CA1096079A - Aqueous dispersed urethane composition - Google Patents
Aqueous dispersed urethane compositionInfo
- Publication number
- CA1096079A CA1096079A CA265,307A CA265307A CA1096079A CA 1096079 A CA1096079 A CA 1096079A CA 265307 A CA265307 A CA 265307A CA 1096079 A CA1096079 A CA 1096079A
- Authority
- CA
- Canada
- Prior art keywords
- parts
- composition
- urethane
- molecular weight
- urethane oligomer
- 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.)
- Expired
Links
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
- C03C17/322—Polyurethanes or polyisocyanates
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
Abstract
Abstract of the Disclosure An aqueous dispersed urethane composition which is excellent in film-forming property and useful in protecting glass bottles when forward into a film can be obtained by producing a urethane oligomer by interacting a polyoxyalkylene glycol having a molecular weight above 1200, a low molecular weight chain-elongating agent selected from a glycol, an aminoalcohol and a diamine each having a molecular weight below 500, an isocyanate-blocking agent selected from an oxime, a lactam and an alcohol, and a diisocyanate, and dispersing the urethane oligomer and a hardener in water by the use of a sur-face active agent such that the sum by weight of the surface active agent contained in the aqueous dispersed urethane composition and the polyoxyalkylene glycol to be one of the starting materials for the production of the urethane oligomer is in the range of 15 to 35% of the sum by weight of the surface active agent, the urethane oligomer and the hardener.
Description
`7~
This invention relates to an aqueous dispersed urethane composition.
More particularly but not exclusively, it relates to an aqueous dispersed urethane composition obtained by dispersing a thermosetting urethane composi-tion in water by means of a surface active agent.
A serious problem has bean encountered upon breakage of glass bottles, particularly in handling carbonated beverages bottled with high internal pressure and there is accordingly a strong demand for preventing accidents to the human body due to scattering of the glass pieces upon breakage.
There is known a method for preventing such accidents by closely laminating a resin film such as polyvinyl chloride, polyester, polyurethane, or the like resin, on the outer surface of glass bottles, with an adhesive agent used as an intermediate layer. United States Patent No. 3,886,226 des-cribes a method for directly adhering a polyurethane film on glass bottles for preventing accidents. In general, films for protecting glass bottles or preventing glass bottles from being scattered upon breakage are required to be excellent in properties, i.e., adhesion to glass, suitable degree of flexibil-ity to prevent glass bottles from being scattered upon breakage, sufficient resistance to hot water and to hot alkali solution employed in washing and sterilizing glass bottles, lubricity characteristics sufficient to permit a flow operation in a manufacturing line, sufficient hardness, mechanical strength, scratch resistance characteristics, abrasion resistance, weather resistance and fungus resistance to withstand handling during the course of the bottling process and transportation, colorless transparency required not ;
to impair the beautiful appearance of the coated glass products, non-toxic etc. -A single protecting layer derived from a urethane composition dis-persed in water has been considered unsatisfactory owing to difficulty in satis-fying the above requirements. An intermediate layer formed from an aqueous dispersed natural rubber or styrene-butadiene rubber and also a top layer from an epoxy resin are generally used fcr this purpose.
it~
The present invention provides an aqueous dispersed urethane com-position which protects glass bottlesJ when formed into a film, when applied as a single layer araund the bottles and which does not require large amount of organic solvents for application.
According to the present invention, there is provided an aqueous dispersed urethane composition comprising a urethane oligomer obtained by interacting a mixture of bifunctional active hydrogen-containing compounds and a monofunctional active hydrogen-containing isocyanate-blocking agent, and a diisocyanate under such conditions that an equivalent ratio of the active hydrogen contained in said mixture to the isocyanate group of said diisocyanate is about 1.0, a hardener mixed with said urethane oligomer in an equivalent ratio of the blocked isocyanate of said urethane oligomer to the active hydrogen of said hardener in the range of 1:0.8 to 1.2 whereby a thermosetting urethane composition is obtained, and a surface active agent for dispersing said thermosetting urethane composition in water, wherein ~1) said bifunctional active hydrogen-containing compounds are composed of a polyoxyalkylene glycol having a molecular weight above 1200 and a low molecular weight chain-elongating agent, (2) the sum by weight Oe said surface active agent contained in said aqueous dispersed urethane composition and said polyoxyalkylene glycol to be one of the starting material for the production of said urethane oligomer is in the range of 15 to 35% of the sum by weight of said surface active agent contained in said aqueous dispersed -urethane composition and said thermosetting urethane composition, (3) the molecular weight of the urethane oligomer is in the range of 1000 to 5000, (4) the amount of the polyoxyalkylene glycol is in the range of 10 to 35 parts by weigh~ per 100 parts by weight of the urethane oligomer, and (5) the amount of the low molecular weight chain-elongating agent is in the range of 15 to 55 parts by weight per 100 parts by weight of the urethane oligomer.
The present invention also provides a method of forming a protective .
; ~ ~ - 2 -37~
filnl cn a glass bottle ~hich comprises co~ting the outer surface of the bottle with the above composition~
Furthe~more, the present invention provides a glass bottle coated on its outer surface ~ith the above composition to form a protective film on the outer surface of the glass ~ottle. ~ -For convenience sake, weights of the respective components con-stituting the aqueous dispersed urethane composition of the invention will be hereinafter referred to simply as A for polyoxyalkylene glycol, B for the low molecular weight chain-elongating agent, C for the blocking agent, D for the diisocyanate, E for the urethane oligomer obtained by the reaction of the above four components, F for the hardener, and G for the surface active agent ` _ 2a -employed for dispersion of the oligomer and the hardener in water.
The relation of the item (2) of the above characterized clause can be expressed by the following equation ~I) A + G x 100 = 15 to 35 (I) E + F + G
The polyoxyalkylene glycols which are one of the bifunctional active hydrogen-containing compounds for use in production of the urethane oligomer ~; include, for example polyether diols including polyoxyethylene glycol, poly-oxypropylene glycol, polyoxytetrametllylene glycol and copolymerized glycols such as polyoxyethylenepropylene glycol, polyoxypropylenetetramethylene glycol, etc. The polyoxyalkylene glycols must have a molecular weight above 1200, preferably in the range of 1200 to 5000. With the molecular weight below 1200, the film for protecting glass bottles obtained from an aqueous dispersed urethane composition using such low molecular weight polyoxyalkylene glycol shows an unfavorable effect on prevention of glass scattering upon breakage of a glass bottle, particularly under low temperature conditions. The poly-ether diols may be used singly or in combination.
The molecular weight of polyoxyalky].ene glycols can be determined by the measurement of the OH value, which is in turn determined by a so-called phthalic anhydride method. That is, polyoxyalkylene glycol is first esteri-fied with 2 reagent of a pyridine solution of phthalic anhydride and then an excess of the reagent is titrated with a sodium hydroxide standard solution.
The OH value means a value of mg of KOH corresponding to the OH group con-tained in 1 g o the sample. The molecular weight of the sample can be cal- - -culated from the obtained OH value on the basis of the following equation molecular weight = 2 x 56-11 x 100 OH value There are usable as the low molecular weight chain-elongating agent which is the :
other bifunctional active hydrogen-containing compound for use in the produc-tion of the urethane oligomer, known chain-elongating agents employed to produce polyurethane elastomers. The usable chain-elongating agents include glycols, aminoalcohols, diamines and the like. The chain-elongating agents having a molecular weight below 500 is preferable. Examples of the ~6~9 glycols are ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-buty-lene glycol, 1,6-hexylene glycol, diethylene glycol, dipropylene glycol and the like. Examples of the aminoalcohols are monoethanolamine, monoisopropanol-amine and the like. Examples of the diamines are ethylene diamine, butylene-diamine, 4,4-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, isophoronediamine and the like. These compounds may be used singly or in combination, and may be used in combination with aminosilane compounds such as N-~-(aminoethyl)-~-aminopropyltrimethoxysilane, N-~-(aminoethyl)-~-amino-propyltriethoxysilane and the like.
The monofunctional active hydrogen-containing isocyanate-blocking agents useful in the present invention include, fGr example, phenols such as phenol, o-cresol, xylenol, nonylphenol, etc., lactams such as ~-butyrolactam, ~-caprolactam, etc., oximes such as methyl ethyl ketoxime, acetoxime, etc., imides such as succinimide, phthalic acid imide, etc., malonic esters, acetoacetic esters, monofunctional alcohols such as butanol, isopropanol, t-butylalcohol, etc. Of these, the lactams, oximes and alcohols are most preferable.
The diisocyanates suitable for the production of the urethane oligomers are those usually employed for the production of polyurethanes and include 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, 4,4'-diphenyl-methanediisocyanate, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, 3,3'-dimethyl-4,4'-diphenyldiisocyanate, 1,6-hexamethylenediisocyanate, 4,4'-dicyclohexylmethanediisocyanate, isophoronediisocyanate and the like. These diisocyanates may be used singly or in mixtures of two or more. Of these, the most preferred diisocyanates are 2,4-tolylenediisocyanate, 2,6-tolylene-diisocyanate, 4,4'-diphenylmethanediisocyanate, 1,6-hexamethylenediisocyanate, 4,4'-dicyclohexylmethanediisocyanate and isophoronediisocyanate. --The amount of the isocyanate-blocking agent has considerable in-fluence on the molecular weight of the urethane oligomer product. A preferred amount of the blocking agent is in the range of 0.4 to 2 gram moles per kg of " . . . .
~: :
,., , : . , : . , . : ::
~96~7~
urethane oligomer. Use of the blocking agent in the above-defined range en-sures formation of a urethane oligomer having a molecular weight of 1000 to 5000. If the molecular weight of the urethane oligomer is below 1000, the film obtained from the resulting aqueous dispersed urethane composition is not sufficiently effective for preventing the glass bottles from being ~ ~-scattered upon breakage. If the aqueous urethane dispersion composition uses a urethane oligomer having a molecular weight above 5000, the protection film obtained from the composition has reduced resistance to water and turns white when immersed in hot water.
In the practice of the invention, the amount of the polyoxyalkylene glycol is preferably in the range of 10 to 35 parts by weight per 100 parts by weight of the urethane oligomer. With the amount below 10 parts by weight, the protection film for glass bottles obtained from the resulting aqueous dispersed urethane composition is not sufficiently effective in preventing the glass bottles from being scattered upon breakage. Use of a polyoxyalkylene glycol in an amount greater than 35 parts by weight per 100 parts by weight of the urethane oligomer reduces the resistance of the film to violent impact which is likely to occur in a bottling line.
