CA1094708A - Process for producing thermosetting binders for cathodic electrodeposition coating - Google Patents
Process for producing thermosetting binders for cathodic electrodeposition coatingInfo
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- CA1094708A CA1094708A CA292,913A CA292913A CA1094708A CA 1094708 A CA1094708 A CA 1094708A CA 292913 A CA292913 A CA 292913A CA 1094708 A CA1094708 A CA 1094708A
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- aqueous binders
- reaction product
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4465—Polyurethanes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Molecular Biology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Cathodically depositable, aqueous coating compositions com-prising the reaction product of (A) diene polymers containing free hydroxyl groups with a hydroxyl number of at least 40 mg KOH/g and an average maximum molecular weight of 4000; and (B) a compound having an average of from about 0.8 to 1.5 free isocyanate groups and at least one basic ali-phatically bound nitrogen atom. Optionally, there can be included in the reaction product a compound having from about 0. 8 to 1. 5 free isocyanate groups and from 1 to 3 ethylenically unsaturated double bonds. The coat-ing compositions cure at relatively low temperatures and relatively short curing times to provide films having excellent resistance to water, chemi-cals, and corrosion.
Cathodically depositable, aqueous coating compositions com-prising the reaction product of (A) diene polymers containing free hydroxyl groups with a hydroxyl number of at least 40 mg KOH/g and an average maximum molecular weight of 4000; and (B) a compound having an average of from about 0.8 to 1.5 free isocyanate groups and at least one basic ali-phatically bound nitrogen atom. Optionally, there can be included in the reaction product a compound having from about 0. 8 to 1. 5 free isocyanate groups and from 1 to 3 ethylenically unsaturated double bonds. The coat-ing compositions cure at relatively low temperatures and relatively short curing times to provide films having excellent resistance to water, chemi-cals, and corrosion.
Description
1229/1340 109470~3 FIELD OF INVENTION AND BACKGROUND
The present invention is directed to the preparation of, and coating compositions which are water-dilutable upon neutralization with acids. The coating compositions are electrically depositable at the cathode of an electrodeposition system and will crosslink through thermal polymer-ization.
Electrodeposition of synthetic resins and plasticsJ although known for substantial time, has gained technic~l importance as a coating process in only recent years. The coating compositions or binders pri-marily used for commercial electrodeposition contain polycarbo~ylic acid resins neutralized with bases. The products deposit at the anode of an - electrodeposition system. Owing to the acidic character of the resins, they are sensitive to corroding influences exerted by salts and particularly by alkalis. Furthermore, coatings of the aforesaid compositions tend to undergo spot discoloration or undergo other chemical changes as a result of the metal ions anodically dissolved from the anode. Accordingly, there has been a desire to use coating compositions which will deposit at the cathode of an electrodeposition system.
A substantial number of binders are disclosed in the literature carrying groupings neutralizable with acids which can be deposited on cathodically wired ob~ects of an electrodeposition system. Many have dis-advantages primarily due to the need to have crosslinking additives in the c~oating compositions which adversely affect film characteristics. Re-cently, however, coating compositions have been provided which are self-crosslinking through thermal polymerization. These self-crossl;nking binders include binders comprising -109~70B
(A) the reaction products of diepoxy compounds with alpha, beta-unsaturated acids and, optionally, long chain fatty acids, and basic monoisocyanates as described in copending Canadian appli- `
cation No. 282,996 filed July 18, 1977, assigned to the assignee of the present application;
(B) reaction products of diepo~y compounds with monoamines and, optionally, fatty acids, and unsaturated monoisocyanates as de-scribed in copending Canadian application No. 282,900 filed July 18, 1977, assigned to the assignee of the present application; and (C) two moles of a diepoxy compound plus one mole of a pri-mary-tertiary or secondary-secondary diamine plus two moles of an alpha,beta-unsaturated monocarboxylic acid and, optionally, an unsat-urated fatty acid, plus an unsaturated monoisocyanate as described in copending Canadian application No. 290,406 filed November 8, 1977, assigned to the assignee of the present application.
The aforesaid binders are highly desirable due to their ability to self-crosslink through the presence of alpha,beta-unsatura-tion; their being water-soluble in the presence of acids due to the basic nitrogen atoms, and their ability to provide excellent films with good performance characteristics, particularly regarding resistance to corroding influences. The aforesaid binders, however, utilize expensive components and, accordingly~ cannot be used for many applications be-cause of cost.
OBJECTS OF THE INVENTION AND GENERAL DESCRIPTION
It has now been found that components containing basic func-tional nitrogen groups for neutralization with inorganic or organic acids can be derived rrom components which are rela~ively inexpensive, but which ~2 IL~ - 4 -~0~ ~708 provide coating compositions having excellent resistance to water, chemicals, and corrosion. The relatively low cost of the components permits the use of cathodic electrodeposition on a substantially wider scale than heretofore possible.
The basic functional nitrogen atoms according to this inven-tion are introduced into substantially non-saponifiable diene polymers having a main polymer chain of co-valent carbon atoms carrying free hydroxyl groups to form the basis for a thermosetting aqueous binder for cathodically depositable coatings, such binders, in accordance with the invention comprise essentially the reaction product of (A) a hydroxyl group containing diene polymer having a hydroxyl number of at least about 40 mg KOH/g and an average maximum molecular weight of 4000; and ~B) compounds carrying per molecule an average of from 0.8 to 1.5, and pre-ferably one free isocyanate group and at least one basic aliphatically bound nitrogen atom, neutralized with an organic or inorganic acid.
Optionally, there can be present a compound ~C) carrying per molecule an average of from 0.8 to about 15, and preferably one free isocyanate group and from l to 3 ethylenically unsaturated double bonds per molecule.
