EP0112391A4 - Stabile wässrige dispersionen härtbarer harzzusammensetzungen und aus diesen hergestellte klebe- und beschichtungszusammensetzungen. - Google Patents

Stabile wässrige dispersionen härtbarer harzzusammensetzungen und aus diesen hergestellte klebe- und beschichtungszusammensetzungen.

Info

Publication number
EP0112391A4
EP0112391A4 EP19830902388 EP83902388A EP0112391A4 EP 0112391 A4 EP0112391 A4 EP 0112391A4 EP 19830902388 EP19830902388 EP 19830902388 EP 83902388 A EP83902388 A EP 83902388A EP 0112391 A4 EP0112391 A4 EP 0112391A4
Authority
EP
European Patent Office
Prior art keywords
dispersion
percent
acid
resin
added
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19830902388
Other languages
English (en)
French (fr)
Other versions
EP0112391A1 (de
Inventor
Michael G Stevens
Rhetta Q David
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0112391A1 publication Critical patent/EP0112391A1/de
Publication of EP0112391A4 publication Critical patent/EP0112391A4/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers

Definitions

  • alkali metal hydroxides While all of the alkali metal hydroxides are useful, sodium hydroxide and potassium hydroxide are preferred.
  • the rubber mat was cut exactly 1/4 inch (6.35 mm) from the point of insertion of the tire cord just deep enough to cut the cord.
  • the mat was placed into an 110°C oven for 30 minutes and then the load necessary to pull the cord out of the rubber was measured for each individual cord. Adhesion was measured at 38.4 lbs/in (6720 N/m); adhesion for the control is 40.32 lbs/in (7061 N/m).
  • a vinyl ester base resin which was the reaction product of a 208 EEW resin (mixture of bisphenol-A epoxy resin and epoxy novolac), methacrylic acid, and maleic anhydride to 4.7 percent acid. That was heated to 70°C and 0.12 g of phenothiazine and 53 g of styrene were added. The mix was stirred for 1 hour and cooled to 40°C. Then 48.9 g of triethanolamine and 5.89 g of monobutyl ether of diethylene glycol were added and mixed well for 30 minutes.
  • a vinyl ester base resin which was the reaction product of a 208 EEW resin (mixture of bisphenol-A epoxy resin and epoxy novolac), methacrylic acid, and maleic anhydride to 4.7 percent acid. That was heated to 70°C and 0.12 g of phenothiazine and 53 g of styrene were added. The mix was stirred for 1 hour and cooled to 40°C. Then 48.9
  • Example 2 To a 1-liter, 5-neck, round-bottom flask, which was equipped as in Example 1, was charged 273 g of the dimethacrylate of a 361 EEW bisphenol-A epoxy base resin of that example. The resin was heated to 110°C and 11.9 g of maleic anhydride and 0.03 g of hydroquinone were added and reaction continued for 1 hour to an acid level of 2.2 percent. Then 0.06 g of oxalic acid dihydrate and 42.74 g of styrene were added. The mix was cooled to 70°C and 0.06 g of phenothiazine was added. After cooling to 50°C, dimethylethanolamine (15.02 g) was added and mixed well for 30 minutes. With stirring, 472 g of water was added at a rate of 15-20 ml/minute. The dispersion had a solids content of 35 percent and a particle size of 2240 A (224 nm).
  • a cord was first dipped into water to. ' saturate and then into the adhesive mixture described above. The cord was then placed into an oven to set the adhesive to the cord. Cure times and temperature are as shown in Table I. The pickup of adhesive onto the cord was
  • the commercial adhesive is a two-stage cure of 45 seconds at 300°F (149°C) and 60 seconds at 475°F (246°C).
  • Example 7 Using the same procedure as Example 7, a dispersion having the following composition was synthe ⁇ sized: the diglycidyl ether of that example (350 g, 1.8460 eq), hydroquinone (0.12 g), glacial methacrylic acid (158.76 g, 1.8460 eq), DMP-30 (0.53 g), maleic anhydride (48.62 g, 0.4961 eq) to give a percent COOH equal to 4.58, phenothiazine (0.08 g), 4-chloro-2- nitrophenol (0.11 g) dimethylethanolamine (60.61 g, 0.681 eq), and water (1150.5 g).
  • the percent solids was 29.0. Brookfield viscosity at 25°C was 1600 cps (1.6 Pa-s).
  • Example 9 Using the same procedure as in Example 9, the following dispersion was made: epoxy resin of Example 2 (228.6 g, 1.2057 eq), bisphenol-A (23.9 g, 0.2095 eq), Hycar* 1300 X 18 (67 g, 0.0944 eq), tetrabutylphosphonium acetate (0.44 g) hydroquinone (0.13 g), glacial methacrylic acid (79.22 g, 0.9212 eq), DMP-30 (0.36 g), maleic anhydride (38.13 g, 0.3891 mole), to give a percent COOH equal to 4.80, phenothiazine (0.05 g), styrene (77.3 g), dimethylethanolamine (49.88 g, 0.5604 eq) and deionized water (1186 g).
  • the final product contained o
  • Example 9 Using the same procedure as in Example 9, the following dispersion was made: epoxy resin of Example 7 (254 g, 1.3417 ⁇ eg), bisphenol-A (55 g, 0.4822 eg), tetrabutylphosphonium acetate (0.22 g), hydroguinone (0.09 g), glacial methacrylic acid (72.44 g, 0.8423 eq), DMP-30 (0.46 g), maleic anhydride (17.43 g, 0.1778 mole) to give a percent COOH egual to 2.5, phenothiazine (0.07 g), 4-chloro-2-nitrophenol (0.09 g), styrene
  • Example 7 epoxy resin of Example 7 (413.9 g, 2.183 eg), bisphenol-A (89.4 g, 0.784 eg), tetrabutyl- phosphonium acetate (0.35 g), hydroguinone (0.14 g), glacial methacrylic acid (119.98 g, 1.3951 eg), DMP-30 (0.75 g), maleic anhydride (59.61 g, 0.6083 mole) to give a percent COOH equal to 4.57, phenothiazine (0.11 g), 4-chloro-2-nitrophenol (0.15 g), styrene (76.0 g), dimethylethanolamine (71.67 g, 0.8053 eg), and water
  • the dispersion had a Brookfield viscosity at 25°C of 3040 cps (3.04 Pa-s) at 15 percent solids.
  • Example 2 Using the same procedure as in Example 1, the following dispersion was prepared: vinyl ester base resin of Example 1 (273 g), maleic anhydride (26.8 g) to give a percent COOH of 4.55, styrene (44.97 g), monoethyl ether of hydroguinone (0.11 g), phenothiazine (0.08 g), dimethylethanolamine (32.4 g) and water (480 g).
  • Example 6 Using the same procedure as in Example 6, the following tire cord adhesive formulation was prepared using the above dispersion (21.15 g); Cymel 303 (1.11 g); deionized water (32.92 g); and styrene/- butadiene/vinyl pyridine latex (15/70/15 weight percent) (12.02 g). A polyester cord was coated and tested by the method of Example 6. The adhesive was cured at 375°F (191°C) for 60 seconds. The resulting adhesion was 42.0 lbs/in (7360 N/m).
  • Example 6 Using the same procedure as in Example 6, the following dispersion was prepared: vinyl ester base resin of Example 1 (273 g), maleic anhydride (41.0 g), oxalic acid dihydrate (0.06 g), phenothiazine (0.06 g), dimethylethanolamine (43.47 g) and water (678 g).
  • Example 6 Using the same procedure as in Example 6, the following tire cord adhesive formulation was prepared using the above dispersion (27.57 g), Cymel 303 (1.2 g), deionized water (30.8 g), and styrene/butadiene/vinyl pyridine latex (15/70/15 weight percent) (12.93 g) .
  • a polyester cord was coated and tested by the method of Example 6. The adhesive was cured at 375°F _(191°C) for 60 seconds. The resulting adhesion was 48.3 lbs/in (8460 N/m). ' , " ' ⁇ ⁇
  • a polyester cord was coated and tested by the method of Example 6. Adhesive pickup was 5 percent. The adhesive was cured at 175°C for 10 minutes. The resulting adhesion was 40 lbs./m (7000 N/m).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Epoxy Resins (AREA)
EP19830902388 1982-06-28 1983-06-28 Stabile wässrige dispersionen härtbarer harzzusammensetzungen und aus diesen hergestellte klebe- und beschichtungszusammensetzungen. Withdrawn EP0112391A4 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US39296882A 1982-06-28 1982-06-28
US392968 1982-06-28

