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    • 专利摘要:
    1470666 Adhesive coatings UNIROYAL INC 14 Feb 1974 [15 Feb 1973] 6688/74 Heading B2E [Also in Divisions C3 and Dl] An article is coated with an adhesive coating by contacting the article with a first dip (1) followed by a second dip (2), or with a single dip (1.2) comprising the components of (1) and (2), where (1) contains a compound of a metal (M) mixed with a liquid carrier (C) containing the reaction products of (A) a polyepoxide and (B) Ar(NCO) n , [Ar(NCO) n ] m , or Ar(NHCOX) n , and where (2) contains a phenol-formaldehyde solution (P) and a rubber latex (R). Metal (M) is Na, K, Rb, Cs, Sr, Ag, Cd, Ba, Ce, U, Ti, V, Cr, Sn, Sb, Mn, Fe, Co, Ni, Cu, Zn, Pb, Bi, Ca, or Zr; and 1000g of the composition comprises 0.00001 to 0.01 moles of the metal compound. Polyepoxide (A) has m.p. <150‹C, av, MW, <3000, and epoxide equivalent <2500. In (B), Ar contains #1 aromatic nucleus, X is aryloxy, arylthio, iminoxy, or lactam-N-yl; and m and n are each #2. (A)/(B) wt. ratio is from 0.01 to 5.0. Carrier (C) comprises 0.05- 15.0% wt of solids (A) and (B). Rubber latex (R) is of natural rubber, SBR, or butadiene-vinylpyridine-styrene rubber. The presence of the metal compound improves the appearance-rating in a hot-strip adhesion test. The article may be of polyester, e.g. as cord, film or fabric. In the coating process, (A) and (B) may optionally be applied separately in either order to the article, and may be in the same or different liquid carriers. Dips (1) and (2), and optionally (A) and (B) + carriers, may be made up in single or multiple packs.
    公开号:SU722489A3
    申请号:SU741999903
    申请日:1974-02-14
    公开日:1980-03-15
    发明作者:Джеймс Келли Роберт；Миллер Роберт；Джордж Адамс Дэвид
    申请人:Юниройял, Инк. (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to an adhesive composition that is used to join molded polyester (polyester based) products with articles made of rubber compositions.
    The invention is intended for the manufacture of products comprising a layer of molded polyester glued with a rubber base, such as driving belts, conveyor belts, fabrics with an insulating coating, and the like.
    Rubbers that are bonded to laminated polyester products are conventional cured sulfur-unsaturated rubbers.
    Polyester products include condensation polymers of dihydric alcohols with dibasic acids, in particular with dicarboxylic acids, and polymers obtained by the condensation of hydroxycarboxylic acids, for example polyethylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate. The polymers can be, for example, in the form of fibers, yarns, fabrics, tapes, fiber tapes and films.
    Rubber latex adhesive compositions, such as vinylpyridine and resorcinol-formaldehyde resin 1, are known for attaching polyester materials to Rubbers.
    However, the known compositions do not provide a sufficiently high bonding strength.
    Closest to the invention of the technical essence and the achieved result is a glue composition comprising a vinyl pyridine rubber latex, resorcinol form hygienic resin, methylene bisphenylene diisocyanate, formaldehyde, epoxy resin and water 2.
    This composition also does not allow for a high holding strength.
    The purpose of the invention is to increase the adhesion strength.
    The goal is achieved by the fact that a composition known to contain latex vinylpyridine rubber, resorcinol formaldehyde resin, methylene bisphenylene diisocyanate, formaldehyde, epoxy resin, water, additionally contains a compound to a metal selected from the group consisting of sodium, potassium, rubidium, strontium, and adhesives, as an example, strthystroms, adhesives, adhesives, strongholds, cesium, cesium, rubidium, epoxy, water, and barium, cerium, uranium, titanium, vanadium, chromium.
    tin, antimony, manganese, iron, cobalt, nickel, copper, zinc, lead, bismuth, calcium and zirconium, and the compound is selected from the group including acetate, acetylacetonate, stearate, oxide, chloride, nitrate, ethylhexoate, malate, o-phenylphenol t and oleate ,. in the following ratio of components, wt.% (calculated on the dry matter):
    Vinylpyridine latex
    10.68-11.2
    rubber
    Reeorcinformalde0, 84-0.97
    hydna resin
    : Methylenebisphenylene0, 57-0.71
    isocyanate
    0.46-0.53
    Formaldehyde
    0.23-0.30
    Epoxy resin
    0.003-0.00
    Metal compound
    Rest
    Water
    When using an adhesive composition, it can be used in the form of two liquid compositions I and I, which are applied to polyester materials sequentially, or the molded polyester product can be brought into contact with a single liquid containing components of the liquid G and liquid P.
    Liquid I contains a metal compound in a mixture with water containing epoxy resin, having on average at least two epoxy groups .. in Each molecule, so pl. below 150 C, the average mol. weight is below 3000, and the epoxy equivalent is below about 2500; and isocyanate. Water is an inert substance at room temperature (for both components) or it can be a solvent for one or both components; in addition, both or one of the components may be suspended in water as a dispersed or emulsified phase (suitable surfactants are used if desired).
    The amount of metal-containing compound added is 0.00001-0.010 mol per 1000 g of adhesive composition; however, it is necessary that the result is an adhesive bond between rubber and polyester that has at least a 5% improvement on external evaluation (for example, 2.5% less protruding cord than when the metal is not added to the glue) when measurements are made using the procedure described in Example 1 below. You can get an external rating of 5 for combining polyester rubber without using the metal compounds of the invention, but this will require a relatively high total amount of solid components in the adhesive and / or working temperatures. tures, adverse polyester for strength, both of which are undesirable and
    expensive. By adding a metal-containing compound according to the invention to an adhesive, external evaluation 5 can be achieved by using the same adhesive composition containing significantly less solids.
    The following molar intervals were determined for the preferred metal compounds listed in the list: cadmium 0.00010 O, 00400; copper 0.00002-0.00189; zinc: 0.00002-0.00185; silver .0,000460, 004000; manganese 0.00005-0.002. All values given above are expressed in moles per 1000 g of solution.
    The liquid formulation T is applied to the polyester molded article by any Conventional methods, for example, dipping, spraying, brushing, priming, or the like, the article may be in a state of relaxation or stress. When the molded article is a fiber in nature, it is preferable to subject it to at least sufficient voltage to prevent wrinkling during wetting and subsequent curing operations.
    The metal-containing compound, epoxy resin and isocyanate must be applied to the polyester article prior to the curing step.
    The components of the liquid formulation P, if a two-stage treatment process is used, are a resorcinol-formaldehyde solution in combination with a vinyl pyridine rubber latex.
    After the polyester article is in contact with the liquid I, the coated article is heated; it is produced up to 171-246 ° C for 20-200 s, preferably 204-232 ° C.
    The coated polyester article is brought into contact with liquid II.
    The polyester treated with liquid P is then heated at 177-232 ° C to 60200 s, preferably 199 and 21b-C to 80-100 s.
    Some excipients can be introduced both in the first and in the second liquid, or in both.
    The metal-containing compound must be introduced into the liquid I when using a two-stage immersion system. If the metal-containing compound is introduced into fluid P, there is no noticeable increase in cross-linking.
    Adhesion can be increased by using a one-time immersion system, but this is not the preferred method. As noted, if a one-time pouring system is used, all the above-mentioned components of the first and second liquids are combined in one container and the molded product is treated with glue and is obtained at least {calculated on dry matter) relative to the product. Then the product is n 177-232; preferably 199-21b with 80-100 s under voltage. Example 1. The use of glue and retention for joining a polyester tire cord with rubber when using a double immersion system. Twisted 3440 denier polyether (polyethylene terephthalate) tire cord consisting of three layers of cord, treated with liquid 1 having the following composition, g: Methylbisbisphenylene diisocyanate-22, 0 Aerosol FROM (dioctyl. Sodium sulfosuccinate) 1.5 Epone 812 (epoxy resin) 1.5 Epon 812 (epoxy resin) 1.5) 0 Water 1200 Metal-containing compound CM The dry residue in the cord after this first immersion is 0.5-1.5% (by weight of the cord). The cord is then cured at 40 seconds with a stretch of 2.0%. Then the cord is treated with liquid II (RFL-liquid)., Having the following composition, g :. Vinylpyridine latex (40%, consisting of terpolymer 70% butadiene, 15% vinylpyri dan and 15% styrene) piratex 100 Ammonium hydroxide 2.5 Table.1 Condensation product of resorcinol with formaldehyde (Coppert Penacolite 2170) 9.0 Formalin (37 %) This composition is diluted with water to 20% concentration. Then the cord is dried and cured at 90 s. The percentage of dry matter from RFL remaining on cordb is 2.5-4.9 by weight of cord. The amount of adhesion is assessed by the method of peeling a glued product. The separated surfaces are examined by considering how much cord becomes visible due to the separation of the rubber from the cord. Evaluation is based on the following scale: Evaluation Destruction pattern - External damage -% damage - type of surface -% visible rubber cord Consequently, the very high rating of the scale shows that the adhesive bond is so strong that the rubber billet is drying out; the very low rating of the scale indicates that the adhesive bond is weak, damage occurs in the intermediate surface of the rubber billet and cord, more than in the rubber molding itself. Table 1 lists the amounts of compounds of metals added to the liquid composition I described above; it also provides an assessment of the appearance. Tab. ita 1
    O, 00029 tetraisopropyl orthotitanate 0.00071 vanadium trisacetylacetonate 0.00071 chromium acetylacetonate 0.00051 bismuth nitrate 0.00097 bisacetyl acetonate nickel 0.00297 potassium chloride 0.00032 cadmium nitrate 0.00043 2-ethylhexoacetate of cobalt 000084 bicamide of one of the neutral quantires; dibutyl tin maleate 0.00038 o-phenylphenol sodium 0.00015 oleate divalent tin
    4.5 4.9 4.0 5.0 5.0 4.3 4.7 4.9 4.5 4.7 4.8 4.0
    The concentration of the metal of the village of rust "his c) lineage, mol per 1000 g of adhesive composition
    0.00023 zinc acetate
    0,00046-0, 00091-0, 03640-0,00016 zinc stearate
    0,00088 zinc acetylacetonate
    0.00014- -.
    0, H0034 zinc nitrate
    0.00020 uranyl nitrate 0.00035 bivalent nitrate
    0.00025 zirconium acetylacetonate
    0.00017 bis- (tri-butyltin) axis
    0,00026 lead acetate
    0,00052 iron acetate
    0.00038 copper acetylacetonate
    0,00034 cobalt nitrate
    0,00135 gooxies
    0.00028 iron acetylacetonate
    , 00246 zinc oxide
    0.00040 cypbNW trifluoride
    (bivalent)
    0,00114 rubidium nitrate
    0.00092 silver nitrate
    0,00121 strontium acetate
    0,00113 cesium nitrate
    0,00114 barium acetate
    0,00113 cerium nitrate
    Experiments have shown that by adding a metal-containing compound to the adhesive in accordance with the invention, a significant increase in adhesion is obtained, as follows from a comparison of the estimates of the appearance of the surfaces after the destruction of the samples.