Components ~A) and (B~, and optionally (C), are reacted at from about 10 to 100C., and preferably from about 50 to 80C., to an NCO-value of substantially zero. The reactionJ if desired, can be carried out in the presence of an isocyanate inert solvent. Catalyst can be included if desired. The reaction product is partially or totally neutralized with inorganic or organic acids.
Unsaturated polymers of dienes with free hydroxy groups, suit-able for use in the present invention, include copolymers of alkane di-enes or cycloalkanedienes with hydroxy groups containing monovinyl com-pounds and, optionally, subordinate quantities of other monovinyl com-pounds. Suitable diene compounds include 1,3-butadiene, 1-3-penta-diene, cyclo-B _ 5 _ 1229/13~0 1094708 pentadiene or isoprene, while hydroxy group containing monovinyl com-pounds are allyl alcohol or hydroxy alkyl esters or hydroxyalkylene oxide esters of acrylic or methacrylic acid. Another known method to introduce preferably chain ending hydroxyl groups into diene polymers is the reaction of so-called "living polymers" with alkylene oxides, preferably ethylene oxide. A group of diene polymers with latent hydroxy groups are epoxidation products of diene polymers. The products are prepared in known manner , through treatment of liquid diene polymers with per-formic acid or per-acetic acid. In oxirane structures, the oxirane group is considered a latent hydroxy group since a hydroxy group is set free upon reaction with a com-pound carrying an active hydrogen atom, The reaction can be carried out ~~ at temperatures of up to 1~0~ C., either with monocarboxylic acids orsaturated or unsaturated fatty acids, benzoic acid, p-tert.-butylbenzoic acid, sorbic acid, and the like, and may optionally be accelerated by alka-line catalysts. Another manner of releasing free hydroxy groups from partially epoxidized diene polymers which is an advantage for the use of the products produced according to the invention is the reaction of the epoxy group with secondary alkylamines or secondary alkanol amines, such as diethylamine, diethanol arnine, diisopropylamine. The introduc-tion of the nitrogen atom into the polymer chain increases the basic char-acter of the macromolecule in the desired way. The secondary hydroxy group which forms on the opening of the oxirane ring is used according to the invention for reaction with the isocyanate containing components.
The basic nitrogen atorns are introduced into the diene polymer containing free hydroxyl groups according to this invention by reaction with compounds carrying per molecule an average Or from 0. 8 to 1.5 1229/1340 109470t3 isocyanate groups and at least one tertiary basic nitrogen atom. Prefer-ably the compounds contain an average of about one isocyanate group in the molecule.
The compounds containing the basic nitrogen atom are pre-pared in a separate step by reacting diisocyanates or polyisocyanates with less than a stoichiometric quantity of an amine of the formula -,R
R - N~
R being an alkanol or hydroxyphenyl radical, and Rl and R2 being alkyl radicals or cycloalkyl radicals. Dialkylalkanol amines are preferred in-~; 10 cluding dimethylethanol amine, diethylethanol amine or higher homologues and isomers thereof.
Suitable polyisocyanates for use in preparing the intermediate basic nitrogen carrying component are aromatic isocyanates such as 2,4-or 2, 6-toluylene diisocyanate or mixtures thereof, 4,4'-diphenyl-methane-diisocSranate or cycloaliphatic isocyanates such as isophorone diisocyanate, cyclohexane-1,4-diisocyanate, as well as aliphatic isocyanates, such as trimethylhexamethylene-1,6-diisocyanate; tris-hexamethylene-triisocyanate.
The reaction between the amine and the polyisocyanate is carried out at from 0 to 80 C., preferably at from 2û to 50 C. The weight ratios between the reaction partners are chosen in order that the formed - compound carries from about 0. 8 to 1. 5, and preferably one free isocyanate g-roup~, This product is at times herein designated as the "basic isocyanate intermediate. "
In order to enhance the thermal crosslinking reaction of the cathodically deposited film, it is desirable to react the reaction products 1229/13ds0 ~09470B
of the hydroxy containing diene polymer and basic isocyanate intermediate with compounds carrying from about 0.8 to 1. 5 free isocyanate groups in the molecule and from 1 to 3 olefinically unsaturated double bonds. These compounds are prepared in a separate reaction step from the aforemen-tioned polyisocyanates and a reaction partner which carries at least one isocyanate reactive hydrogen atom and from 1 to 3 olefinic double bonds.
Suitable unsaturated compounds include hydroxyalkyl esters of acrylic acid or methacrylic acid, triethyleneglycol mono(meth3acrylate, trimethylol-propanedi(meth)acrylate, allyl alcohol, tripropyleneglycol manoabietate, oleyl alcohoLor linoleyl alcohol. The reaction between the polyisocyanate and the isocyanate reactive olefinically unsaturated compound is carried -- out, optionally in an isocyanate inert solvent, at temperatures of from 10 to 100 C., and preferably from about 50 to 80 C. Organic stannous com-pounds, as catalysts, can be advantageously used. The weight ratios of the reactants are chosen such that the formed compound carries from about 0.8 to 1.5, and preferably one free isocyanate group in the molecule. The compound is at times herein designated as the "olefinically unsaturated isocyanate intermediate. "
The reaction components used in preparing the binders of the ~0 present invention are effected in order that the hydroxy group containing unsaturated diene polymers, preferably dissolved in isocyanate-inert solvents, are reacted at from 10 to 100 C., preferably at from 50 to 80 C., with the desired quantity of the basic isocyanate intermediate and, option-ally, with the olefinically unsaturated isocyanate intermediate, optionally in the presence of organic stannous compounds as catalysts, until an NCO-value of zero is obtained. The quantity of basic isocyanate interme-~094708 diate is chosen in order that the basicity of the binder upon neutralization with the acid will provide sufficient water dilutability at a pH-value of from 4 to 9, and preferably 6 to 8. The reaction between the hydroxy group containing polycondensates, the basic isocyanate intermediate, and the olefinically unsaturated intermediate may be effected in random sequence, separately or jointly.