The preferred amount of the low molecular weight chain-elongating agent is in the range of 15 to 55 parts by weight per 100 parts by weight of the urethane oligomer. The film prepared from an aqueous dispersed urethane composition containing the chain-elongating agent in an amount above 55 parts by weight is inferior in the scattering-preventing effect. ~ith a composition containing the chain-elongating agent below 15 parts by weight per 100 parts by weight of the urethane oligomer the film obtained from the composition has reduced resistance to violent impact which may occur in a bot~ling line.
The amount of the diisocyanates is determined by a requirement that the isocyanate group of the diisocyanate is almost equivalent by mole to a total of the active hydrogen of the three active hydrogen-containing compounds, i.e., the polyoxyalkylene glycol and the low molecular weight chain-elongating ~9~
agent each to be a bifunctional active hydrogen-containing compound and the isocyanate-blocking agent to be a monofunctional active hydrogen-containing compound.
Though the urethane oligomer can be prepared by introducing for oligomerization reaction all of the starting materials into a reactor together with a solvent, it is preferred to conduct the reaction by the following steps.
First, a polyoxyalkylene glycol is reacted with some of the diisocyanate to prepare a prepolymer, to which the balance of the diisocyanate and a solvent are added, then the reaction with an isocyanate-blocking agent is carried out at a temperature in the range of from 25C to 50C. As a matter of course, all of the diisocyanate may be charged upon preparing the prepolymer. The blocking reaction time depends on the kind of blocking agent employed. In the production of the urethane oligomer in accordance with the present inven-tion, the reaction takes about 2 hours. Then, a predetermined amount of a low molecular weight chain-elongating agent is charged into the reaction mass for reaction to obtain a desired oligomer. The reaction of the chain-elongat-ing agent and the diisocyanate should preferably be effected at a temperature below 80C. It will be noted that the blocking reaction is Eeasible in the absence of solvent but, in such a case, it is necessary to add a solvent to the reaction system prior to the charging of the low molecular weight chain-elon-gating agent. Almost all solventswllich are inert to the diisocyanates and readily miscible with the urethane polymer may be used as reaction solvent.
However, a reaction solvent which is capable of being removed with ease by suitable means is preferred. Methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, cellosolve acetate and toluene are preferred though dimethylformamide is unfavorable.
The reaction solvent is generally used in such an amount that the concentration of the urethane oligomer obtained after completion of the oligomerization reaction is in the range of from 50 to 95% by weight. When a diamine is used as the chain-elongating agent~ the reaction with the chain-: 6 .' "' ~' ' ' ~ .' ~96~
elongatlng agent is Eeasible at a temperature of 10 to 50C and generally complete within a time period of 1 to 5 hours. If an aminoalcohol being used as the chain-elongating agent the reaction is conducted at a temperature of 50 to 80C. Use of a glycol as the chain-elongating agent requires a fairly long period of reaction time even when the reaction is effected at 80C. In order to shorten the reaction time, a catalyst is generally used so that the reaction is feasible at a reaction temperature of 50 to 80 and complete within about 5 hours. Examples of suitable catalysts include organic tin compounds such as dibutyl tin dilaurate, dibutyl tin di~2-ethylhexoate), tin
This invention relates to an aqueous dispersed urethane composition.
More particularly but not exclusively, it relates to an aqueous dispersed urethane composition obtained by dispersing a thermosetting urethane composi-tion in water by means of a surface active agent.
A serious problem has bean encountered upon breakage of glass bottles, particularly in handling carbonated beverages bottled with high internal pressure and there is accordingly a strong demand for preventing accidents to the human body due to scattering of the glass pieces upon breakage.
There is known a method for preventing such accidents by closely laminating a resin film such as polyvinyl chloride, polyester, polyurethane, or the like resin, on the outer surface of glass bottles, with an adhesive agent used as an intermediate layer. United States Patent No. 3,886,226 des-cribes a method for directly adhering a polyurethane film on glass bottles for preventing accidents. In general, films for protecting glass bottles or preventing glass bottles from being scattered upon breakage are required to be excellent in properties, i.e., adhesion to glass, suitable degree of flexibil-ity to prevent glass bottles from being scattered upon breakage, sufficient resistance to hot water and to hot alkali solution employed in washing and sterilizing glass bottles, lubricity characteristics sufficient to permit a flow operation in a manufacturing line, sufficient hardness, mechanical strength, scratch resistance characteristics, abrasion resistance, weather resistance and fungus resistance to withstand handling during the course of the bottling process and transportation, colorless transparency required not ;
to impair the beautiful appearance of the coated glass products, non-toxic etc. -A single protecting layer derived from a urethane composition dis-persed in water has been considered unsatisfactory owing to difficulty in satis-fying the above requirements. An intermediate layer formed from an aqueous dispersed natural rubber or styrene-butadiene rubber and also a top layer from an epoxy resin are generally used fcr this purpose.
it~
The present invention provides an aqueous dispersed urethane com-position which protects glass bottlesJ when formed into a film, when applied as a single layer araund the bottles and which does not require large amount of organic solvents for application.
According to the present invention, there is provided an aqueous dispersed urethane composition comprising a urethane oligomer obtained by interacting a mixture of bifunctional active hydrogen-containing compounds and a monofunctional active hydrogen-containing isocyanate-blocking agent, and a diisocyanate under such conditions that an equivalent ratio of the active hydrogen contained in said mixture to the isocyanate group of said diisocyanate is about 1.0, a hardener mixed with said urethane oligomer in an equivalent ratio of the blocked isocyanate of said urethane oligomer to the active hydrogen of said hardener in the range of 1:0.8 to 1.2 whereby a thermosetting urethane composition is obtained, and a surface active agent for dispersing said thermosetting urethane composition in water, wherein ~1) said bifunctional active hydrogen-containing compounds are composed of a polyoxyalkylene glycol having a molecular weight above 1200 and a low molecular weight chain-elongating agent, (2) the sum by weight Oe said surface active agent contained in said aqueous dispersed urethane composition and said polyoxyalkylene glycol to be one of the starting material for the production of said urethane oligomer is in the range of 15 to 35% of the sum by weight of said surface active agent contained in said aqueous dispersed -urethane composition and said thermosetting urethane composition, (3) the molecular weight of the urethane oligomer is in the range of 1000 to 5000, (4) the amount of the polyoxyalkylene glycol is in the range of 10 to 35 parts by weigh~ per 100 parts by weight of the urethane oligomer, and (5) the amount of the low molecular weight chain-elongating agent is in the range of 15 to 55 parts by weight per 100 parts by weight of the urethane oligomer.
The present invention also provides a method of forming a protective .
; ~ ~ - 2 -37~
filnl cn a glass bottle ~hich comprises co~ting the outer surface of the bottle with the above composition~
Furthe~more, the present invention provides a glass bottle coated on its outer surface ~ith the above composition to form a protective film on the outer surface of the glass ~ottle. ~ -For convenience sake, weights of the respective components con-stituting the aqueous dispersed urethane composition of the invention will be hereinafter referred to simply as A for polyoxyalkylene glycol, B for the low molecular weight chain-elongating agent, C for the blocking agent, D for the diisocyanate, E for the urethane oligomer obtained by the reaction of the above four components, F for the hardener, and G for the surface active agent ` _ 2a -employed for dispersion of the oligomer and the hardener in water.
The relation of the item (2) of the above characterized clause can be expressed by the following equation ~I) A + G x 100 = 15 to 35 (I) E + F + G
The polyoxyalkylene glycols which are one of the bifunctional active hydrogen-containing compounds for use in production of the urethane oligomer ~; include, for example polyether diols including polyoxyethylene glycol, poly-oxypropylene glycol, polyoxytetrametllylene glycol and copolymerized glycols such as polyoxyethylenepropylene glycol, polyoxypropylenetetramethylene glycol, etc. The polyoxyalkylene glycols must have a molecular weight above 1200, preferably in the range of 1200 to 5000. With the molecular weight below 1200, the film for protecting glass bottles obtained from an aqueous dispersed urethane composition using such low molecular weight polyoxyalkylene glycol shows an unfavorable effect on prevention of glass scattering upon breakage of a glass bottle, particularly under low temperature conditions. The poly-ether diols may be used singly or in combination.
The molecular weight of polyoxyalky].ene glycols can be determined by the measurement of the OH value, which is in turn determined by a so-called phthalic anhydride method. That is, polyoxyalkylene glycol is first esteri-fied with 2 reagent of a pyridine solution of phthalic anhydride and then an excess of the reagent is titrated with a sodium hydroxide standard solution.
The OH value means a value of mg of KOH corresponding to the OH group con-tained in 1 g o the sample. The molecular weight of the sample can be cal- - -culated from the obtained OH value on the basis of the following equation molecular weight = 2 x 56-11 x 100 OH value There are usable as the low molecular weight chain-elongating agent which is the :
other bifunctional active hydrogen-containing compound for use in the produc-tion of the urethane oligomer, known chain-elongating agents employed to produce polyurethane elastomers. The usable chain-elongating agents include glycols, aminoalcohols, diamines and the like. The chain-elongating agents having a molecular weight below 500 is preferable. Examples of the ~6~9 glycols are ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-buty-lene glycol, 1,6-hexylene glycol, diethylene glycol, dipropylene glycol and the like. Examples of the aminoalcohols are monoethanolamine, monoisopropanol-amine and the like. Examples of the diamines are ethylene diamine, butylene-diamine, 4,4-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, isophoronediamine and the like. These compounds may be used singly or in combination, and may be used in combination with aminosilane compounds such as N-~-(aminoethyl)-~-aminopropyltrimethoxysilane, N-~-(aminoethyl)-~-amino-propyltriethoxysilane and the like.
The monofunctional active hydrogen-containing isocyanate-blocking agents useful in the present invention include, fGr example, phenols such as phenol, o-cresol, xylenol, nonylphenol, etc., lactams such as ~-butyrolactam, ~-caprolactam, etc., oximes such as methyl ethyl ketoxime, acetoxime, etc., imides such as succinimide, phthalic acid imide, etc., malonic esters, acetoacetic esters, monofunctional alcohols such as butanol, isopropanol, t-butylalcohol, etc. Of these, the lactams, oximes and alcohols are most preferable.
The diisocyanates suitable for the production of the urethane oligomers are those usually employed for the production of polyurethanes and include 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, 4,4'-diphenyl-methanediisocyanate, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, 3,3'-dimethyl-4,4'-diphenyldiisocyanate, 1,6-hexamethylenediisocyanate, 4,4'-dicyclohexylmethanediisocyanate, isophoronediisocyanate and the like. These diisocyanates may be used singly or in mixtures of two or more. Of these, the most preferred diisocyanates are 2,4-tolylenediisocyanate, 2,6-tolylene-diisocyanate, 4,4'-diphenylmethanediisocyanate, 1,6-hexamethylenediisocyanate, 4,4'-dicyclohexylmethanediisocyanate and isophoronediisocyanate. --The amount of the isocyanate-blocking agent has considerable in-fluence on the molecular weight of the urethane oligomer product. A preferred amount of the blocking agent is in the range of 0.4 to 2 gram moles per kg of " . . . .
~: :
,., , : . , : . , . : ::
~96~7~
urethane oligomer. Use of the blocking agent in the above-defined range en-sures formation of a urethane oligomer having a molecular weight of 1000 to 5000. If the molecular weight of the urethane oligomer is below 1000, the film obtained from the resulting aqueous dispersed urethane composition is not sufficiently effective for preventing the glass bottles from being ~ ~-scattered upon breakage. If the aqueous urethane dispersion composition uses a urethane oligomer having a molecular weight above 5000, the protection film obtained from the composition has reduced resistance to water and turns white when immersed in hot water.
In the practice of the invention, the amount of the polyoxyalkylene glycol is preferably in the range of 10 to 35 parts by weight per 100 parts by weight of the urethane oligomer. With the amount below 10 parts by weight, the protection film for glass bottles obtained from the resulting aqueous dispersed urethane composition is not sufficiently effective in preventing the glass bottles from being scattered upon breakage. Use of a polyoxyalkylene glycol in an amount greater than 35 parts by weight per 100 parts by weight of the urethane oligomer reduces the resistance of the film to violent impact which is likely to occur in a bottling line.
The preferred amount of the low molecular weight chain-elongating agent is in the range of 15 to 55 parts by weight per 100 parts by weight of the urethane oligomer. The film prepared from an aqueous dispersed urethane composition containing the chain-elongating agent in an amount above 55 parts by weight is inferior in the scattering-preventing effect. ~ith a composition containing the chain-elongating agent below 15 parts by weight per 100 parts by weight of the urethane oligomer the film obtained from the composition has reduced resistance to violent impact which may occur in a bot~ling line.
The amount of the diisocyanates is determined by a requirement that the isocyanate group of the diisocyanate is almost equivalent by mole to a total of the active hydrogen of the three active hydrogen-containing compounds, i.e., the polyoxyalkylene glycol and the low molecular weight chain-elongating ~9~
agent each to be a bifunctional active hydrogen-containing compound and the isocyanate-blocking agent to be a monofunctional active hydrogen-containing compound.
Though the urethane oligomer can be prepared by introducing for oligomerization reaction all of the starting materials into a reactor together with a solvent, it is preferred to conduct the reaction by the following steps.
First, a polyoxyalkylene glycol is reacted with some of the diisocyanate to prepare a prepolymer, to which the balance of the diisocyanate and a solvent are added, then the reaction with an isocyanate-blocking agent is carried out at a temperature in the range of from 25C to 50C. As a matter of course, all of the diisocyanate may be charged upon preparing the prepolymer. The blocking reaction time depends on the kind of blocking agent employed. In the production of the urethane oligomer in accordance with the present inven-tion, the reaction takes about 2 hours. Then, a predetermined amount of a low molecular weight chain-elongating agent is charged into the reaction mass for reaction to obtain a desired oligomer. The reaction of the chain-elongat-ing agent and the diisocyanate should preferably be effected at a temperature below 80C. It will be noted that the blocking reaction is Eeasible in the absence of solvent but, in such a case, it is necessary to add a solvent to the reaction system prior to the charging of the low molecular weight chain-elon-gating agent. Almost all solventswllich are inert to the diisocyanates and readily miscible with the urethane polymer may be used as reaction solvent.
However, a reaction solvent which is capable of being removed with ease by suitable means is preferred. Methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, cellosolve acetate and toluene are preferred though dimethylformamide is unfavorable.
The reaction solvent is generally used in such an amount that the concentration of the urethane oligomer obtained after completion of the oligomerization reaction is in the range of from 50 to 95% by weight. When a diamine is used as the chain-elongating agent~ the reaction with the chain-: 6 .' "' ~' ' ' ~ .' ~96~
elongatlng agent is Eeasible at a temperature of 10 to 50C and generally complete within a time period of 1 to 5 hours. If an aminoalcohol being used as the chain-elongating agent the reaction is conducted at a temperature of 50 to 80C. Use of a glycol as the chain-elongating agent requires a fairly long period of reaction time even when the reaction is effected at 80C. In order to shorten the reaction time, a catalyst is generally used so that the reaction is feasible at a reaction temperature of 50 to 80 and complete within about 5 hours. Examples of suitable catalysts include organic tin compounds such as dibutyl tin dilaurate, dibutyl tin di~2-ethylhexoate), tin
2-ethylcaproate, tin oleate, etc. Of these, dibutyl tin dilaurate is most preferred and is generally used in an amount of 0.001 to 0.1 part by weight per 100 parts by weight of the oligomer. The reaction for the preparation of the prepolymer is conducted at a temperature of 30 to 80C, preferably at about 60C.
The hardeners which are used with the urethane oligomer in the present invention are those ordinarily employed for polyurethane, including polyfunc-tional alcohols, amines and amino-alcohols, etc. These compoun~s preferably have a Inolecular weight below 500. Examples of the polyEunctional alcohols are pentaerythritol, trimethylolpropane, glycerol, adducts having an OH value greater than 450 and obtained by addition reaction of propylene oxide with trimethylolpropane and adducts having an OH value above 450 and obtained by ~;
addition reaction of glycerine wtih propylene oxide, etc. Examples of the polyfunctional amines include triethylenetetramine, diethylenetriamine, etc.
Examples of the aminoalcohols include diethanolamine, triethanolamine, tri- ~ ~
isopropanolamine, diisopropanolamine, an adduct of 1 mole of ethylenediamine ~ -and less than 4 moles of propylene oxide.
The amount of the hardener is determined such that an equivalent ratio of the blocked isocyanate contained in the urethane oligomer to the active hydrogen of the hardener is in the range of 1:0.8 to 1.2.
The surface active agents employed for dispersing the thermosetting .
7~
urethane composition in water are conventional nonionic active agents including, for example, an addition product of nonylphenol and ethylene oxide, a copolymer of propylene oxide and ethylene oxide, and the like. In view of chemical stability and water resistance, the propylene oxide-ethylene oxide copolymer having a molecular weight above 10,000 and an ethylene oxide content of above 60% by weight is preferred. In addition, polyethyleneglycol alkylphenyl ethers may also be used as the surface active agent. The preferred amount of the surface active agent is in the range of 4 to 25 parts by weight per 100 parts by weight of the urethane oligomer which is used for preparing the thermo- -s setting urethane composition. As a matter of course, the amount of surface active agent depends on the amounts of the other components essentially re-quired for the production of the aqueous dispersed urethane composition of the invention and may appropriately vary within the above defined range such that, as indicated hereinbefore in the equation ~I), the sum of the weight A
of the polyoxyalkylene glycol used for the preparation of the urethane oligomer and the weight G of the surface active agent employed for dispersing the urethane oligomer and a hardener in water is in the range of 15 to 35% by weight based on the sum of the weight E of the oligomer, the weight ~ of the hardener and the weight G of the surface active agent emyloyed for the dispersion. With the range below 15%, the film obtained from such aqueous urethanedispersion composition is inferior in preventing the film-applied glass bottle from being scattered upon breakage thereof. The range above 35%
is unfavorable since the resulting film becomestoo soft and exhibits poor durability when used for protecting purpose.
The dispersion or emulsification is feasible by adding a surface active agent to the thermosetting urethane composition which is prepared by mixing a urethane oligomer with a hardener, and mixing the mixture under high shearing conditions while gradually adding water. Use of a urethane oligomer having a relatively high molecular weight requires use of solvent ` ~ -so as to reduce the viscosity of the dispersion. The solvent usable for this purpose is that which is employable upon the preparation of the urethane oligomer and which can be readily distilled off after completion of the dis-persion. Examples of the solvent are methyl ethyl ketone, toluene, tetra-hydrofuran, acetone, dioxane, etc. On]y for viscosity-reducing purpose there are used various kinds of solvents such as cellosolve acetate, butylcellosolve acetate, 2-nitropropane, ethylene glycol, diethyl ether and the like.
The emulsification method will be particularly described.
The urethane oligomer is first dissolved in solvent to prepare a urethane oligomer solution having a viscosity of 100,000 cps at room tempera-ture. In order to prepare such solution, it will suffice to use 50 parts of the solvent per 100 parts of the urethane oligomer. To the oligomer solution are added a hardener and then a surface active agent to obtain a uniform solution. Then, water is added to the solution in an amount of 100 to 250 parts per 100 parts of the urethane oligomer employed. Water to be added to the solution is preferred to be divided into three portions and added stepwise.
That is, 1/3 of a predetermined amount of water is added under conditions to revolutions of above 1,000 r.p.m. when a propeller-type agitation blade is used for agitation. Each 1/3 of the balance of water may be added without any limitation of the number of revolutions but is preferred to agitate for more than 15 min in each step after completion of the addition of water.
After completion of the dispersion in water, the solvent used is preferably removed by distillation at a temperature of 20 to ~0C under reduced pressure.
Known aqueous dispersed polyurethane compositions using surface active agents have detrimental disadvantages in low waterproof properties and also in that the dispersion is unstable and accordingly the dispersed phase tends to precipitate with a lapse of time.
The composition of the invention is a novel one which overcomes the ;
disadvantages of the prior compositions and in which the molecular weight and amount of the polyoxyalkylene glycol, the molecular weight of the urethane oligomer and the amount of the surface active agent are so interdependent that 9_ 6~7~1 the dispersion composition in an optimum region of composition exhibits un-expected excellent characteristic properties suitable for glass bottle protec-tion. Known aqueous dispersed polyurethane compositions using surface active agents are also disadvantageous because they suffer a loss of transparency when formed into films and immersed in water and can not be used at all as coatings for glass bottles.
In order to improve the waterproof properties of an aqueous emulsion, generally use is made of crosslinkage of a polymeric resin. There has been proposed an improved aqueous dispersed polyurethane composition which can yield a film with improved waterproof properties. However, this composition has drawbacks that the film is poor in ability for preventing glass bottles from being scattered upon breakage of the bottles and also in durability. The composition can not be used as coatings for protecting glass bottles by application of single protecting film layer thereof.
The film prepared from the composition of the invention has, as will be particularly indicated in Table mentioned hereinafter, excellent mechanical strength and waterproof properties and does not lose its transparency when placed in hot water at 70C. The composition of the invention provides a coating for protecting glass bottles by single coating layer with excellent properties such as the scattering-preventing ability and a prolonged dura-bility.