Publications (2)

Publication Number Publication Date
EP0112391A1 EP0112391A1 (de) 1984-07-04
EP0112391A4 true EP0112391A4 (de) 1984-10-16

Family

ID=23552748

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19830902388 Withdrawn EP0112391A4 (de) 1982-06-28 1983-06-28 Stabile wässrige dispersionen härtbarer harzzusammensetzungen und aus diesen hergestellte klebe- und beschichtungszusammensetzungen.

Country Status (2)

Country Link
EP (1) EP0112391A4 (de)
WO (1) WO1984000170A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004058909A1 (fr) * 2002-12-27 2004-07-15 Conception Et Developpement Michelin S.A. Composition adhesive pour le collage direct d'un composite polyester ou vinylester pregelifie a du caoutchouc cru
FR2872820B1 (fr) 2004-07-07 2008-09-05 Conception & Dev Michelin Sa Systeme adhesif pour le collage direct d'un polyurethane cuit a du caoutchouc cru
JP2015503661A (ja) * 2011-12-29 2015-02-02 ダウ グローバル テクノロジーズ エルエルシー 硬化性水溶性エポキシアクリレート樹脂組成物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE710257A (de) * 1967-02-22 1968-06-17
GB1146693A (en) * 1965-03-13 1969-03-26 Reichhold Chemie Ag Method for producing water-dilutable coating compositions based on epoxy resin esters
US3464939A (en) * 1966-02-22 1969-09-02 Shell Oil Co Process for preparing water-soluble epoxy resin esters
AU424518B1 (en) * 1966-07-05 1972-05-26 Dunlop Rubber Australia Limited Process for bonding glass to rubber
FR2171231A1 (de) * 1972-02-09 1973-09-21 Shell Int Research
DE2522329A1 (de) * 1973-03-21 1976-12-02 Dow Chemical Co Wasser-in-harz-emulsion
EP0060506A1 (de) * 1981-03-14 1982-09-22 Hoechst Aktiengesellschaft Mit Wasser verdünnbares Epoxyd, Verfahren zu seiner Herstellung und dessen Verwendung

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2615826A (en) * 1946-08-02 1952-10-28 Wingfoot Corp Article comprising cord bonded to rubber by a vinylpyridine adhesive
DE957884C (de) * 1952-05-03 1957-01-17 American Cyanamid Company, New York, N Y (V St A) Verfahren zur Herstellung von polyestergebundenen Glasfaserschichtstoffen mit erhöhter Haftfestigkeit der Kunstharzschicht auf Glas
US2772248A (en) * 1953-05-04 1956-11-27 Interchem Corp Water-soluble epoxy-amine resins
US2824851A (en) * 1953-08-24 1958-02-25 Minnesota Mining & Mfg Acrylic acid derivatives of epoxide resins and method of curing same
US3373075A (en) * 1961-12-18 1968-03-12 Robertson Co H H Diacrylate compositions, heat resistant polymers containing the same and method of making electrical laminates therefrom
US3317465A (en) * 1963-06-26 1967-05-02 Robertson Co H H Combination catalyst-inhibitor for betahydroxy carboxylic esters
US3367992A (en) * 1964-06-05 1968-02-06 Dow Chemical Co 2-hydroxyalkyl acrylate and methacrylate dicarboxylic acid partial esters and the oxyalkylated derivatives thereof
US3414432A (en) * 1965-10-04 1968-12-03 Exxon Research Engineering Co Sizing glass fibers with polybutadienedicarboxylic acid anhydride amino salt adducts
US3564074A (en) * 1966-11-28 1971-02-16 Dow Chemical Co Thermosetting vinyl resins reacted with dicarboxylic acid anhydrides
US3560237A (en) * 1968-04-15 1971-02-02 Weyerhaeuser Co Process of curing polymerizable resins having terminal vinyl ester groups using high energy electrons
US3634542A (en) * 1969-08-04 1972-01-11 Shell Oil Co Unsaturated polyesters esterified with polycarboxylic acid anhydride and containing polyepoxide
US3661576A (en) * 1970-02-09 1972-05-09 Brady Co W H Photopolymerizable compositions and articles
US3827230A (en) * 1970-04-13 1974-08-06 Owens Corning Fiberglass Corp Glass fiber size
FR2109065A5 (en) * 1970-08-14 1972-05-26 Showa Highpolymer Unsatd polyester resins - prepd by reacting a comonomer with a reaction product of an unsatd acid and an epoxy cpd
US3962165A (en) * 1971-06-29 1976-06-08 Ppg Industries, Inc. Quaternary ammonium salt-containing resin compositions
US3787224A (en) * 1972-04-24 1974-01-22 Owens Corning Fiberglass Corp Glass fiber reinforced elastomers
US3926886A (en) * 1974-03-27 1975-12-16 Esb Inc Epoxy resin-amine salt emulsion composition
US4212776A (en) * 1978-10-16 1980-07-15 Mobil Oil Corporation Self crosslinking water dispersible epoxy ester-acrylate polymers
US4347343A (en) * 1981-01-21 1982-08-31 The Dow Chemical Company Thickened vinyl ester resin compositions
US4355131A (en) * 1981-01-26 1982-10-19 The General Tire & Rubber Company Adhesion of rubber to glass fibers

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1146693A (en) * 1965-03-13 1969-03-26 Reichhold Chemie Ag Method for producing water-dilutable coating compositions based on epoxy resin esters
US3464939A (en) * 1966-02-22 1969-09-02 Shell Oil Co Process for preparing water-soluble epoxy resin esters
AU424518B1 (en) * 1966-07-05 1972-05-26 Dunlop Rubber Australia Limited Process for bonding glass to rubber
BE710257A (de) * 1967-02-22 1968-06-17
FR2171231A1 (de) * 1972-02-09 1973-09-21 Shell Int Research
DE2522329A1 (de) * 1973-03-21 1976-12-02 Dow Chemical Co Wasser-in-harz-emulsion
EP0060506A1 (de) * 1981-03-14 1982-09-22 Hoechst Aktiengesellschaft Mit Wasser verdünnbares Epoxyd, Verfahren zu seiner Herstellung und dessen Verwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8400170A1 *

Also Published As

Publication number Publication date
WO1984000170A1 (en) 1984-01-19
EP0112391A1 (de) 1984-07-04

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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Effective date: 19840224

AK Designated contracting states

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RIN1 Information on inventor provided before grant (corrected)

Inventor name: DAVID, RHETTA Q.

Inventor name: STEVENS, MICHAEL G.