    Example 2. The use of the adhesive composition of the invention for its component
    Vinylpyridine latex
    (piratex) 100100
    Ammonium hydroxide 2,52,5
    7224898
    Continuation of table 1
    Appearance
    Sample
    Control
    4.5 4.8 5.0 2.5 4.4 4.6 5.0 4.7 4.0 4.4 4.3 4.5 4.2 3.8 3.8 4.0 3, 5 3,6 4,6
    4.5 2.5 4.3 2.0 2.0 4.0 4.1
    Polyester tire cord with rubber using a single dip system.
    3440 Denier Twisted Three Layer
    The polyester tire cord described in example 1 is treated with core A, and the identical cord is treated with composition B, cocTaBtii compositions are shown in Table 2.
    table 2
    Content, g in composition
    The total dry matter content of cord adhesive is 4.5-5%. Then the cord is cured 90s at 199 C. Evaluation of the destruction of the samples in appearance with composition A 3.0, composition B 3.5.
    Component
    Methyl bisphenylene diisocyanate
    Aerosol OT Epon 812 Water
    Zinc Acetate
    权利要求:
    Claims (2)
    [1]
    Zinc stearate In vul x per 1000 g of co. The dry matter content after treatment of the cord is 1.501, 75%. The cord is cured for 40 s at 210 ° with a voltage of 2.0%. The cord samples are treated with the second immersion liquid described in Example 1, dried and cured at 90 s. Solid components from RFL remain on the cord in the amount of 4.0–4.25%. The results of testing the samples are given below. Sample with Composition Evaluation of Destruction by Appearance 2.0 4.6 5.0 5.0 5.0 Claims of the Invention Glue composition for bonding polyester materials containing 72248910
    Continuation of table 2
    Example 3. Samples of a three-layered 3440 denier polyester tire cord. treated with one of the following liquids I, the compositions of which are given in table. 3
    Table3
    in composition
    one
    d
    0,00009 0,00450
    0.0003 itii. vinylprida rubber latex resorcinol-formaldehyde resin, methylene bisphenylene diisocyanate, formaldehyde, epoxy resin and water, characterized in that, in order to increase the adhesion strength, it additionally contains a compound of a metal selected from the group including sodium, potassium, rubidate, and tide, ian, i), adhesion strength, additionally contains a compound of a metal selected from the group comprising sodium, potassium, rubidium, including tide, and adhesion. , silver, cadmium, barium, cerium, uranium, titanium, vanadium, chromium, tin, antimony, manganese, iron, cobalt, nickel, copper, zinc, lead, bismuth, calcium and zirconium, and the compound is selected from the group comprising acetate acetylacetate tension stearate, oxide, chloride, nitrate, ethylhexoate, maleate, o-phenylphenol, m and oleate, when sleduyusootnoshenii komponentevi weight%. based on dry substance):
    Latex vinylpyridine rubber 10,68-11,24
    Resorcinol formaldehyde resin 0.84-0.97
    Methylenebisphenylene diisocyanate, 57-0.71
    formaldehyde0.46-0.53
    Epoxy resin 0.23-0.30
    Compound metal 0,003-0,006 Water Else
    Sources of information taken into account in the examination
    .one. Kardashov D.A. Synthetic adhesives. M., Himi, 1976, p. 380.
    [2]
    2. US patent No. 3307996, cl. 117-76, published. 03/07/67
    (prototype).
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    同族专利:
    公开号 | 公开日
    BE811041A|1974-08-14|
    FR2217397A1|1974-09-06|
    USRE29699E|1978-07-11|
    US3903332A|1975-09-02|
    TR19302A|1979-01-01|
    DE2407408A1|1974-09-05|
    AU6557574A|1975-08-14|
    CA997630A|1976-09-28|
    BR7401084D0|1974-09-10|
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    JPS5046783A|1975-04-25|
    FR2217397B1|1978-05-05|
    GB1470666A|1977-04-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2795515A|1953-08-11|1957-06-11|Permacel Tape Corp|Pressure sensitive adhesive tape and method of making same|
    US3417069A|1963-10-10|1968-12-17|Wyandotte Chemical Corp|Polyhalogenous epoxy copolymers|
    US3307966A|1963-10-29|1967-03-07|Du Pont|Shaped structures treated with polyepoxide and polyisocyanate for improving adherence to rubbers|
    US3579490A|1964-08-31|1971-05-18|Ashland Oil Inc|Method of producing resins for use in adhesives|
    ES344146A1|1966-08-17|1968-11-01|Shell Int Research|Rubber articles reinforced with fibrous polylactones|
    DE1719096B2|1967-10-31|1976-11-04|Beiersdorf Ag, 2000 Hamburg|PROCESS FOR THE PRODUCTION OF SELF-ADHESIVE TAPES OR FILMS|
    US3539443A|1968-10-10|1970-11-10|Eastman Kodak Co|Laminates of oxidized epoxy resins with linear thermoplastic polyesters or polyamides and methods of making same|
    US3578614A|1968-10-21|1971-05-11|Grace W R & Co|Alpha-hydroxy-carboxylic acids as curing rate accelerators for curable polymer systems|
    US3628991A|1969-01-21|1971-12-21|Johns Manville|Method of bonding epoxy resins to polyvinyl chloride|
    US3740366A|1969-04-28|1973-06-19|Rohm & Haas|Pressure sensitive adhesive containing carboxylic acid groups and polyvalent metal|
    US3628992A|1969-12-03|1971-12-21|Ashland Oil Inc|Bonding of rubber to fibrous reinforcers|
    US3642937A|1969-12-22|1972-02-15|Minnesota Mining & Mfg|Sealant having epoxide encapsulated by aminoplast shell and polymeric binder|
    US3740414A|1970-06-05|1973-06-19|Minnesota Mining & Mfg|Composition of matter|
    US3753755A|1971-04-26|1973-08-21|Minnesota Mining & Mfg|Sheet material coated with heat hardenable tacky adhesive|DE2739949A1|1977-09-05|1979-03-15|Uniroyal Inc|Polyester-rubber bonding agent for tyre cord, etc. - includes metal cpd. which is added to a polyepoxide-poly:isocyanate reaction mixt.|
    WO1979001013A1|1978-05-01|1979-11-29|Minnesota Mining & Mfg|Cross-linked pressure-sensitive tape adhesive of a copolymer of alkyl acrylate and copolymerizable acid|
    JPS5531307U|1978-08-18|1980-02-29|
    US4397985A|1980-04-04|1983-08-09|Allied Corporation|Polyester yarn finish composition|
    FR2501700B1|1981-03-16|1985-08-09|Michelin & Cie|SULFUR VULCANIZABLE RUBBER COMPOSITIONS|
    US4680346A|1985-12-13|1987-07-14|Ppg Industries, Inc.|Flexible primer composition and method of providing a substrate with a flexible multilayer coating|
    US6780922B2|2002-01-17|2004-08-24|Honeywell International Inc.|Adhesion promoters with epoxy-reactive groups|
    WO2004058909A1|2002-12-27|2004-07-15|Conception Et Developpement Michelin S.A.|Adhesive composition for the direct joining of a pre-gelled polyester or vinyl ester to raw rubber|
    US20040245670A1|2003-06-03|2004-12-09|Janssen Robert A.|Method of forming a low tack elastomeric article|
    US20040262546A1|2003-06-25|2004-12-30|Axel Thiess|Radiation protection material, especially for use as radiation protection gloves|
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    US10364375B2|2010-06-14|2019-07-30|Gates Corporation|Article with self-bonding fully cured elastomer|
    US10005935B2|2015-05-01|2018-06-26|Lord Corporation|Adhesive for rubber bonding|
    CN112049278B|2020-09-04|2021-08-03|瑞洲建设集团有限公司|Waterproof building external wall heat insulation structure and construction method thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05332833|US3903332A|1973-02-15|1973-02-15|Adhesion of polyester to rubber using an adhesive containing added metal compounds|
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