The present invention will be particularly described by way of the following examples and comparative examples, in which parts are by weight.
2000 parts of polyoxypropylene glycol having a molecular weight of 2000 and 870 parts of 2,4-tolylenediisocyanate ~hereinafter referred to simply as TDI-100) were placed in a reactor and heated to 60C with agitation, followed by reaction at 60C for 3 hours under agitating conditions to obtain a prepolymer compound (hereinafter referred to as prepolymer P-l).
284 parts of the thus obtained prepolymer P-l, 261 parts of 2,4-.. . .~ :. .- , tolylenediisocyanate and 337 parts of cellosolve acetate were mixed and main-tained at 20C with agitation, to which was dropwise added 52 parts of methyl ethyl ketoxime over 1 hours. After completion of the dropping, 189 parts of 1,6-hexylene glycol was added to the reaction mass, which was heated up to 60C in 30 min and maintained at 60C for 1 hour. Thereafter, 0.25 parts of dibutyl tin dilaurate was added to the reaction mass, followed by further heating to 80C and maintaining at 80C for 3 hours to obtain a urethane oligomer ~hereinafter referred to urethane oligomer E-l). 107 parts of the urethane oligomer E-l (including the reaction solvent) was added with 2.3 `
o B parts of trimethylolpropane and 5.2 parts of a surface active agent, Epan 785 (polyoxypropylenepolyoxyethylene ether produced by Daiichi Kogyo Seiyaku K.K.), ;;
to which was gradually added 85.5 parts of water under high shearing conditions to give an aqueous dispersed urethane composition (hereinafter referred to as aqueous dispersed urethane composition H-l). The aqueous dispersed urethane composition H-l has a viscosity of 120 cps at 30C and was stable over 6 months at room temperature.
A thin layer of the composition H-l was subjected to film formation, that is, dried and cured at 60C for 30 min and then at 150C for 120 min to obtain a film with excellent mechanical strengths. Tlle properties and strengths of the film are tabulated in Table appearing below.
1500 parts of polyoxytetramethylene glycol having a molecular weight of 1500 and 870 parts of a mixture of 2,4-tolylenediisocyanate and 2,6-toly-lenediisocyanate in a ratio by weight of 8:2 (hereinafter referred to simply as TDI 80/20) were placed in a reactor and heated up to 60C while agitating, followed by reaction at 60C for 2 hours, thereby obtaining a prepolymer (hereina~ter referred to as prepolymer P-2). 351 parts of the thus obtained prepolymer P-2, 155 parts of TDI 80/20, 150 parts of toluene and 150 parts of tetrahydrofuran were mixed and maintained at 40C with agitation, to which was ; 30 stepwise added over 1 hour 100 parts of ~-caprolactam which had been divided ~ ~ule :- . . ................... ~ - . :
. ~ .
into three portions. The reaction mass was heated to 50C and kept at 50C
for 1 hour for reactionJ to which was further added 93 parts of 1,4-butylene glycol, followed by heating to 70C. Then, 0.21 parts of dibutyl tin di-laurate was added to the heated reaction mass for further reaction at 70C
for 5 hours to obtain a urethane oligomer (hereinafter referred to as urethane oligomer E-2).
125.5 parts of the urethane oligomer E-2 ~including the reaction solvent), 5.0 parts of trimethylolpropane, 3.5 parts of surface active agent, Emulsit 16 ~polyethylene glycol alkylphenyl ether produced by Daiichi Kogyo Seiyaku K.K.) and 3.5 parts of Epan 785 were mixed with one another, to which ~-was gradually added 163 parts of water under high shearing conditions. After completion of the dispersion, the reaction solvent was distilled off under reduced pressure to obtain an aqueous dispersed urethane composition H-2. The composition H-2 had a viscosity of 80 cps at 30C and was stable over 3 months at room temperature.
A thin layer of the composition H-2 was subjected to film formation, tllat is, dried and cured at 60C for 30 min and then at 150C for 120 min to obtain a tough film. The characteristic properties oE the Eilm are shown in the Table below.
2000 parts of polyoxypropylene glycol having a molecular weight of ~ -3000 and 870 parts of TDI 80/20 were mixed and heated to 60C with agitation, followed by reaction at 60C for 3 hours under agitating conditions, thereby yielding a prepolymer P-3. 77.4 parts of the thus obtained prepolymer P-3, 361.9 parts of TDI 80/20, 267 parts of tetrahydrofuran and 200 parts of cellosolve acetate were mixed and kept at 25C with agitation, to which was ` stepwise added over 1 hour 30.7 parts, in total, of acetoxime which had been ~ divided into three portions, followed by further reaction at 25C for 30 min.
: Then 230 parts of 1,6-hexylene glycol was added to the reaction mass, followed by heating to 70C and adding 0.21 parts of dibutyl tin dilaurate for reaction ~ ~ Q, k ``
6~79 at 70C Eor 5 hours, thereby obtaining a urethane oligomer E-3. 146.4 parts of the urethane oligomer E-3 ~including the reaction solvent) was added with 6.2 parts of PPG-Triol-450 ~adduct of glycerine and propylene oxide with an OH value of 450, product of Mitsui Toatsu Chem. Ind. Co.) and 9.1 parts of surface active agent Adekapluronic F-108~polyoxypropylenepolyoxyethylene ether, product of Asahi Denka Ind. Co.), to which was further gradually added 138.3 parts of water under high shearing conditions. After completion of the addition, the reaction solvent was removed by distillation under reduced pressure to obtain an aqueous dispersed urethane composition H-3. The compo-sition H-3 had a viscosity of 105 cps at 30C and was stable over 6 months at room temperature.
A thin layer of the composition H-3 was subjected to film formation, that is, dried and cured at 60C for 60 min and then at 150C for 120 min to obtain a tough film. The characteristic properties of the film are summarized in the Table appearing below.
1500 parts of polyoxytetramethylene glycol having a molecular weight of 1500 and 870 parts o:E a mixture o:E 2.~-tolylenecliisocyanate and 2,6-toly-lenedilsocyanate in a mixing weight ratio of 65:35 ~hereinafter referred to as TDI 65/35) were mixed with each other and heated to 60C while agitating, followed by reaction at 60C for 2 hours under agitating conditions, thereby obtaining a prepolymer ~hereinafter referred to as prepolymer P-4). 274.9 parts of the prepolymer P-4, 242.2 parts of TDI 65/35, 150 parts of methyl ethyl ketone and 150 parts of cellosolve acetate were mixed and kept at 25C
with agitation, to which was added dropwise 30.3 parts of methyl ethyl ket-oxime over 30 min. Thereafter, 39.3 parts of ~-caprolactam was added to the reaction mass, which was then heated to 45C for further reaction a~ 45C for 1 hour. Then, 114.6 parts of 1,3-propylene glycol was added to the reaction mass, which was heated to 70C and added with 0.21 parts of dibutyl tin dilaurate for reaction at 70C for 5 hours thereby to obtain a urethane ~ tr~
- - : . .
~96~
o]igomer (hereinafter referred to as urethane oligomer E-4).
125.5 parts of the urethane oligomer E-4 ~including the reaction solvent) was added with 6.5 parts of PPG-ED-760 (adduct of ethylenediamine and propylene oxide with an OH value of 760, product of Mitsui Toatsu Chem.
Ind. Co.) and 6.5 parts of surface active agent Epan 785, to which was further -gradually added 161.5 parts of water under high shearing conditions. After completion of the addition. the solvent was removed by distillation under reduced pressure to obtain an aqueous dispersed urethane composition H-4.
The composition H-4 had a viscosity of 95 cps at 30C and was stable at room temperature over 6 months.
A thin layer of the composition H-4 was subjected to film formation, that,is, dried and cured at 60C for 30 min and then at 150C for 120 min to obtain a tough film. The characteristic properties and mechanical strengths of the film are summarized in the Table appearing below.
86.6 parts of polyoxypropylene glycol having a molecuLar weight of 1600 and 351.4 parts of TDI 80/20 were mixed ~md heated to 60C with agitation, followed by reaction at 60C for 3 hours under agitating conditions. To the reaction mass was added 63.3 parts of -capro:Lactam for further reaction at 60C for 1 hour. Then, 0.15 parts of dibutyl tin dilaurate and 300 parts of cellosolve acetate were added to and uniformly mixed with the reaction system under agitation, to which was further added 198.8 parts of 1,6-hexanediol for reaction at 80C for 3 hoursJ thereby obtaining a urethane oligomer (herein-after referred to as urethane oligomer E-5). 143 parts of the urethane `-oligomer solution E-5 (including the reaction solvent), 6.3 parts of tri- -B methylolpropane, and 5 parts of surface active agent Epan U-108 (polyoxypropy-lenepolyoxyethylene ether, product of Daiichi Kogyo Seiyaku K.K.) were mixed ;~
with one another and gradually added with 98.4 parts of water under high shearing conditions to obtain an aqueous dispersed urethane composition H-5.
The composition H-5 had a viscosity of 110 cps at 30C and was stable at room ~ ~YPl~Q ~
`;' ,;
6~79 temperature over 6 months. A tough film was obtained when the composition H-5 was subjected to film formation under the same conditions as in Example 1.
The characteristic properties and mechanical strengths of the film are summa-rized in the Table appearing below.
156.2 parts of polyoxypropylene glycol having a molecular weight of 3000 and 312.8 parts of TDI 80/20 were mixed with each other under agitation, to which was added 0.02 parts of dibutyl tin dilaurate and heated to 60C with agitation, followed by reaction at 60C for 1.5 hours. Then, 300 parts of cellosolve acetate was added to the reaction mass kept at 80C with agitation, to which was added 103.4 parts of 1,6-hexylene glycol, followed by reaction at 80C for 10 minutes. Then, 78.3 parts of dipropylene glycol was gradually added at 80C, followed by reaction at 80C for 1.5 hours. Then the reaction mass was allowed to cool till 60C, and 49.2 parts of methyl ethyl ketoxime was added to the reaction mass at 60C, followed by reaction at 70C for I
hour, thereby obtaining a urethane oligomer E-6. 143 parts of the urethane oligomer E-6 (including the reaction solvent) was added with 2.5 parts of trimethylol propane and 2 parts oE surEace active agent Epan 785 and 3 parts of surface active agent Epan U-108, to which was further gradually added 99.5 parts of water under high shearing conditions to obtain an aqueous dispersed urethane composition H-6. The composition H-6 had a viscosity of 120 cps at 30C and was stable over 6 months at room temperature.
A tough film was obtained when the composition H-6 was subjected to film formation under the same conditions as in Example 1. The characteristic properties and mechanical strength of the film are summarized in the Table appearing bel-ow.
Comparative Example 1 67.5 parts of the urethane oligomer E-2 obtained in Example 2 was mixed with 2.7 parts of trimethylolpropane and 6.5 parts of Epan 785, followed by treating the mixture in the same procedure as in Example 2 to yield an : , . .
: ;,; ' " ;' :, :
aqueous dispersed urethane composition CH-l. As indicated in the Table~ in the composition CH-l, the proportion of the sum by weight of the polyoxytetra-methylene glycol and the surface active agent to all the components of the composition CH-l other than water was 38%. The composition CH-l was subjected to film formation under the same conditions as in Example 2 to obtain a film.
The characteristic properties and mechanical strengths of the film are shown in the column of Comparative Example 1 of the Table appearing below.
Comparative Example 2 146.4 parts of the urethane oligomer obtained in Example 3 was mixed with 6.2 parts of PPG-Triol-450 (product of Mitsui Toatsu Chem. Ind. Co.) and 4.3 parts of surface active agent Adekapluronic F-108, followed by ~reating in the same manner as in Example 3 to obtain an aqueous dispersed urethane compo-sition CH-2. As indicated in the l'able, in the composition CH-2, the proportion by weight of the sum of the polyoxypropylene glycol and the surface active agent to the sum of all the components of the composition CH-2 other than water was 12%.
The composition CH-2 was subjected to fllm formation under the same conditions as in Example 3 to obta:in a film. The characteristic properties and mechanical strengths of the thus obtained film are summarized in the Table appearing below.
Comparative Example 3 .:
1000 parts of polyoxypropylene glycol having a molecular weight of 1000 and 870 parts of TDI 80/20 were mixed with each other and heated to 60C
while agitating, followed by reaction at 60C for 2 hours under agitating conditions to obtain a prepolymer (hereinafter referred to as prepolymer CP-6).
187 parts of the prepolymer CP-6, 261 parts of TDI 80/20 and 302 parts of cellosolve acetate were mixed and agitated at 40C, to which was stepwise added over 1 hour 67.8 parts, in total, of -caprolactam which had been divided into three portions. The resulting reaction mass was heated to 50C and subjected to reaction at 50C for 1 hour, to which was further added ~16-. . -. . ~ .
37~
188.8 parts of 1,6-hexylene glycol, followed by heating to 80C and adding 0.21 parts of dibutyl tin dilaurate for reaction at 80C for 2 hours, thereby obtaining a urethane oligomer CE-7.
100.7 parts of the urethane oligomer CE-7 (including the reaction sol-vent) was added with 2.6 parts of trimethylolpropane and 17.0 parts of surface active agent Epan 785, to which was gradually added 90 parts of water under high shearing conditions to obtain an aqueous dispersed urethane composition CH-3. A thin layer of the composition CH-3 was subjected to film formation under drying and curing conditions of 60 C-30 min and then 150C-120 min. The characteristic properties and mechanical strengths of the resulting film are summarized in the Table appearing below in the columnof Comparative Example 3.
Comparat_ve_Ex_mple 4 45.1 parts of polyoxypropylene glycol having a molecuLar weight of 1500 and 369.8 parts of TDI 80/20 were mixed with each other and heated to 60C
while agitating, followed by reaction at 60C for 3 hours under agitating con-; ditions. To the reaction mass was added 79.1 parts of e-caprolactam for reac-tion at 60C for 1 h~ur. Thereafter, the reaction mass was added with 0.15 parts of dibutyl tin dilaurate and 300 parts of cellosolve acetate and uniformly mixed with agitation, and further added wtih 206 parts of 1,6-hexanediol for reaction at 80C for 3 hours, thereby yielding a urethane oligomer CE-8. 143 parts of the urethane oligomer solution CE-8~including the - reaction solvent) was mixed wtih 4.98 parts of trietllanolamine and 5 parts of surface active agent Epan U-108, to which was gradually added 97 parts of water under high shearing conditions to obtain an aqueous dispersed urethane compo-sition CH-4. The composition CH-4 was subjected to film Eormation under the same conditions as in Comparative Example 1. The characteristic properties and mechanical strengths of the resulting film are summarized in the Table appearing below in the column of Comparative Example 4.
, .
.
:. ., , ~ ., ;,~, , , ~ ;
~6~7~
Comparative Example 5 .
230.3 parts of polyoxypropylene glycol having a molecular weight of 3000 and 277.5 parts of IDI 80/20 were mixed with each other and heated to 60C under agitation, followed by reaction at 60C for 3 hours under agitating conditions. To the reaction mass was added 300 parts of cellosolve acetate, which was kept at 25C while agitating. Then, 40.6 parts of methyl ethyl ketoxime was drapwise added to the reaction mass over 30 min, followed by reaction at 25C for further 30 min. The reaction system was added with 151.6 parts of 1,6-hexanediol and heated to 70C, to which was added 0.15 parts of 10dibutyl tin dilaurate, followed by reaction at 70C for 5 hours thereby ~;
obtaining a urethane oligomer solution CE-9. 143 parts of the oligomer solu-tion CE-9 (including the reaction solvent), 2.98 parts of trimethylolpropane and 10 parts of surface active agent Epan U-108 were mixed and gradually added with 94 parts of water under high shearing conditions to obtain an aqueous dispersed urethane composition CH-5. The characteristic properties and - mechanical strengths of the film obtained from the composition CH-5 are summarized in the Table appearing below in the column of Comparative Example 5.
, . .. l Ux' .
~ ~ o oo o o U~ X o A O A _ A , X 11 ) N ~ O O X X
~_ ___ ._ _ ~X
~ U~ O O 00 O O X ~
~ O ~ N ~ Il'~
_. _ ~ I :
O N
N U~ O N O O X X
f~c ~
~ ~ ~ O 00 00 O N X O
._ _ .
J~ ~Ç) ~ O N N U~ O O O
h 3~ X O r ) N ~t 0~ _ _ h h Lt~ g V N o NO o C ~ :
Cl ~ 11~ ~ _~1 ".~ _ ~ ' O ~ ~ O N Lt~ O 111 O O
~d ~ ~ X u~ N t~) Ll~
$1 ¢ . _ _ . ....
~7 0 ~ ~ O~D L~ O Lr~ O ~
~c x o ~ ~ u~
-----------l N N O11~ O O U) O O
_ O ~ N L~ Ct) ,_ __ _ . _ _ ~ I .
The hardeners which are used with the urethane oligomer in the present invention are those ordinarily employed for polyurethane, including polyfunc-tional alcohols, amines and amino-alcohols, etc. These compoun~s preferably have a Inolecular weight below 500. Examples of the polyEunctional alcohols are pentaerythritol, trimethylolpropane, glycerol, adducts having an OH value greater than 450 and obtained by addition reaction of propylene oxide with trimethylolpropane and adducts having an OH value above 450 and obtained by ~;
addition reaction of glycerine wtih propylene oxide, etc. Examples of the polyfunctional amines include triethylenetetramine, diethylenetriamine, etc.
Examples of the aminoalcohols include diethanolamine, triethanolamine, tri- ~ ~
isopropanolamine, diisopropanolamine, an adduct of 1 mole of ethylenediamine ~ -and less than 4 moles of propylene oxide.
The amount of the hardener is determined such that an equivalent ratio of the blocked isocyanate contained in the urethane oligomer to the active hydrogen of the hardener is in the range of 1:0.8 to 1.2.
The surface active agents employed for dispersing the thermosetting .
7~
urethane composition in water are conventional nonionic active agents including, for example, an addition product of nonylphenol and ethylene oxide, a copolymer of propylene oxide and ethylene oxide, and the like. In view of chemical stability and water resistance, the propylene oxide-ethylene oxide copolymer having a molecular weight above 10,000 and an ethylene oxide content of above 60% by weight is preferred. In addition, polyethyleneglycol alkylphenyl ethers may also be used as the surface active agent. The preferred amount of the surface active agent is in the range of 4 to 25 parts by weight per 100 parts by weight of the urethane oligomer which is used for preparing the thermo- -s setting urethane composition. As a matter of course, the amount of surface active agent depends on the amounts of the other components essentially re-quired for the production of the aqueous dispersed urethane composition of the invention and may appropriately vary within the above defined range such that, as indicated hereinbefore in the equation ~I), the sum of the weight A
of the polyoxyalkylene glycol used for the preparation of the urethane oligomer and the weight G of the surface active agent employed for dispersing the urethane oligomer and a hardener in water is in the range of 15 to 35% by weight based on the sum of the weight E of the oligomer, the weight ~ of the hardener and the weight G of the surface active agent emyloyed for the dispersion. With the range below 15%, the film obtained from such aqueous urethanedispersion composition is inferior in preventing the film-applied glass bottle from being scattered upon breakage thereof. The range above 35%
is unfavorable since the resulting film becomestoo soft and exhibits poor durability when used for protecting purpose.
The dispersion or emulsification is feasible by adding a surface active agent to the thermosetting urethane composition which is prepared by mixing a urethane oligomer with a hardener, and mixing the mixture under high shearing conditions while gradually adding water. Use of a urethane oligomer having a relatively high molecular weight requires use of solvent ` ~ -so as to reduce the viscosity of the dispersion. The solvent usable for this purpose is that which is employable upon the preparation of the urethane oligomer and which can be readily distilled off after completion of the dis-persion. Examples of the solvent are methyl ethyl ketone, toluene, tetra-hydrofuran, acetone, dioxane, etc. On]y for viscosity-reducing purpose there are used various kinds of solvents such as cellosolve acetate, butylcellosolve acetate, 2-nitropropane, ethylene glycol, diethyl ether and the like.
The emulsification method will be particularly described.
The urethane oligomer is first dissolved in solvent to prepare a urethane oligomer solution having a viscosity of 100,000 cps at room tempera-ture. In order to prepare such solution, it will suffice to use 50 parts of the solvent per 100 parts of the urethane oligomer. To the oligomer solution are added a hardener and then a surface active agent to obtain a uniform solution. Then, water is added to the solution in an amount of 100 to 250 parts per 100 parts of the urethane oligomer employed. Water to be added to the solution is preferred to be divided into three portions and added stepwise.
That is, 1/3 of a predetermined amount of water is added under conditions to revolutions of above 1,000 r.p.m. when a propeller-type agitation blade is used for agitation. Each 1/3 of the balance of water may be added without any limitation of the number of revolutions but is preferred to agitate for more than 15 min in each step after completion of the addition of water.
After completion of the dispersion in water, the solvent used is preferably removed by distillation at a temperature of 20 to ~0C under reduced pressure.