In order to reduce the stoving temperatures or to obtain a par-ticular corrosion protection it can be of advant age, although not essential, to co-employ additional known crosslinking agents, such as melamine- or phRnol-formaldehyde condensates. Such resins are prepared according to known methods by alkaline condensation of formaldehyde or of formaldehyde-splitting substances with urea, melamine, benzoguanamine? acetoguanarnine, phenolJ cresol, p.-tert. -butylphenol, Bishpenol A, and the like. The methylol compounds may be optionally etherified with alcohols. A preferred product in this group is the reaction product of phenol with formaldehyde - carrying allyl ether groups. If the crosslinking agents are non-water-soluble, it is advantageous to combine them by careful condensation with the binder of the invention at temperatures of from 50 to 120 C. The reac-tion is carried out until excellent dilutability with water of the reaction mass upon neutralization with low molecular weight organic acids is ob-tained.
The basic nitrogen atoms of the coating compositions of the invention are partially or totally neutralized with organic and~or inorganic acids such as formic acid, acetic acid, lactic acid, and phosphoric acid.
The degree of neutralization in the individual case depends upon the prop-erties of the binder employed. In generalJ sufficient acid is added to allow , 10947B
dispersion or dilution with water at a pH-value of the coating of from about 4 to 9, and preferably of from about 6 to 8.
The concentration in water of the binder depends upon the para-meters of electrodeposition and may lie in a range of between about 3 to 30 percent by weight, preferably at from about 5 to 15 percent by weight.
The applied coating composition can optionally contain various additives, such as pigments, extenders, surface active agents~ etc. Upon electro-deposition, the binder of the invention as a vehicle of the aqueous coating composition is wired to a conductive anode and cathode, the surface of the cathode being coated with the coating composition. The conductive sub-strates to be coated may be of a variety of materials, and particularly -- metals such as ~teel, aluminum, copper, or the like. Other metalized materials or materials rendered conductive through a conductive coating can be employed. AMer deposition, the coating is cured at a stoving tem-perature of from about 130 to 200C., preferably 150 to 180C. for about 5 to 30 minutes, preferably 10 to 25 minutes.
The following examples illustrate the invention without limiting its scope.
Description Of The Intermediates Used In The Exarnples ~A) HydroxylGroup Containing Diene Polymers_ Intermediate (A 1): Commercially available liquid polybutadiene with a hydroxyl number of 67 mg KoHJg. a molec~ar weight of about 1400 and a microstructure of about 90 percent 1, 2-vinyl- and about 10 percent 1, 4-trans configuration is used. (Polybutadiene G 1000 manufactured by Nippon Soda Co. Ltd. ) j 10~ ~708 Intermediate (A 2): Commercially available liquid polybutadiene with a hydroxyl number of 47 mg KOH/g, a molecular weight of about 2800 and a microstructure of about 20 percent 1, 2-vinyl- and about 60 percent 1, 4-trans and 20 percent 1> 4-cis- configuration. (Polybutadiene R 45 HT
manufactured by Arco Chemical Company) Intermediate (A 3): In a three-neck llask equipped with stirrer, inert gas duct and reflux condensor, 1000 g of an epoxidized polybutadiene (1) are heated to 100~C. and mixed with 885 g of p-tert.-butylbenzoic acid and 2 g of triethylamine. The temperature is raised to 180 C. and the reaction is carried to an acid value of below 3 mg KOH/g. Hydroxyl number of the end product is approximately 200 mg KOH/g. The epoxidized polybutadiene -- has a molecular weight of about 1500, an epoxy equivalent of about 160, and a microstructure of 75 percent of 1, 4-cis and 25 percent of 1, 4-trans configuration.
Intermediate (A 4): 1000 g of the epoxidized polybutadiene used for .
intermediate (A 3) are heated to 180C. within 3 hours together with 525 g of diethanol amine, maintaining reflux condensation and inert gas protection.
After another three hours at this temperature, 95 percent of the used amine has reacted. A product with a hydroxyl number of about 600 mg KOH/g 20 results~
(B) Basic Isocyanate Intermediates Intermediate (B 1): 174 g OI toluylene diisocyanate (a blend of 80 -percent of 2> 4- and 20 percent of 2, 6-isomers) are charged to a three-neck flask equipped with reflux condensor and inert gas duct, and, with 25 absolute protection from moisture and effective cooling, 89 g of dimethyl-1229/1340 109~'~708 ethanol arnine, 60 percent in ethyleneglycol monoethylether acetate, are continuously added. The reaction temperature is held below 25C.
The reaction is finished when the theoretical isocyanate value is 16 percent or lower.
S Intermediate (B 2): 174 g of toluylene diisocyanate (a blend of 80 percent of 2, 4- and 20 percent of 2, 6-isomers) are mixed with 194 g of ethyleneglycol monoethylether acetate in a three-neck flask equipped with reflux condensor and inert gas duct. Access of moisture is absolutely prevented. With intense cooling, 117 g of diethylethanolamine are added continuously within one hour at a temperature of below 25 C. The iso-cyanate value of the final product is 14.4 percent.
-(C) Olefinically Unsaturated Isocyanate Intermediates ~ = . . .
Intermediate (C 1): 168 g of hexamethylene diisocyanate are mixed -with 200 g of ethyleneglycol monoethylether acetate in a three-neck flask with reflux condensor and inert gas duct and, while maintaining total pre-vention of moisture access, is heated to 60 C. At the stated temperature a blend of 130 g of hydroxyethylmethacrylate, stabilized with 0.1 g of hydroquinone, are added dropwise. The reaction is finished, about 2 hours, when the isocyanate value has attained 14.1 percent or slightly less.
Intermediate (C 2): In a three-neck ilask equipped with reflux condensor and inert gas duct, with no possible access of moisture, 222 g of isophorone diisocyanate are blended with 325 g of ethyleneglycol mono-ethylether acetate and heated to 40C. 265 g of linoleyl alcohol are then added continuously and, after the end of the addition, the temperature is raised to 90 C. and held, until the isocyanate value has attained 8. 6.
i ~ 1094708 Examples 1 - 4: In a reaction vessel equipped with stirrer, addîtion funnel, thermometer and reflux condensorJ the hydroxy-rich diene polymer (Intermediate A), in the presence of ethylene glycol monoethylether acetate, an isocyanate inert solvent, is blended with a basic isocyanate intermediate (Intermediate B), preventing access of moisture, and is re-acted at 40 to 100 C. to an NCO-value of approximately zero. Swbsequently, the reaction product is optionally mixed with an alpha, beta-olefinically unsaturated isocyanate intermediate (Intermediate C) and reacted, also at from 40 to 100 C., until an NCO-value of zero is obtained.
The reaction of Intermediate A with Intermediate B and Inter-mediate C may also be effected in one reaction step at from 40 to 100 C., - with the same results.
It is also possible to blend the described reaction products with crosslinking agents such as urea resins, melamine resins, or phenol-formaldehyde resins and carefully reacted until substantial water dilutability is attained.
The quantities of the Intermediates and the reactions conditions for Examples 1 - 4 are tabulated in Table 1.
1229/1340 109470~
Reaction Intermediates (g) ) Crosslinkers +) Conditions h/C.
The present invention is directed to the preparation of, and coating compositions which are water-dilutable upon neutralization with acids. The coating compositions are electrically depositable at the cathode of an electrodeposition system and will crosslink through thermal polymer-ization.
Electrodeposition of synthetic resins and plasticsJ although known for substantial time, has gained technic~l importance as a coating process in only recent years. The coating compositions or binders pri-marily used for commercial electrodeposition contain polycarbo~ylic acid resins neutralized with bases. The products deposit at the anode of an - electrodeposition system. Owing to the acidic character of the resins, they are sensitive to corroding influences exerted by salts and particularly by alkalis. Furthermore, coatings of the aforesaid compositions tend to undergo spot discoloration or undergo other chemical changes as a result of the metal ions anodically dissolved from the anode. Accordingly, there has been a desire to use coating compositions which will deposit at the cathode of an electrodeposition system.
A substantial number of binders are disclosed in the literature carrying groupings neutralizable with acids which can be deposited on cathodically wired ob~ects of an electrodeposition system. Many have dis-advantages primarily due to the need to have crosslinking additives in the c~oating compositions which adversely affect film characteristics. Re-cently, however, coating compositions have been provided which are self-crosslinking through thermal polymerization. These self-crossl;nking binders include binders comprising -109~70B
(A) the reaction products of diepoxy compounds with alpha, beta-unsaturated acids and, optionally, long chain fatty acids, and basic monoisocyanates as described in copending Canadian appli- `
cation No. 282,996 filed July 18, 1977, assigned to the assignee of the present application;
(B) reaction products of diepo~y compounds with monoamines and, optionally, fatty acids, and unsaturated monoisocyanates as de-scribed in copending Canadian application No. 282,900 filed July 18, 1977, assigned to the assignee of the present application; and (C) two moles of a diepoxy compound plus one mole of a pri-mary-tertiary or secondary-secondary diamine plus two moles of an alpha,beta-unsaturated monocarboxylic acid and, optionally, an unsat-urated fatty acid, plus an unsaturated monoisocyanate as described in copending Canadian application No. 290,406 filed November 8, 1977, assigned to the assignee of the present application.
The aforesaid binders are highly desirable due to their ability to self-crosslink through the presence of alpha,beta-unsatura-tion; their being water-soluble in the presence of acids due to the basic nitrogen atoms, and their ability to provide excellent films with good performance characteristics, particularly regarding resistance to corroding influences. The aforesaid binders, however, utilize expensive components and, accordingly~ cannot be used for many applications be-cause of cost.
OBJECTS OF THE INVENTION AND GENERAL DESCRIPTION
It has now been found that components containing basic func-tional nitrogen groups for neutralization with inorganic or organic acids can be derived rrom components which are rela~ively inexpensive, but which ~2 IL~ - 4 -~0~ ~708 provide coating compositions having excellent resistance to water, chemicals, and corrosion. The relatively low cost of the components permits the use of cathodic electrodeposition on a substantially wider scale than heretofore possible.
The basic functional nitrogen atoms according to this inven-tion are introduced into substantially non-saponifiable diene polymers having a main polymer chain of co-valent carbon atoms carrying free hydroxyl groups to form the basis for a thermosetting aqueous binder for cathodically depositable coatings, such binders, in accordance with the invention comprise essentially the reaction product of (A) a hydroxyl group containing diene polymer having a hydroxyl number of at least about 40 mg KOH/g and an average maximum molecular weight of 4000; and ~B) compounds carrying per molecule an average of from 0.8 to 1.5, and pre-ferably one free isocyanate group and at least one basic aliphatically bound nitrogen atom, neutralized with an organic or inorganic acid.
Optionally, there can be present a compound ~C) carrying per molecule an average of from 0.8 to about 15, and preferably one free isocyanate group and from l to 3 ethylenically unsaturated double bonds per molecule.
Components ~A) and (B~, and optionally (C), are reacted at from about 10 to 100C., and preferably from about 50 to 80C., to an NCO-value of substantially zero. The reactionJ if desired, can be carried out in the presence of an isocyanate inert solvent. Catalyst can be included if desired. The reaction product is partially or totally neutralized with inorganic or organic acids.
Unsaturated polymers of dienes with free hydroxy groups, suit-able for use in the present invention, include copolymers of alkane di-enes or cycloalkanedienes with hydroxy groups containing monovinyl com-pounds and, optionally, subordinate quantities of other monovinyl com-pounds. Suitable diene compounds include 1,3-butadiene, 1-3-penta-diene, cyclo-B _ 5 _ 1229/13~0 1094708 pentadiene or isoprene, while hydroxy group containing monovinyl com-pounds are allyl alcohol or hydroxy alkyl esters or hydroxyalkylene oxide esters of acrylic or methacrylic acid. Another known method to introduce preferably chain ending hydroxyl groups into diene polymers is the reaction of so-called "living polymers" with alkylene oxides, preferably ethylene oxide. A group of diene polymers with latent hydroxy groups are epoxidation products of diene polymers. The products are prepared in known manner , through treatment of liquid diene polymers with per-formic acid or per-acetic acid. In oxirane structures, the oxirane group is considered a latent hydroxy group since a hydroxy group is set free upon reaction with a com-pound carrying an active hydrogen atom, The reaction can be carried out ~~ at temperatures of up to 1~0~ C., either with monocarboxylic acids orsaturated or unsaturated fatty acids, benzoic acid, p-tert.-butylbenzoic acid, sorbic acid, and the like, and may optionally be accelerated by alka-line catalysts. Another manner of releasing free hydroxy groups from partially epoxidized diene polymers which is an advantage for the use of the products produced according to the invention is the reaction of the epoxy group with secondary alkylamines or secondary alkanol amines, such as diethylamine, diethanol arnine, diisopropylamine. The introduc-tion of the nitrogen atom into the polymer chain increases the basic char-acter of the macromolecule in the desired way. The secondary hydroxy group which forms on the opening of the oxirane ring is used according to the invention for reaction with the isocyanate containing components.
The basic nitrogen atorns are introduced into the diene polymer containing free hydroxyl groups according to this invention by reaction with compounds carrying per molecule an average Or from 0. 8 to 1.5 1229/1340 109470t3 isocyanate groups and at least one tertiary basic nitrogen atom. Prefer-ably the compounds contain an average of about one isocyanate group in the molecule.
The compounds containing the basic nitrogen atom are pre-pared in a separate step by reacting diisocyanates or polyisocyanates with less than a stoichiometric quantity of an amine of the formula -,R
R - N~
R being an alkanol or hydroxyphenyl radical, and Rl and R2 being alkyl radicals or cycloalkyl radicals. Dialkylalkanol amines are preferred in-~; 10 cluding dimethylethanol amine, diethylethanol amine or higher homologues and isomers thereof.
Suitable polyisocyanates for use in preparing the intermediate basic nitrogen carrying component are aromatic isocyanates such as 2,4-or 2, 6-toluylene diisocyanate or mixtures thereof, 4,4'-diphenyl-methane-diisocSranate or cycloaliphatic isocyanates such as isophorone diisocyanate, cyclohexane-1,4-diisocyanate, as well as aliphatic isocyanates, such as trimethylhexamethylene-1,6-diisocyanate; tris-hexamethylene-triisocyanate.
The reaction between the amine and the polyisocyanate is carried out at from 0 to 80 C., preferably at from 2û to 50 C. The weight ratios between the reaction partners are chosen in order that the formed - compound carries from about 0. 8 to 1. 5, and preferably one free isocyanate g-roup~, This product is at times herein designated as the "basic isocyanate intermediate. "
In order to enhance the thermal crosslinking reaction of the cathodically deposited film, it is desirable to react the reaction products 1229/13ds0 ~09470B
of the hydroxy containing diene polymer and basic isocyanate intermediate with compounds carrying from about 0.8 to 1. 5 free isocyanate groups in the molecule and from 1 to 3 olefinically unsaturated double bonds. These compounds are prepared in a separate reaction step from the aforemen-tioned polyisocyanates and a reaction partner which carries at least one isocyanate reactive hydrogen atom and from 1 to 3 olefinic double bonds.
Suitable unsaturated compounds include hydroxyalkyl esters of acrylic acid or methacrylic acid, triethyleneglycol mono(meth3acrylate, trimethylol-propanedi(meth)acrylate, allyl alcohol, tripropyleneglycol manoabietate, oleyl alcohoLor linoleyl alcohol. The reaction between the polyisocyanate and the isocyanate reactive olefinically unsaturated compound is carried -- out, optionally in an isocyanate inert solvent, at temperatures of from 10 to 100 C., and preferably from about 50 to 80 C. Organic stannous com-pounds, as catalysts, can be advantageously used. The weight ratios of the reactants are chosen such that the formed compound carries from about 0.8 to 1.5, and preferably one free isocyanate group in the molecule. The compound is at times herein designated as the "olefinically unsaturated isocyanate intermediate. "
The reaction components used in preparing the binders of the ~0 present invention are effected in order that the hydroxy group containing unsaturated diene polymers, preferably dissolved in isocyanate-inert solvents, are reacted at from 10 to 100 C., preferably at from 50 to 80 C., with the desired quantity of the basic isocyanate intermediate and, option-ally, with the olefinically unsaturated isocyanate intermediate, optionally in the presence of organic stannous compounds as catalysts, until an NCO-value of zero is obtained. The quantity of basic isocyanate interme-~094708 diate is chosen in order that the basicity of the binder upon neutralization with the acid will provide sufficient water dilutability at a pH-value of from 4 to 9, and preferably 6 to 8. The reaction between the hydroxy group containing polycondensates, the basic isocyanate intermediate, and the olefinically unsaturated intermediate may be effected in random sequence, separately or jointly.
In order to reduce the stoving temperatures or to obtain a par-ticular corrosion protection it can be of advant age, although not essential, to co-employ additional known crosslinking agents, such as melamine- or phRnol-formaldehyde condensates. Such resins are prepared according to known methods by alkaline condensation of formaldehyde or of formaldehyde-splitting substances with urea, melamine, benzoguanamine? acetoguanarnine, phenolJ cresol, p.-tert. -butylphenol, Bishpenol A, and the like. The methylol compounds may be optionally etherified with alcohols. A preferred product in this group is the reaction product of phenol with formaldehyde - carrying allyl ether groups. If the crosslinking agents are non-water-soluble, it is advantageous to combine them by careful condensation with the binder of the invention at temperatures of from 50 to 120 C. The reac-tion is carried out until excellent dilutability with water of the reaction mass upon neutralization with low molecular weight organic acids is ob-tained.
The basic nitrogen atoms of the coating compositions of the invention are partially or totally neutralized with organic and~or inorganic acids such as formic acid, acetic acid, lactic acid, and phosphoric acid.
The degree of neutralization in the individual case depends upon the prop-erties of the binder employed. In generalJ sufficient acid is added to allow , 10947B
dispersion or dilution with water at a pH-value of the coating of from about 4 to 9, and preferably of from about 6 to 8.
The concentration in water of the binder depends upon the para-meters of electrodeposition and may lie in a range of between about 3 to 30 percent by weight, preferably at from about 5 to 15 percent by weight.
The applied coating composition can optionally contain various additives, such as pigments, extenders, surface active agents~ etc. Upon electro-deposition, the binder of the invention as a vehicle of the aqueous coating composition is wired to a conductive anode and cathode, the surface of the cathode being coated with the coating composition. The conductive sub-strates to be coated may be of a variety of materials, and particularly -- metals such as ~teel, aluminum, copper, or the like. Other metalized materials or materials rendered conductive through a conductive coating can be employed. AMer deposition, the coating is cured at a stoving tem-perature of from about 130 to 200C., preferably 150 to 180C. for about 5 to 30 minutes, preferably 10 to 25 minutes.
The following examples illustrate the invention without limiting its scope.
Description Of The Intermediates Used In The Exarnples ~A) HydroxylGroup Containing Diene Polymers_ Intermediate (A 1): Commercially available liquid polybutadiene with a hydroxyl number of 67 mg KoHJg. a molec~ar weight of about 1400 and a microstructure of about 90 percent 1, 2-vinyl- and about 10 percent 1, 4-trans configuration is used. (Polybutadiene G 1000 manufactured by Nippon Soda Co. Ltd. ) j 10~ ~708 Intermediate (A 2): Commercially available liquid polybutadiene with a hydroxyl number of 47 mg KOH/g, a molecular weight of about 2800 and a microstructure of about 20 percent 1, 2-vinyl- and about 60 percent 1, 4-trans and 20 percent 1> 4-cis- configuration. (Polybutadiene R 45 HT
manufactured by Arco Chemical Company) Intermediate (A 3): In a three-neck llask equipped with stirrer, inert gas duct and reflux condensor, 1000 g of an epoxidized polybutadiene (1) are heated to 100~C. and mixed with 885 g of p-tert.-butylbenzoic acid and 2 g of triethylamine. The temperature is raised to 180 C. and the reaction is carried to an acid value of below 3 mg KOH/g. Hydroxyl number of the end product is approximately 200 mg KOH/g. The epoxidized polybutadiene -- has a molecular weight of about 1500, an epoxy equivalent of about 160, and a microstructure of 75 percent of 1, 4-cis and 25 percent of 1, 4-trans configuration.
Intermediate (A 4): 1000 g of the epoxidized polybutadiene used for .
intermediate (A 3) are heated to 180C. within 3 hours together with 525 g of diethanol amine, maintaining reflux condensation and inert gas protection.
After another three hours at this temperature, 95 percent of the used amine has reacted. A product with a hydroxyl number of about 600 mg KOH/g 20 results~
(B) Basic Isocyanate Intermediates Intermediate (B 1): 174 g OI toluylene diisocyanate (a blend of 80 -percent of 2> 4- and 20 percent of 2, 6-isomers) are charged to a three-neck flask equipped with reflux condensor and inert gas duct, and, with 25 absolute protection from moisture and effective cooling, 89 g of dimethyl-1229/1340 109~'~708 ethanol arnine, 60 percent in ethyleneglycol monoethylether acetate, are continuously added. The reaction temperature is held below 25C.
The reaction is finished when the theoretical isocyanate value is 16 percent or lower.
S Intermediate (B 2): 174 g of toluylene diisocyanate (a blend of 80 percent of 2, 4- and 20 percent of 2, 6-isomers) are mixed with 194 g of ethyleneglycol monoethylether acetate in a three-neck flask equipped with reflux condensor and inert gas duct. Access of moisture is absolutely prevented. With intense cooling, 117 g of diethylethanolamine are added continuously within one hour at a temperature of below 25 C. The iso-cyanate value of the final product is 14.4 percent.
-(C) Olefinically Unsaturated Isocyanate Intermediates ~ = . . .
Intermediate (C 1): 168 g of hexamethylene diisocyanate are mixed -with 200 g of ethyleneglycol monoethylether acetate in a three-neck flask with reflux condensor and inert gas duct and, while maintaining total pre-vention of moisture access, is heated to 60 C. At the stated temperature a blend of 130 g of hydroxyethylmethacrylate, stabilized with 0.1 g of hydroquinone, are added dropwise. The reaction is finished, about 2 hours, when the isocyanate value has attained 14.1 percent or slightly less.
Intermediate (C 2): In a three-neck ilask equipped with reflux condensor and inert gas duct, with no possible access of moisture, 222 g of isophorone diisocyanate are blended with 325 g of ethyleneglycol mono-ethylether acetate and heated to 40C. 265 g of linoleyl alcohol are then added continuously and, after the end of the addition, the temperature is raised to 90 C. and held, until the isocyanate value has attained 8. 6.
i ~ 1094708 Examples 1 - 4: In a reaction vessel equipped with stirrer, addîtion funnel, thermometer and reflux condensorJ the hydroxy-rich diene polymer (Intermediate A), in the presence of ethylene glycol monoethylether acetate, an isocyanate inert solvent, is blended with a basic isocyanate intermediate (Intermediate B), preventing access of moisture, and is re-acted at 40 to 100 C. to an NCO-value of approximately zero. Swbsequently, the reaction product is optionally mixed with an alpha, beta-olefinically unsaturated isocyanate intermediate (Intermediate C) and reacted, also at from 40 to 100 C., until an NCO-value of zero is obtained.
The reaction of Intermediate A with Intermediate B and Inter-mediate C may also be effected in one reaction step at from 40 to 100 C., - with the same results.
It is also possible to blend the described reaction products with crosslinking agents such as urea resins, melamine resins, or phenol-formaldehyde resins and carefully reacted until substantial water dilutability is attained.
The quantities of the Intermediates and the reactions conditions for Examples 1 - 4 are tabulated in Table 1.
1229/1340 109470~
Reaction Intermediates (g) ) Crosslinkers +) Conditions h/C.
2 1000 A 2 352 B1 - - - 1/40
3 1887 A 3 485 B2 249 Cl 580 BP - 1/80 ~)
4 1525 A 4 220 Bl 253 C2 - 452 PA 3/60 I t 1) +) All quantities refer to resin solids ~) Subsequent reaction with Intermediates B and C
+++) Simultaneous reaction with Intermediates B and C
Key to abbreviations in Table 1:
PE~ : Bisphenol A-formaldehyde resin PA : Phenol-formaldehyde resin with allyl ether groups (Methylon 75108 manufactured by General E:lectric) 15 Eval uation Of The Binders Of the binders each 100 g resin solids samples were mixed with the corresponding quantity of acid and made up to 1000 g with deionized water while stirring. The 10 percent solutions were deposited using direct current on steel panels as the cathode. Deposition time in all cases was 20 60 secondsO The coated substrates were rinsed with deionized water and cured at elevated temperature, Average film thich~ess o~ the cured ~ilms was between 13 to 17 ~am. Table 2 gives a summary of the evaluation.
12291l340 10~4708 u, TABLE 2 Neutralization Deposition Evaluation Q tity1) Type2) pH3) Volt Min/ C 4) Inde5n)ta- Resis 1 3.8 E 6.0 190 20/190 165 7.8 320/120 2 3.5 M 5,8 180 30/180 155 7.2 320/240 3 4.0 M 6.2 240 30/170 185 8.1 320/360 4 3.8 E 6.0 220 25/180 170 8.3 ~80/360 1) quantity of acid in g added to 100 g of resin solids 2) E: acetic acid; M: lactic acid 3) measured as a 10% aqueous solution 4) Konig pendulum hardness MN 53 157 (sec)
+++) Simultaneous reaction with Intermediates B and C
Key to abbreviations in Table 1:
PE~ : Bisphenol A-formaldehyde resin PA : Phenol-formaldehyde resin with allyl ether groups (Methylon 75108 manufactured by General E:lectric) 15 Eval uation Of The Binders Of the binders each 100 g resin solids samples were mixed with the corresponding quantity of acid and made up to 1000 g with deionized water while stirring. The 10 percent solutions were deposited using direct current on steel panels as the cathode. Deposition time in all cases was 20 60 secondsO The coated substrates were rinsed with deionized water and cured at elevated temperature, Average film thich~ess o~ the cured ~ilms was between 13 to 17 ~am. Table 2 gives a summary of the evaluation.
12291l340 10~4708 u, TABLE 2 Neutralization Deposition Evaluation Q tity1) Type2) pH3) Volt Min/ C 4) Inde5n)ta- Resis 1 3.8 E 6.0 190 20/190 165 7.8 320/120 2 3.5 M 5,8 180 30/180 155 7.2 320/240 3 4.0 M 6.2 240 30/170 185 8.1 320/360 4 3.8 E 6.0 220 25/180 170 8.3 ~80/360 1) quantity of acid in g added to 100 g of resin solids 2) E: acetic acid; M: lactic acid 3) measured as a 10% aqueous solution 4) Konig pendulum hardness MN 53 157 (sec)
5) Erichsen indentation DIN 53 156 (mm)
6) hours of water soak at 40~C. until corrosion or blistering become visible -- 7) salt spray ASTM-B 117-64: 2 mm of corrosion at the cross incision after the stated hours For the evaluation degreased non-pretreated steel panels were coated with a pigmented paint consisting of 100 parts by weight of resin 20 solids, 20 parts by weight of aluminum silicate pigment and 2 parts by weight of carbon black.
In the above illustrative examples various modifications can be made falling within the scope of the claimed invention. Such modifica-tions being within the abi~ity of one sl~illed in the art are within the scope 25 of the present invention.
In the above illustrative examples various modifications can be made falling within the scope of the claimed invention. Such modifica-tions being within the abi~ity of one sl~illed in the art are within the scope 25 of the present invention.
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Thermosetting aqueous binders for cathodically depositable coat-ings comprising the reaction product of (A) a hydroxyl group-containing diene polymer having a hydroxyl number of at least about 40 mg KOH/g, and an average maximum molecular weight of about 4000; and (B) compounds carrying per mole-cule an average of from about 0.8 to 1.5 free isocyanate groups and at least one basic aliphatically bound nitrogen atom, neutralized with an inorganic or organic acid.
2. The thermosetting aqueous binders of claim 1 wherein the free iso-cyanate groups per molecule of compound (B) is 1.
3. The thermosetting aqueous binders of claim 1 including within the reaction product component (C) having per molecule an average of from 0.8 to 1.5 free isocyanate groups and from about 1 to 3 olefinic double bonds.
4. The thermosetting aqueous binders of claim 1 wherein component (A) is a copolymer of a diene and a hydroxyl group-containing monovinyl com-pound.
5. The thermosetting aqueous binders of claim 1 wherein component (A) is an unsaturated diene polymer having free hydroxyl groups at the chain end of the polymers.
6. The thermosetting aqueous binders of claim 1 wherein component (A) is the reaction product of an epoxidized diene polymer with a compound con-taining an active hydrogen atom.
7. The thermosetting aqueous binders of claim 1 wherein component (B) is the reaction product of a polyisocyanate with an amine of the formula wherein R is an alkanol or hydroxyphenol radical, and R1 and R2 are alkyl or cycloalkyl radicals.
8. The thermosetting aqueous binders of claim 1 including an addi-tional crosslinking agent.
9. The thermosetting aqueous binders of claim 8 wherein the additional crosslinking agent is urea-, melamine-, or phenyl-formaldehyde condensate.
10. The thermosetting aqueous binders of claim 8 wherein the additional crosslinking agent is a phenol-formaldehyde condensate carrying allyl-ether groups.
11. The process of providing coating compositions which will cathod-ically deposit when used in an electrodeposition process including reacting at a temperature of from about 10 to 100°C. (A) a diene polymer having free hydroxyl groups and a hydroxyl number of at least about 40 mg KOH/g and an average molecular weight of about 4000; and (B) compounds carrying per mole-cule an average of from about 0.8 to 1.5 free isocyanate groups and at least one basic aliphatically bound nitrogen atom, said reaction being carried to an NCO-value of substantially zero, and neutralizing said reaction product with an inorganic or organic acid.
12. The process of claim 11 including in the reaction product a com-ponent (C) carrying per molecule an average of from 0.8 to 1.5 free isocyanate groups and from 1 to 3 ethylenically unsaturated double bonds.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT921076A AT343770B (en) | 1976-12-13 | 1976-12-13 | PROCESS FOR THE PRODUCTION OF WARM-HARDENABLE BINDERS FOR CATHODICALLY SEPARABLE COATING COMPOUNDS |
| ATA9211/76 | 1976-12-13 | ||
| AT921176A AT343771B (en) | 1976-12-13 | 1976-12-13 | PROCESS FOR THE PRODUCTION OF WARM-HARDENABLE BINDERS FOR CATHODICALLY SEPARABLE COATING COMPOUNDS |
| ATA9210/76 | 1976-12-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1094708A true CA1094708A (en) | 1981-01-27 |
Family
ID=25605369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,913A Expired CA1094708A (en) | 1976-12-13 | 1977-12-12 | Process for producing thermosetting binders for cathodic electrodeposition coating |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5394597A (en) |
| CA (1) | CA1094708A (en) |
| DE (1) | DE2755538C3 (en) |
| FR (1) | FR2373594A1 (en) |
| GB (1) | GB1576159A (en) |
| IT (1) | IT1088537B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT356226B (en) * | 1977-10-24 | 1980-04-10 | Vianova Kunstharz Ag | METHOD FOR PRODUCING CATHODICALLY DEPOSIBLE BINDERS |
| AT366401B (en) * | 1979-11-05 | 1982-04-13 | Vianova Kunstharz Ag | METHOD FOR PRODUCING WATER-DETERMINATABLE BINDERS CARRYING OXAZOLIDING GROUPS |
| DE3124088A1 (en) * | 1981-06-19 | 1983-01-05 | Basf Ag, 6700 Ludwigshafen | BATH COMPOSITION FOR CATAPHORETIC ELECTRO DIP PAINTING |
| AT376231B (en) * | 1982-12-20 | 1984-10-25 | Vianova Kunstharz Ag | METHOD FOR PRODUCING CATIONIC LACQUER |
| US6423425B1 (en) | 1998-05-26 | 2002-07-23 | Ppg Industries Ohio, Inc. | Article having a chip-resistant electrodeposited coating and a process for forming an electrodeposited coating |
| US6248225B1 (en) | 1998-05-26 | 2001-06-19 | Ppg Industries Ohio, Inc. | Process for forming a two-coat electrodeposited composite coating the composite coating and chip resistant electrodeposited coating composition |
| DE19958488A1 (en) * | 1999-12-04 | 2001-06-21 | Dupont Performance Coatings | Aqueous electrocoating paints, their manufacture and use |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3799854A (en) * | 1970-06-19 | 1974-03-26 | Ppg Industries Inc | Method of electrodepositing cationic compositions |
| US3823118A (en) * | 1970-12-29 | 1974-07-09 | Mitsubishi Chem Ind | Process for preparing thermosettable urethane resin |
| AU472873B2 (en) * | 1971-07-29 | 1976-06-10 | Ppg Industries Inc | Zwitterion-containing compositions |
| CA986639A (en) * | 1971-10-28 | 1976-03-30 | Robert R. Zwack | Cationic electrodepositable compositions |
-
1977
- 1977-12-12 CA CA292,913A patent/CA1094708A/en not_active Expired
- 1977-12-13 GB GB5182177A patent/GB1576159A/en not_active Expired
- 1977-12-13 JP JP14889277A patent/JPS5394597A/en active Pending
- 1977-12-13 DE DE19772755538 patent/DE2755538C3/en not_active Expired
- 1977-12-13 IT IT3067377A patent/IT1088537B/en active
- 1977-12-13 FR FR7737520A patent/FR2373594A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2755538A1 (en) | 1978-06-15 |
| DE2755538C3 (en) | 1986-10-02 |
| GB1576159A (en) | 1980-10-01 |
| IT1088537B (en) | 1985-06-10 |
| JPS5394597A (en) | 1978-08-18 |
| FR2373594B1 (en) | 1981-01-23 |
| FR2373594A1 (en) | 1978-07-07 |
| DE2755538B2 (en) | 1980-09-25 |
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