at room temperature, then they were heated and tested at 120 s (stretching rate 200 mm / min) to determine their bond strength.
    Table 15 shows the relationship between the amount of copper deposition and the strength of the bond.
    T a b l and d a .. 15 Example1bA. Steel bead wires (sis -SV / RH-72A, d 0.96 mm) were degreased in a solvent, etched for 20 s at 55 ° C in concentrated hydrochloric acid, and washed in water. They were then immersed in a 10% aqueous solution of copper nitrate UH ph 1 installed using nitric acid to form copper coatings of 2 g / m. After washing in water, the wires were immersed in latex No. 2 (12% solid resin) and dried for 45 s at 120 ° C. Thus, the treated volcano E1 wires were formed in an H-test form for a certain time and at a certain temperature under a pressure of 60 kg / cm with a composition of 2 filled rubber. Vulcanized samples were aged for 24 hours at room temperature and were tested for heat aging.
    In this test, the samples were aged in a constant air bath () for certain times, and 1 were taken out to be cooled. They were also heated and tested (stretching rate was 200 NtM / min) to determine their bond strengths.
    For control, samples were prepared by vulcanizing brass-coated tire cords above with filled rubber. They were subjected to similar tests.
    5 for heat aging.
    The results are shown in table. T a blitz -16
    I The power of communication
    Example
    20 j Jpeam (: tars, h
    25
    Example 16 B. The process of Example 1BL was repeated, except that the following changes were made:
    1) an aqueous solution of copper nitrate
    0 was changed to a 5% aqueous solution of copper sulfate (P), pI 2 was set-up with sulfuric acid (precipitation I; di: 0.6 g / m;
    2) latex 2 was replaced with latex
    5 -1
    -L;
    3) Composition 2 of the filled rubber was replaced with the following composition.
    12 composite rubber composition, Natural rubber SBR HAF black Sulfur Stearic acid Zinc oxide Treated oil Disulfide benzothiazine The results obtained are presented in Table. 17. Table 17. Thus, the proposed method provides: high bond strength; high bond strength at elevated temperatures;
    d / ital preservation of such high strength at elevated temperatures;
    the possibility of widespread use of natural and synthetic rubbers and formulations that can be linked;
    manufacturability of the process.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of attaching rubber based on unsaturated rubber to metal by degreasing the metal surface, applying latex based glue, applying rubber compound and vulcanizing, characterized in that, with the purpose of increasing bond strength, after degreasing the metal surface is treated with a solution of salt, copper selected from the group : sulfate, nitrate, formate, pyrophosphate, bromide, chloride, and glue based on copolymer latex 55-99 wt.% diene with conjugated double bonds and 1-45 wt.% vinyl-substituted heterocyclic nitrogen-containing appropriate base or sopolimerukazannyh monomerov- with an olefin in the
    the ratio, respectively. 50-98: 1-45: 1-40.
    Sources of information taken into account in the examination 1. US Patent No. 2978377,
    cl. 161-217, pub. 1961 (prototype).
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    同族专利:
    公开号 | 公开日
    SE431097B|1984-01-16|
    ES445979A1|1977-06-01|
    FR2322010A1|1977-03-25|
    BE839548A|1976-07-01|
    DE2610487C2|1982-06-03|
    FR2322010B1|1982-11-05|
    NL7602622A|1977-03-02|
    US4096009A|1978-06-20|
    SE7602909L|1977-03-01|
    BR7601523A|1977-09-13|
    CA1068179A|1979-12-18|
    JPS5431514B2|1979-10-08|
    JPS5228580A|1977-03-03|
    DE2609956A1|1977-03-10|
    IT1058413B|1982-04-10|
    DE2610487A1|1977-03-10|
    ZA761580B|1977-03-30|
    GB1520974A|1978-08-09|
    引用文献:
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    DE963094C|1949-09-16|1957-05-02|Gen Tire & Rubber Co|Process for the production of an adhesive for rubber on metal|
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    DE102010014258A1|2010-04-08|2011-10-13|Benteler Automobiltechnik Gmbh|Method for connecting a rubber bearing or a rubber-metal bearing with a bearing receptacle|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP10468675A|JPS5431514B2|1975-08-29|1975-08-29|
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