Known aqueous dispersed polyurethane compositions using surface active agents have detrimental disadvantages in low waterproof properties and also in that the dispersion is unstable and accordingly the dispersed phase tends to precipitate with a lapse of time.
The composition of the invention is a novel one which overcomes the ;
disadvantages of the prior compositions and in which the molecular weight and amount of the polyoxyalkylene glycol, the molecular weight of the urethane oligomer and the amount of the surface active agent are so interdependent that 9_ 6~7~1 the dispersion composition in an optimum region of composition exhibits un-expected excellent characteristic properties suitable for glass bottle protec-tion. Known aqueous dispersed polyurethane compositions using surface active agents are also disadvantageous because they suffer a loss of transparency when formed into films and immersed in water and can not be used at all as coatings for glass bottles.
In order to improve the waterproof properties of an aqueous emulsion, generally use is made of crosslinkage of a polymeric resin. There has been proposed an improved aqueous dispersed polyurethane composition which can yield a film with improved waterproof properties. However, this composition has drawbacks that the film is poor in ability for preventing glass bottles from being scattered upon breakage of the bottles and also in durability. The composition can not be used as coatings for protecting glass bottles by application of single protecting film layer thereof.
The film prepared from the composition of the invention has, as will be particularly indicated in Table mentioned hereinafter, excellent mechanical strength and waterproof properties and does not lose its transparency when placed in hot water at 70C. The composition of the invention provides a coating for protecting glass bottles by single coating layer with excellent properties such as the scattering-preventing ability and a prolonged dura-bility.
The present invention will be particularly described by way of the following examples and comparative examples, in which parts are by weight.
2000 parts of polyoxypropylene glycol having a molecular weight of 2000 and 870 parts of 2,4-tolylenediisocyanate ~hereinafter referred to simply as TDI-100) were placed in a reactor and heated to 60C with agitation, followed by reaction at 60C for 3 hours under agitating conditions to obtain a prepolymer compound (hereinafter referred to as prepolymer P-l).
284 parts of the thus obtained prepolymer P-l, 261 parts of 2,4-.. . .~ :. .- , tolylenediisocyanate and 337 parts of cellosolve acetate were mixed and main-tained at 20C with agitation, to which was dropwise added 52 parts of methyl ethyl ketoxime over 1 hours. After completion of the dropping, 189 parts of 1,6-hexylene glycol was added to the reaction mass, which was heated up to 60C in 30 min and maintained at 60C for 1 hour. Thereafter, 0.25 parts of dibutyl tin dilaurate was added to the reaction mass, followed by further heating to 80C and maintaining at 80C for 3 hours to obtain a urethane oligomer ~hereinafter referred to urethane oligomer E-l). 107 parts of the urethane oligomer E-l (including the reaction solvent) was added with 2.3 `
o B parts of trimethylolpropane and 5.2 parts of a surface active agent, Epan 785 (polyoxypropylenepolyoxyethylene ether produced by Daiichi Kogyo Seiyaku K.K.), ;;
to which was gradually added 85.5 parts of water under high shearing conditions to give an aqueous dispersed urethane composition (hereinafter referred to as aqueous dispersed urethane composition H-l). The aqueous dispersed urethane composition H-l has a viscosity of 120 cps at 30C and was stable over 6 months at room temperature.
A thin layer of the composition H-l was subjected to film formation, that is, dried and cured at 60C for 30 min and then at 150C for 120 min to obtain a film with excellent mechanical strengths. Tlle properties and strengths of the film are tabulated in Table appearing below.
1500 parts of polyoxytetramethylene glycol having a molecular weight of 1500 and 870 parts of a mixture of 2,4-tolylenediisocyanate and 2,6-toly-lenediisocyanate in a ratio by weight of 8:2 (hereinafter referred to simply as TDI 80/20) were placed in a reactor and heated up to 60C while agitating, followed by reaction at 60C for 2 hours, thereby obtaining a prepolymer (hereina~ter referred to as prepolymer P-2). 351 parts of the thus obtained prepolymer P-2, 155 parts of TDI 80/20, 150 parts of toluene and 150 parts of tetrahydrofuran were mixed and maintained at 40C with agitation, to which was ; 30 stepwise added over 1 hour 100 parts of ~-caprolactam which had been divided ~ ~ule :- . . ................... ~ - . :
. ~ .
into three portions. The reaction mass was heated to 50C and kept at 50C
for 1 hour for reactionJ to which was further added 93 parts of 1,4-butylene glycol, followed by heating to 70C. Then, 0.21 parts of dibutyl tin di-laurate was added to the heated reaction mass for further reaction at 70C
for 5 hours to obtain a urethane oligomer (hereinafter referred to as urethane oligomer E-2).
125.5 parts of the urethane oligomer E-2 ~including the reaction solvent), 5.0 parts of trimethylolpropane, 3.5 parts of surface active agent, Emulsit 16 ~polyethylene glycol alkylphenyl ether produced by Daiichi Kogyo Seiyaku K.K.) and 3.5 parts of Epan 785 were mixed with one another, to which ~-was gradually added 163 parts of water under high shearing conditions. After completion of the dispersion, the reaction solvent was distilled off under reduced pressure to obtain an aqueous dispersed urethane composition H-2. The composition H-2 had a viscosity of 80 cps at 30C and was stable over 3 months at room temperature.
A thin layer of the composition H-2 was subjected to film formation, tllat is, dried and cured at 60C for 30 min and then at 150C for 120 min to obtain a tough film. The characteristic properties oE the Eilm are shown in the Table below.
2000 parts of polyoxypropylene glycol having a molecular weight of ~ -3000 and 870 parts of TDI 80/20 were mixed and heated to 60C with agitation, followed by reaction at 60C for 3 hours under agitating conditions, thereby yielding a prepolymer P-3. 77.4 parts of the thus obtained prepolymer P-3, 361.9 parts of TDI 80/20, 267 parts of tetrahydrofuran and 200 parts of cellosolve acetate were mixed and kept at 25C with agitation, to which was ` stepwise added over 1 hour 30.7 parts, in total, of acetoxime which had been ~ divided into three portions, followed by further reaction at 25C for 30 min.
: Then 230 parts of 1,6-hexylene glycol was added to the reaction mass, followed by heating to 70C and adding 0.21 parts of dibutyl tin dilaurate for reaction ~ ~ Q, k ``
6~79 at 70C Eor 5 hours, thereby obtaining a urethane oligomer E-3. 146.4 parts of the urethane oligomer E-3 ~including the reaction solvent) was added with 6.2 parts of PPG-Triol-450 ~adduct of glycerine and propylene oxide with an OH value of 450, product of Mitsui Toatsu Chem. Ind. Co.) and 9.1 parts of surface active agent Adekapluronic F-108~polyoxypropylenepolyoxyethylene ether, product of Asahi Denka Ind. Co.), to which was further gradually added 138.3 parts of water under high shearing conditions. After completion of the addition, the reaction solvent was removed by distillation under reduced pressure to obtain an aqueous dispersed urethane composition H-3. The compo-sition H-3 had a viscosity of 105 cps at 30C and was stable over 6 months at room temperature.
A thin layer of the composition H-3 was subjected to film formation, that is, dried and cured at 60C for 60 min and then at 150C for 120 min to obtain a tough film. The characteristic properties of the film are summarized in the Table appearing below.
1500 parts of polyoxytetramethylene glycol having a molecular weight of 1500 and 870 parts o:E a mixture o:E 2.~-tolylenecliisocyanate and 2,6-toly-lenedilsocyanate in a mixing weight ratio of 65:35 ~hereinafter referred to as TDI 65/35) were mixed with each other and heated to 60C while agitating, followed by reaction at 60C for 2 hours under agitating conditions, thereby obtaining a prepolymer ~hereinafter referred to as prepolymer P-4). 274.9 parts of the prepolymer P-4, 242.2 parts of TDI 65/35, 150 parts of methyl ethyl ketone and 150 parts of cellosolve acetate were mixed and kept at 25C
with agitation, to which was added dropwise 30.3 parts of methyl ethyl ket-oxime over 30 min. Thereafter, 39.3 parts of ~-caprolactam was added to the reaction mass, which was then heated to 45C for further reaction a~ 45C for 1 hour. Then, 114.6 parts of 1,3-propylene glycol was added to the reaction mass, which was heated to 70C and added with 0.21 parts of dibutyl tin dilaurate for reaction at 70C for 5 hours thereby to obtain a urethane ~ tr~
- - : . .
~96~
o]igomer (hereinafter referred to as urethane oligomer E-4).
125.5 parts of the urethane oligomer E-4 ~including the reaction solvent) was added with 6.5 parts of PPG-ED-760 (adduct of ethylenediamine and propylene oxide with an OH value of 760, product of Mitsui Toatsu Chem.
Ind. Co.) and 6.5 parts of surface active agent Epan 785, to which was further -gradually added 161.5 parts of water under high shearing conditions. After completion of the addition. the solvent was removed by distillation under reduced pressure to obtain an aqueous dispersed urethane composition H-4.
The composition H-4 had a viscosity of 95 cps at 30C and was stable at room temperature over 6 months.
A thin layer of the composition H-4 was subjected to film formation, that,is, dried and cured at 60C for 30 min and then at 150C for 120 min to obtain a tough film. The characteristic properties and mechanical strengths of the film are summarized in the Table appearing below.
86.6 parts of polyoxypropylene glycol having a molecuLar weight of 1600 and 351.4 parts of TDI 80/20 were mixed ~md heated to 60C with agitation, followed by reaction at 60C for 3 hours under agitating conditions. To the reaction mass was added 63.3 parts of -capro:Lactam for further reaction at 60C for 1 hour. Then, 0.15 parts of dibutyl tin dilaurate and 300 parts of cellosolve acetate were added to and uniformly mixed with the reaction system under agitation, to which was further added 198.8 parts of 1,6-hexanediol for reaction at 80C for 3 hoursJ thereby obtaining a urethane oligomer (herein-after referred to as urethane oligomer E-5). 143 parts of the urethane `-oligomer solution E-5 (including the reaction solvent), 6.3 parts of tri- -B methylolpropane, and 5 parts of surface active agent Epan U-108 (polyoxypropy-lenepolyoxyethylene ether, product of Daiichi Kogyo Seiyaku K.K.) were mixed ;~
with one another and gradually added with 98.4 parts of water under high shearing conditions to obtain an aqueous dispersed urethane composition H-5.
The composition H-5 had a viscosity of 110 cps at 30C and was stable at room ~ ~YPl~Q ~
`;' ,;
6~79 temperature over 6 months. A tough film was obtained when the composition H-5 was subjected to film formation under the same conditions as in Example 1.
The characteristic properties and mechanical strengths of the film are summa-rized in the Table appearing below.
156.2 parts of polyoxypropylene glycol having a molecular weight of 3000 and 312.8 parts of TDI 80/20 were mixed with each other under agitation, to which was added 0.02 parts of dibutyl tin dilaurate and heated to 60C with agitation, followed by reaction at 60C for 1.5 hours. Then, 300 parts of cellosolve acetate was added to the reaction mass kept at 80C with agitation, to which was added 103.4 parts of 1,6-hexylene glycol, followed by reaction at 80C for 10 minutes. Then, 78.3 parts of dipropylene glycol was gradually added at 80C, followed by reaction at 80C for 1.5 hours. Then the reaction mass was allowed to cool till 60C, and 49.2 parts of methyl ethyl ketoxime was added to the reaction mass at 60C, followed by reaction at 70C for I
hour, thereby obtaining a urethane oligomer E-6. 143 parts of the urethane oligomer E-6 (including the reaction solvent) was added with 2.5 parts of trimethylol propane and 2 parts oE surEace active agent Epan 785 and 3 parts of surface active agent Epan U-108, to which was further gradually added 99.5 parts of water under high shearing conditions to obtain an aqueous dispersed urethane composition H-6. The composition H-6 had a viscosity of 120 cps at 30C and was stable over 6 months at room temperature.
A tough film was obtained when the composition H-6 was subjected to film formation under the same conditions as in Example 1. The characteristic properties and mechanical strength of the film are summarized in the Table appearing bel-ow.
Comparative Example 1 67.5 parts of the urethane oligomer E-2 obtained in Example 2 was mixed with 2.7 parts of trimethylolpropane and 6.5 parts of Epan 785, followed by treating the mixture in the same procedure as in Example 2 to yield an : , . .
: ;,; ' " ;' :, :
aqueous dispersed urethane composition CH-l. As indicated in the Table~ in the composition CH-l, the proportion of the sum by weight of the polyoxytetra-methylene glycol and the surface active agent to all the components of the composition CH-l other than water was 38%. The composition CH-l was subjected to film formation under the same conditions as in Example 2 to obtain a film.
The characteristic properties and mechanical strengths of the film are shown in the column of Comparative Example 1 of the Table appearing below.
Comparative Example 2 146.4 parts of the urethane oligomer obtained in Example 3 was mixed with 6.2 parts of PPG-Triol-450 (product of Mitsui Toatsu Chem. Ind. Co.) and 4.3 parts of surface active agent Adekapluronic F-108, followed by ~reating in the same manner as in Example 3 to obtain an aqueous dispersed urethane compo-sition CH-2. As indicated in the l'able, in the composition CH-2, the proportion by weight of the sum of the polyoxypropylene glycol and the surface active agent to the sum of all the components of the composition CH-2 other than water was 12%.
The composition CH-2 was subjected to fllm formation under the same conditions as in Example 3 to obta:in a film. The characteristic properties and mechanical strengths of the thus obtained film are summarized in the Table appearing below.
Comparative Example 3 .:
1000 parts of polyoxypropylene glycol having a molecular weight of 1000 and 870 parts of TDI 80/20 were mixed with each other and heated to 60C
while agitating, followed by reaction at 60C for 2 hours under agitating conditions to obtain a prepolymer (hereinafter referred to as prepolymer CP-6).
187 parts of the prepolymer CP-6, 261 parts of TDI 80/20 and 302 parts of cellosolve acetate were mixed and agitated at 40C, to which was stepwise added over 1 hour 67.8 parts, in total, of -caprolactam which had been divided into three portions. The resulting reaction mass was heated to 50C and subjected to reaction at 50C for 1 hour, to which was further added ~16-. . -. . ~ .
37~
188.8 parts of 1,6-hexylene glycol, followed by heating to 80C and adding 0.21 parts of dibutyl tin dilaurate for reaction at 80C for 2 hours, thereby obtaining a urethane oligomer CE-7.
100.7 parts of the urethane oligomer CE-7 (including the reaction sol-vent) was added with 2.6 parts of trimethylolpropane and 17.0 parts of surface active agent Epan 785, to which was gradually added 90 parts of water under high shearing conditions to obtain an aqueous dispersed urethane composition CH-3. A thin layer of the composition CH-3 was subjected to film formation under drying and curing conditions of 60 C-30 min and then 150C-120 min. The characteristic properties and mechanical strengths of the resulting film are summarized in the Table appearing below in the columnof Comparative Example 3.
Comparat_ve_Ex_mple 4 45.1 parts of polyoxypropylene glycol having a molecuLar weight of 1500 and 369.8 parts of TDI 80/20 were mixed with each other and heated to 60C
while agitating, followed by reaction at 60C for 3 hours under agitating con-; ditions. To the reaction mass was added 79.1 parts of e-caprolactam for reac-tion at 60C for 1 h~ur. Thereafter, the reaction mass was added with 0.15 parts of dibutyl tin dilaurate and 300 parts of cellosolve acetate and uniformly mixed with agitation, and further added wtih 206 parts of 1,6-hexanediol for reaction at 80C for 3 hours, thereby yielding a urethane oligomer CE-8. 143 parts of the urethane oligomer solution CE-8~including the - reaction solvent) was mixed wtih 4.98 parts of trietllanolamine and 5 parts of surface active agent Epan U-108, to which was gradually added 97 parts of water under high shearing conditions to obtain an aqueous dispersed urethane compo-sition CH-4. The composition CH-4 was subjected to film Eormation under the same conditions as in Comparative Example 1. The characteristic properties and mechanical strengths of the resulting film are summarized in the Table appearing below in the column of Comparative Example 4.
, .
.
:. ., , ~ ., ;,~, , , ~ ;
~6~7~
Comparative Example 5 .
230.3 parts of polyoxypropylene glycol having a molecular weight of 3000 and 277.5 parts of IDI 80/20 were mixed with each other and heated to 60C under agitation, followed by reaction at 60C for 3 hours under agitating conditions. To the reaction mass was added 300 parts of cellosolve acetate, which was kept at 25C while agitating. Then, 40.6 parts of methyl ethyl ketoxime was drapwise added to the reaction mass over 30 min, followed by reaction at 25C for further 30 min. The reaction system was added with 151.6 parts of 1,6-hexanediol and heated to 70C, to which was added 0.15 parts of 10dibutyl tin dilaurate, followed by reaction at 70C for 5 hours thereby ~;
obtaining a urethane oligomer solution CE-9. 143 parts of the oligomer solu-tion CE-9 (including the reaction solvent), 2.98 parts of trimethylolpropane and 10 parts of surface active agent Epan U-108 were mixed and gradually added with 94 parts of water under high shearing conditions to obtain an aqueous dispersed urethane composition CH-5. The characteristic properties and - mechanical strengths of the film obtained from the composition CH-5 are summarized in the Table appearing below in the column of Comparative Example 5.
, . .. l Ux' .
~ ~ o oo o o U~ X o A O A _ A , X 11 ) N ~ O O X X
~_ ___ ._ _ ~X
~ U~ O O 00 O O X ~
~ O ~ N ~ Il'~
_. _ ~ I :
O N
N U~ O N O O X X
f~c ~
~ ~ ~ O 00 00 O N X O
._ _ .
J~ ~Ç) ~ O N N U~ O O O
h 3~ X O r ) N ~t 0~ _ _ h h Lt~ g V N o NO o C ~ :
Cl ~ 11~ ~ _~1 ".~ _ ~ ' O ~ ~ O N Lt~ O 111 O O
~d ~ ~ X u~ N t~) Ll~
$1 ¢ . _ _ . ....
~7 0 ~ ~ O~D L~ O Lr~ O ~
~c x o ~ ~ u~
-----------l N N O11~ O O U) O O
_ O ~ N L~ Ct) ,_ __ _ . _ _ ~ I .
3: X N N N O N O O
_ _ ~ ~ r~~ _ _ ___ ~ ~ ~
g ~ ~ ~ ~ _ ~ ~0 ~ ~ri h ~ ~ O ~ ~
O U~ O I X U~ N ~ r~ ~V ~N rl ~ ~rl g h ,~ ~ o a> o ~ ~ o\O ~ cd o\ ~ ~O ~ ~ I O
1~ bO ~~ ~ O ~ bO O ~ h ~O h ~d h ~ ~rl .,~ ~ ~, _ 3 o ~, ~, ¢ o o .Y a> ~_ _ ~ h ~ .
~.
~6~
Note:
(1) These physical characteristics were determined by the respective methods prescribed in JIS K-6301. In our tests, films having a thickness of about lO0 1l were used.
~ 2) The durability was determined as follows. The urethane compositions were each applied to large-size Coca Cola~Drink bottles to form a film layer on the outer surface of each of the bottles in an amount of 6.0 to 7.0 g per bottle. Then, the thus applied bottles were each passed 20 times only to the washing step of the Coca Cola~brink bottling line for large-size bottles.
The durability was determined on the basis of a degree of scratch marks pro-duced during the passages. ~ -o...... a ratio of the number of bottles having at least one scratch mark with a length above 5 mm to the number of all tested bottles < 10 ~%) x...... the ratio deEined above > lO ~%) (3) The glass-scratching-preventing ability was determined in accordance with the method as prescribed in Ordinance No, 18 of the Japanese International Trade and Industry Ministry, entitled "Ordinance Concerning Safety Standards For Speciic Articles Related To The International Trade And Industry Ministry"
(March, 1974). The test was conducted at ~0C and 15C.
o...... accepted, ~..... rejected at 15C, x..... rejected In the durability and the glass-scattering-preventing ability tests, bottles were coated by the following method.
Large-size bottles for Coca Cola drinks were used for coating. The neck of the bottle was fixedly set to a holder connected to a motor axle and kept at a level with the bottle. Then, the motor was started and rotated at lO r.p.m. An aqueous dispersed urethane composition was unifcrmly sprayed over the rotated bottle, followed by drying and curing the sprayed urethane composition in a hot air dryer while rotating the sprayed glass bottle. The drying and curing conditions were as follows:
~1) Drying at 60C for 30 min.
~ t~ ~u-k : . .
1~9G~7~
(2) Heating up to 150C in 30 min.
~3) Curing at 150C for 150 min.
_ _ ~ ~ r~~ _ _ ___ ~ ~ ~
g ~ ~ ~ ~ _ ~ ~0 ~ ~ri h ~ ~ O ~ ~
O U~ O I X U~ N ~ r~ ~V ~N rl ~ ~rl g h ,~ ~ o a> o ~ ~ o\O ~ cd o\ ~ ~O ~ ~ I O
1~ bO ~~ ~ O ~ bO O ~ h ~O h ~d h ~ ~rl .,~ ~ ~, _ 3 o ~, ~, ¢ o o .Y a> ~_ _ ~ h ~ .
~.
~6~
Note:
(1) These physical characteristics were determined by the respective methods prescribed in JIS K-6301. In our tests, films having a thickness of about lO0 1l were used.
~ 2) The durability was determined as follows. The urethane compositions were each applied to large-size Coca Cola~Drink bottles to form a film layer on the outer surface of each of the bottles in an amount of 6.0 to 7.0 g per bottle. Then, the thus applied bottles were each passed 20 times only to the washing step of the Coca Cola~brink bottling line for large-size bottles.
The durability was determined on the basis of a degree of scratch marks pro-duced during the passages. ~ -o...... a ratio of the number of bottles having at least one scratch mark with a length above 5 mm to the number of all tested bottles < 10 ~%) x...... the ratio deEined above > lO ~%) (3) The glass-scratching-preventing ability was determined in accordance with the method as prescribed in Ordinance No, 18 of the Japanese International Trade and Industry Ministry, entitled "Ordinance Concerning Safety Standards For Speciic Articles Related To The International Trade And Industry Ministry"
(March, 1974). The test was conducted at ~0C and 15C.
o...... accepted, ~..... rejected at 15C, x..... rejected In the durability and the glass-scattering-preventing ability tests, bottles were coated by the following method.
Large-size bottles for Coca Cola drinks were used for coating. The neck of the bottle was fixedly set to a holder connected to a motor axle and kept at a level with the bottle. Then, the motor was started and rotated at lO r.p.m. An aqueous dispersed urethane composition was unifcrmly sprayed over the rotated bottle, followed by drying and curing the sprayed urethane composition in a hot air dryer while rotating the sprayed glass bottle. The drying and curing conditions were as follows:
~1) Drying at 60C for 30 min.
~ t~ ~u-k : . .
1~9G~7~
(2) Heating up to 150C in 30 min.
~3) Curing at 150C for 150 min.
(4) The value of E+F+Gx 100 which has appeared on the left side of the afore-indicated equation ~I) and is one of the most important limitations of the present invention must be in the range of 15 to 35 in the present inven-tion.
.
~'
.
~'
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous dispersed urethane composition comprising a urethane oligomer obtained by interacting a mixture of bifunctional active hydrogen-containing compounds and a monofunctional active hydrogen-containing iso-cyanate-blocking agent, and a diisocyanate under such conditions that an equivalent ratio of the active hydrogen contained in said mixture to the isocyanate group of said diisocyanate is about 1.0, a hardener mixed with said urethane oligomer in an equivalent ratio of the blocked isocyanate of said urethane oligomer to the active hydrogen of said hardener in the range of 1:0.8 to 1.2 whereby a thermosetting urethane composition is obtained, and a surface active agent for dispersing said thermosetting urethane com-position in water, wherein (1) said bifunctional active hydrogen-containing compounds are composed of a polyoxyalkylene glycol having a molecular weight above 1200 and a low molecular weight chain-elongating agent, (2) the sum by weight of said surface active agent contained in said aqueous dispersed urethane composition and said polyoxyalkylene glycol to be one of the starting material for the production of said urethane oligomer is in the range of 15 to 35% of the sum by weight of said surface active agent con-tained in said aqueous dispersed urethane composition and said thermosetting urethane composition, (3) the molecular weight of the urethane oligomer is in the range of 1000 to 5000, (4) the amount of the polyoxyalkylene glycol is in the range of 10 to 35 parts by weight per 100 parts by weight of the urethane oligomer, and (5) the amount of the low molecular weight chain-elongating agent is in the range of 15 to 55 parts by weight per 100 parts by weight of the urethane oligomer.
2. The composition according to claim 1, wherein said polyoxyalkylene glycol has a molecular weight of 1200 to 1500, said low molecular weight chain-elongating agent is a member selected from the group consisting of a glycol, an aminoalcohol and a diamine having a molecular weight below 500, said monofunctional active hydrogen-containing isocyanate-blocking agent is a member selected from the group consisting of a phenol, a lactam, an oxime, an imide, a malonic ester, an acetoacetic ester and an alcohol, said hardener is a member selected from the group consisting of a multifunctional alcohol, a multifunctional amine and a multifunctional aminoalcohol having a molecular weight below 500, and said surface active agent is a nonionic active agent.
3. The composition according to Claim 2, wherein said polyoxyalkylene glycol is a member selected from the group consisting of polyoxypropylene glycol, polyoxytetramethylene glycol and polyoxyethylene-propylene glycol, said monofunctional active hydrogen-containing isocyanate-blocking agent is a member selected from the group consisting of an oxime, a lactam and an alcohol, said diisocyanate is a member selected from the group consisting of 2,4-tolylenediisocyanate,2,6-tolylenediisocyanate, 4,4'-diphenylmethane-diiocyanate, 1,6-hexamethylenediisocyanate, 4,4'-dicyclohexylmethanediisocyanate and isophoronediisocyanate,and said surface active agent is propylene oxide-ethylene oxide copolymer.
4. The composition according to Claim 3, wherein the amount of said monofunctional active hydrogen-containing isocyanate-blocking agent is in the range of 0.4 to 2 gram moles per kg of said urethane oligomer, the amount of said polyoxyalkylene glycol is in the range of 10 to 35 parts by weight per 100 parts by weight of said urethane oligomer, and the amount of said low molecular weight chain-elongating agent is in the range of 15 to 55 parts by weight per 100 parts by weight of said urethane oligomer.
5. A method of forming a protective film on a glass bottle which com-prises coating the outer surface of the bottle with the composition of Claim 1, 2 or 3.
6. A method of forming a protective film on a glass bottle which com-prises coating the outer surface of the bottle with the composition of Claim 4.
7. A glass bottle coated on its outer surface with the composition of Claim 1, 2 or 3 to form a protective film on the outer surface of the glass bottle.
8. A glass bottle coated on its outer surface with the composition of Claim 4 to form a protective film on the outer surface of the glass bottle.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50135645A JPS5259657A (en) | 1975-11-13 | 1975-11-13 | Water-dispersed urethane composition |
| JP50-135645 | 1975-11-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1096079A true CA1096079A (en) | 1981-02-17 |
Family
ID=15156635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA265,307A Expired CA1096079A (en) | 1975-11-13 | 1976-11-10 | Aqueous dispersed urethane composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5259657A (en) |
| CA (1) | CA1096079A (en) |
| DE (1) | DE2651798A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56819A (en) * | 1979-05-17 | 1981-01-07 | Mitui Toatsu Chem Inc | Thermosetting polyurethane resin and coating agent |
| DE3337395A1 (en) * | 1983-10-14 | 1985-05-02 | Herberts Gmbh, 5600 Wuppertal | NON-AQUEOUS VARNISH WITH HIGH STONE IMPACT PROTECTION, METHOD FOR THE PRODUCTION AND USE THEREOF |
| JPH0680104B2 (en) * | 1985-12-26 | 1994-10-12 | 三菱化成株式会社 | Water-based urethane emulsion |
| BR9915981B1 (en) * | 1998-12-07 | 2008-11-18 | process for the coagulation of post-crosslinkable aqueous dispersions, dispersions thus obtained and their use. | |
| CO5231252A1 (en) * | 1999-11-05 | 2002-12-27 | Dow Chemical Co | CARPET BACKUP COMPOSITIONS CONTAINING MIXTURES OF ANIONIC SILOXANIC ALCOXYLATE / ORGANIC COSURFACTANT AS MEANS OF FOAMING AND USE IN CARPET PRODUCTION |
| US20080004395A1 (en) * | 2005-02-11 | 2008-01-03 | Invista North America S.A.R.L. | Aqueous polyurethaneurea compositions including dispersions and films |
| JP5512233B2 (en) * | 2009-11-04 | 2014-06-04 | 第一工業製薬株式会社 | Aqueous resin composition and metal material |
-
1975
- 1975-11-13 JP JP50135645A patent/JPS5259657A/en active Pending
-
1976
- 1976-11-10 CA CA265,307A patent/CA1096079A/en not_active Expired
- 1976-11-12 DE DE19762651798 patent/DE2651798A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE2651798A1 (en) | 1977-05-18 |
| JPS5259657A (en) | 1977-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0416819B1 (en) | Aliphatic spray polyurea elastomers | |
| US4280944A (en) | Thermosetting polyurethane resin and coating agent thereof prepared from at least two polyoxyalkylene polyols, blocking agent, chain-elongating agent, cross-linking agent and a mixture of diisocyanates | |
| US3886226A (en) | Polyurethane composition | |
| CA1301981C (en) | Thermosetting composition for an interpenetrating polymer network system | |
| US4093759A (en) | Glass container coated with polyurethane | |
| US5442034A (en) | Spray polyurea elastomers containing organic carbonates to improve processing characteristics | |
| CA1336734C (en) | Flexible breathable polyurethane coating and films and the prepolymers from which they are made | |
| US4847319A (en) | Sealant compositions or coating mixtures containing functional silane or siloxane adhesion promotors nonreactive with blocked isocyanates | |
| US3963680A (en) | One-part, room-temperature latent, curable isocyanate compositions | |
| EP0505889B1 (en) | Aqueous dispersions of encapsulated polyisocyanates | |
| CA1208992A (en) | Process for adhering polyurethane elastomer to metal | |
| US20040122253A1 (en) | MDI-based polyurethane prepolymer with low monomeric MDI content | |
| US4163814A (en) | Method of coating glass bottle with aqueous dispersed urethane composition | |
| CA2364598A1 (en) | Polyurethane solutions containing alkoxysilane structural units | |
| EP0126297A1 (en) | Method for adhering two different surfaces by means of water dispersible polyurethane adhesive compostitions | |
| CA2406330A1 (en) | Phenolic/polyurea coating co-polymer compositions and process | |
| JP3131224B2 (en) | Heat curable composition | |
| US20030220463A1 (en) | Polyurethane dispersions | |
| CA1096079A (en) | Aqueous dispersed urethane composition | |
| CN108659202A (en) | A kind of solvent-free Waterborne Blocked Polyurethane and preparation method | |
| US4870150A (en) | Polyurethanes made from blends of polypropyleneoxide polyol and polybutyleneoxide polyol intermediates | |
| EP0790263A1 (en) | Finely dispersed polyurethane polyurea crosslinked particles and process for producing the same | |
| CA2016189C (en) | Abrasion resistant polyurethane blend compositions | |
| US4618667A (en) | Nucleation of urethane compositions | |
| JP3961689B2 (en) | Hydrophilic polyurethane resin and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |