[go: up one dir, main page]

WO1996014360A1 - Vesicules d'ester epoxy et peintures - Google Patents

Vesicules d'ester epoxy et peintures Download PDF

Info

Publication number
WO1996014360A1
WO1996014360A1 PCT/US1995/013877 US9513877W WO9614360A1 WO 1996014360 A1 WO1996014360 A1 WO 1996014360A1 US 9513877 W US9513877 W US 9513877W WO 9614360 A1 WO9614360 A1 WO 9614360A1
Authority
WO
WIPO (PCT)
Prior art keywords
paint
epoxide
lipid vesicle
latex
vesicles
Prior art date
Application number
PCT/US1995/013877
Other languages
English (en)
Inventor
Donald F. H. Wallach
Rajiv Mathur
Original Assignee
Micro-Pak, Inc.
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 Micro-Pak, Inc. filed Critical Micro-Pak, Inc.
Priority to AU39695/95A priority Critical patent/AU3969595A/en
Publication of WO1996014360A1 publication Critical patent/WO1996014360A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/10—Dispersions; Emulsions
    • A61K9/127—Synthetic bilayered vehicles, e.g. liposomes or liposomes with cholesterol as the only non-phosphatidyl surfactant
    • A61K9/1271—Non-conventional liposomes, e.g. PEGylated liposomes or liposomes coated or grafted with polymers
    • A61K9/1272—Non-conventional liposomes, e.g. PEGylated liposomes or liposomes coated or grafted with polymers comprising non-phosphatidyl surfactants as bilayer-forming substances, e.g. cationic lipids or non-phosphatidyl liposomes coated or grafted with polymers

Definitions

  • the present invention concerns a new type of vesicles having an epoxy ester as the major wall component.
  • These vesicles can be used in a variety of products but have particular usefulness in paints, coatings and adhesives.
  • Using the vesicles of the invention it is possible to have a water-based latex paint which hardens into a polymer when drying rather than merely an aggregated film. This latex paint is shelf stable in a single container and only polymerizes upon application and drying.
  • Epoxies have been used for many years in the adhesive and paint fields. Epoxies are all based on the epoxide ring, which has the following structure:
  • This epoxide ring has bond angles which average sixty degrees (60°), considerably less than normal tetrahedral carbon angle of 109.5°, or the divalent oxygen angle of 110°.
  • This three membered ring is highly strained so the bonds open easily, causing the epoxide to have high reactivity.
  • Epoxides can under go acid catalyzed reactions, base catalyzed cleavage, and a variety of other reactions. When an epoxide such as a bw-phenol epoxide is reacted with an acid bearing material such as carboxylic acid, it can polymerize and crosslink to form polymers.
  • a familiar form of epoxides is the two-part epoxy resin often used as an adhesive.
  • the epoxide and hardener are both stable when kept separate but upon mixing, the polymerization reaction takes place and the epoxy readily hardens into a solid. Those who have worked with epoxies know the rapid speed and hard bond that can be formed with this process.
  • Latex paints have some advantageous properties as compared with the alkyd or oil based paints, particularly in terms of their water solubility and ease of clean up. However, this same water solubility can be a problem. For many industrial applications, the fact that the latex is water soluble is detrimental since weathering or water under high force under water can cause the latex to deteriorate. This is particularly important in covering metallic, as compared to wooden, structures since the latex can not form as strong a bond with the metal surface as it can with wood. In practice, the latex is painted or coated on to the surface and then allowed to dry, forming a film on the surface.
  • an object of the invention is to provide a unitary product having both a latex paint and a harder or polymerization agent which will form a latex polymer.
  • Another object of the invention is to provide vesicles having an epoxide delivery system.
  • a further object of the invention is to provide a method of forming a unitary product containing both latex and a polymerization agent.
  • the present invention features lipid vesicles having an epoxy as the primary wall material, preferably encapsulating an epoxide which can act as an hardener or polymerization agent. These vesicles have primary use in the paint field but also are advantageous in the manufacture and use of other polymers such as polyurethane, polyacrylics, and different types of coatings.
  • the lipid vesicles of the invention have an epoxy ester as the primary lipid of the bilayer.
  • the vesicles have an epoxide encapsulated therein.
  • the epoxy ester wall is not reactive with the epoxide and acts as a barrier against the release of the epoxide.
  • the preferred vesicles are paucilamellar vesicles which have an amorphous central cavity surrounding 2-10 lipid bilayers, so that substantially all of the epoxide (which is water immicible) is segregated in that amorphous central cavity.
  • the preferred epoxy esters are esters of C12-C20 f attv acids, and mixtures thereof.
  • Preferred epoxides include those with a phenol derivative, preferably bw-phenol epoxide compounds.
  • a secondary surfactant such as sodium lauryl sulfate or ammonium lauryl sulfate helps to provide stability to the vesicles.
  • the epoxide containing lipid vesicles are used as a "hardener" in a paint having a hardener and a paint base.
  • a latex most preferably a latex being substantially free of ammonium ions, is used as the paint.
  • ammonium ions to neutralize the acid in the latex appears counterproductive because ammonia (in equilibrium with ammonium ions) can penetrate the vesicle membrane, allowing ammonium ions to react with the epoxide and inactivating the system during storage.
  • an ammonium lauryl sulfate could be used as the secondary surfactant in the vesicle, its use is contraindicated with a latex paint in the present system.
  • the paint is shelf stable, and can be spread on a wall or other area, whereby the latex and the hardener will combine, and react only upon drying. It is believed that the vesicles desiccate and fracture upon drying, thereby releasing the epoxide, which then reacts with the latex to form the latex polymer.
  • vesicle could be used in an adhesive system whereby the fracture of the vesicle allows one part of a two-part epoxide adhesive to mix with the other while segregating the components before mechanical stress or drying frees the reactants.
  • This technique can also be with other polymerizable materials such as urethane monomers.
  • the present invention provides both epoxy ester lipid vesicles as well as a paint or coating made therefrom. These epoxy ester lipid vesicles allow the formation of a unitary latex-epoxy paint, a paint which can be kept in a single container until use. It is only upon drying of the preparation and fracture of the vesicles that the polymerization reaction occur.
  • the vesicles are made of an epoxy ester resin solution, an epoxide, a secondary surfactant, a neutralizing agent (if necessary), an anti- foaming agent (if necessary), and deionized water. These vesicles are made using procedures similar to those described in United States Patent No. 4,911,928 and United States Patent No. 5,160,669, the disclosures of which are incorporated herein by reference. Briefly, the epoxy ester and the epoxide are heated together to flowability, e.g., a temperature of approximately 75°C.
  • the aqueous phase which contains water soluble materials such as the secondary surfactant, e.g., sodium lauryl sulfate, a neutralizing agent if needed such as ammonium hydroxide or sodium hydroxide, and any anti-foaming agent, all dissolved in deionized water, is then heated to the temperature slightly below that of the epoxy ester/epoxide phase.
  • the phases are blended using a shear mixing device such as the NovaMi ⁇ TM lipi vesicle maker from IGI, Inc. or a homogenizer until a vesicular product with a thin, lotion-like consistency is achieved.
  • the vesicular product can then be stored as is or mixed with a paint or other material.
  • the following reaction sequence is believed to generate the polymer.
  • the b/s-phenol epoxide formed by the reaction of a bw-phenol with epoxides: (1) reacts with the carboxylic acid of the latex, (2) releasing a phenol epoxide, and (3) forming the polymer.
  • This polymer hardens rapidly, forming an exceptionally hard coating on the surface.
  • epoxy ester vesicles were made and then mixed with an off-the-shelf latex paint to see whether it is possible to make the paint combination of the present invention.
  • the latex has carboxylic acid functional groups and is neutralized with ammonium hydroxide.
  • Ammonium lauryl sulfate was used as the secondary surfactant in making the vesicles.
  • Table 1 shows the formulation used in manufacture of the vesicles. TABLE 1
  • Epoxide 52.0 Araldite G Y6010, Ciba-Geigy Corp.
  • the epoxy ester and epoxide were blended together and heated to approximately 75°C, forming the lipophilic phase.
  • the epoxide used has the following general formulation:
  • the ammonium lauryl sulfate, ammonium hydroxide and water were heated to 70°C, forming the aqueous phase.
  • a laboratory size homogenizer was lowered into the aqueous phase and while homogenizing, the lipid phase was added to the aqueous phase.
  • the combination was mixed for ten minutes, yielding a product with a temperature of about 69°C, having a thin, lotion-like consistency and a pH of 8.0-8.5. Microscopic examination showed heterogeneous size vesicles with no free epoxy. No separation of phases occurred upon centrifugation at 3500 RPM for ten minutes.
  • the epoxy vesicles were then blended with Maincote AE-58 (Rohm and Hass), a commercial latex paint. The proportions were one part vesicles to two, three or four parts latex paint. The mixtures were placed in closed containers and kept at 50°C for observation. On the tenth day, all three mixtures began to solidify. The mixtures were heated in a water bath to 90°C, which caused the latex and epoxide to react, yielding a solid within five minutes. The 90°C bath reliquifies the epoxy ester of the vesicle walls, releasing all the epoxide.
  • Table 2 shows the formulation used in making the vesicles.
  • Example 2 This same procedure was used as in Example 1 to make the vesicles except that, because after five minutes of homogenization a great deal of foam resulted, 2 ml of Silicone Medical Anti-Foam (Dow Corning) was added. The solution was then homogenized an additional five minutes.
  • the temperature after homogenization was approximately 60°C and microscopic examination again showed heterogeneous vesicles. Centrifugation showed no separation of free epoxy.
  • the vesicles were then blended with one-four parts of an acid functional latex, not neutralized, with a pH of 6.2 (obtained from the Sherwin-Williams Company). The combined product was stored in closed containers and kept at 50°C. Solidification did not commence occurring until 16 days after formation, showing that the ammonium ion was a contributory factor in solidification.
  • Example 2 the vesicles described in Example 2 were used except they were checked for pH and neutralized prior to addition to the latex. When the vesicular pH was found to be 7.1, IN NaOH was added until a pH of 7.8 was achieved.
  • Example 2 The same latex was used as in Example 2, except it also was neutralized with IN NaOH to reach a pH of 7.0.
  • Table 3 shows the proportions of epoxy vesicles and sodium neutralized latex used in this experiment, as well as the resulting pH of each preparation.
  • Similar uses of the epoxy vesicles could be made with other materials such adhesives, polyurethanes, and other coating materials.
  • urethane monomers or styrene monomers can react with the epoxide to form a hard epoxide co-polymer.
  • Those skilled in the arts may determine other uses for the vesicles. Such other uses are deemed to be encompassed in the following claims.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Biophysics (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)

Abstract

Un nouveau type de vésicule lipidique paucilamellaire comprenant un ester époxy constituant le matériau de base d'une paroi a été développé. Cette vésicule lipidique peut être utilisée pour encapsuler des époxydes sans perte. Ces vésicules contenant des époxydes sont notamment utilisées dans la fabrication de peintures polymères latex-époxy qui sont stables à la conservation et se polymérisent lors du séchage.
PCT/US1995/013877 1994-11-03 1995-10-26 Vesicules d'ester epoxy et peintures WO1996014360A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39695/95A AU3969595A (en) 1994-11-03 1995-10-26 Epoxy ester vesicles and paints

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US33375794A 1994-11-03 1994-11-03
US08/333,757 1994-11-03

Publications (1)

Publication Number Publication Date
WO1996014360A1 true WO1996014360A1 (fr) 1996-05-17

Family

ID=23304135

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/013877 WO1996014360A1 (fr) 1994-11-03 1995-10-26 Vesicules d'ester epoxy et peintures

Country Status (3)

Country Link
AU (1) AU3969595A (fr)
CA (1) CA2204398A1 (fr)
WO (1) WO1996014360A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505428A (en) * 1966-01-03 1970-04-07 Inmont Corp Curable normally stable compositions containing cross linking agent in capsule form
US4908209A (en) * 1983-08-16 1990-03-13 Interface, Inc. Biocidal delivery system of phosphate ester and method of preparation thereof
US5160669A (en) * 1988-03-03 1992-11-03 Micro Vesicular Systems, Inc. Method of making oil filled paucilamellar lipid vesicles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505428A (en) * 1966-01-03 1970-04-07 Inmont Corp Curable normally stable compositions containing cross linking agent in capsule form
US4908209A (en) * 1983-08-16 1990-03-13 Interface, Inc. Biocidal delivery system of phosphate ester and method of preparation thereof
US5160669A (en) * 1988-03-03 1992-11-03 Micro Vesicular Systems, Inc. Method of making oil filled paucilamellar lipid vesicles

Also Published As

Publication number Publication date
AU3969595A (en) 1996-05-31
CA2204398A1 (fr) 1996-05-17

Similar Documents

Publication Publication Date Title
JP2642867B2 (ja) 水基材撥水性塗布組成物
KR950703413A (ko) 코팅물질의 제조 방법(method of preparing coating materrials)
US4921912A (en) Epoxy resin composition containing acrylic oligomer, amine and amine-terminated nitrile rubber
JP2015514824A (ja) 水媒性エポキシ樹脂分散物およびエポキシ硬化剤組成物
EP0666885B1 (fr) Nouveaux polymeres en emulsion ionique, et leur preparation
EP1748801A2 (fr) Compositions et articles contenant une matrice polymere reticulee et un liquide actif immobilise et procedes de fabrication et d'utilisation de ceux-ci
US4639475A (en) Adhesive stick and a process for its production
US5087647A (en) Two-component systems based on epoxides and diamines
US4442245A (en) Emulsion based on epoxy resins and diammonium salts and its preparation
DE50304724D1 (de) Addukte von Epoxidharzen und von Phosphor abgeleiteten Säuren sowie Verfahren zu deren Herstellung
WO1996014360A1 (fr) Vesicules d'ester epoxy et peintures
EP3946711A1 (fr) Microcapsules d'époxyde avec émulsifiants de pickering
TW502043B (en) Process for preparing self-emulsified aqueous epoxy resin dispersion, single-pack double curable aqueous resin composition comprising the same and single-pack curable composition of aqueous hybrid resin comprising the same
US4440882A (en) Emulsion based on epoxy resin and polyammonium salts and its preparation
CN106432616B (zh) 一种含有可聚合乳化剂结构的丙烯酸树脂药用辅料及其制备方法
CA1261756A (fr) Preparations antimycotiques en gel
JPH05156225A (ja) 二液型接着剤
JP2022526958A (ja) エポキシドマイクロカプセルを有する構造接着テープ
JPS61108680A (ja) ポリ塩化ビニル床材用接着剤組成物
JPH03220246A (ja) マイクロカプセル型アミン系硬化剤
JPH0693211A (ja) プライマー組成物
JPH06128545A (ja) 接着剤組成物
CN109467676A (zh) 一种耐冲击水性环氧固化剂的制备方法
GB1600933A (en) Liquid membrane encapsulated reactive products
CN119403856A (zh) 用于生产用于水性环氧涂料配制品的固化剂的方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA JP KR MX

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2204398

Country of ref document: CA

Ref country code: CA

Ref document number: 2204398

Kind code of ref document: A

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase