CA2120860A1 - Coating composition to be processed as two components, for the preparation of pur elastomers - Google Patents
Coating composition to be processed as two components, for the preparation of pur elastomersInfo
- Publication number
- CA2120860A1 CA2120860A1 CA 2120860 CA2120860A CA2120860A1 CA 2120860 A1 CA2120860 A1 CA 2120860A1 CA 2120860 CA2120860 CA 2120860 CA 2120860 A CA2120860 A CA 2120860A CA 2120860 A1 CA2120860 A1 CA 2120860A1
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- Prior art keywords
- coating composition
- weight
- carbon atoms
- components
- composition according
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1021—Polyurethanes or derivatives thereof
-
- 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
-
- 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
- C08G18/16—Catalysts
- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0652—Polyisocyanates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
ABSTRACT:
Coating composition to be processed as two components, for the preparation of PUR elastomers A solvent-free or low-solvent coating composition to be processed as two components is disclosed. The composition comprises an isocyanate component A and a curing agent component B, wherein A) is an aliphatic or cycloaliphatic polyisocyanate prepolymer having an NCO content of from 1 to 15% by weight, B 1) a diketimine of the general formula I
Coating composition to be processed as two components, for the preparation of PUR elastomers A solvent-free or low-solvent coating composition to be processed as two components is disclosed. The composition comprises an isocyanate component A and a curing agent component B, wherein A) is an aliphatic or cycloaliphatic polyisocyanate prepolymer having an NCO content of from 1 to 15% by weight, B 1) a diketimine of the general formula I
Description
212~8~1 ~ Huls Aktiengesell~chaft - 1 - o.z. 4737 Patent Department Coatin~ comDosition to be Processed as two comPonents for the ~reParation of P~R elastomers .
The pre~ent invention relates to a solvent-free or low~
solvent coating compo~ition to be procecsed as two component~, and to the use thereof for the preparation of elastomers.
Due to their excellent hardness/elasticity ratio, excellent light stability and good processing properties, low-solvent or solvent-free polyisocyanate prepolymers based on aliphatic or cycloaliphatic diisocyanates are widely used in the area of thick-layer application, for example as grouts, roof and floor coatings or window putties.
In order to achieve uniform and complete curing over the entire layer thickness, inert aromatic diamines, for example 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine (DETDA 80), are added to the pre-polymers shortly before processing when the latter are used as two components. Due to their reduced reactivity towards aliphatic and cycloaliphatic isocyanate groups, an acceptable balance is obtained between processing time and curing time. Disadvantages of this class of curing agent which may be mentioned are the intense inherent colour of the curing agents, the high su~ceptibility toward yellowing of the cured elastomers and the fre-quently high toxicity of the aromatic diamines.
Aliphatic or cycloaliphatic diamines, which are regarded as being more favourable as the curing agent component with respect to their toxicity and the weathering stability of the cured materials, are generally too reactive towards isocyanates to ensure an adequate processing time.
::,. . .
2~ 2~860 According to EP-A 359 456, blocked aliphatic or cyclo-aliphatic diamines in the form of, for example, ketimine~
or aldimines are used, due to their reduced reactivity, in RIM technology a~ curing agents for aromatic polyiso-cyanates.
Compared to aliphatic or cycloaliphatic polyisocyanates, these compounds are frequently so stable that they are used in the area of paint technology in one-component, solvent-containing paint systems with a long shelf life which react with moisture, i.e. via hydrolysis of the ketimine or aldimine, in the application of thin coatings (DE-A 15 20 139, US Patent 3,523,925, US
Patent 3,493,543, US Patent 3,535,353, see also Becker/Braun, ~unætstoffhandbuch tPlastics Handbook], Vol. 7: Polyurethane, Hanser-Verlag, 1983, pp. 427 ff.).
Latent amines of this type are also employed as curing agents for isocyanate prepolymers in combination with moisture in the area of low-solvent or solvent-free one-component systems for very flexible, highly elastic elastomer materials, including in the form of certain aldimines having steric hindrance which promotes the shelf life, for example in accordance with DE-A
33 06 373. However, the reactivity in said D~-A must be increased by addition of acids.
All one-component systems based on ketimines and aldimines as latent curing agents and polyisocyanate prepolymers have low basic reactivity 80 that an adequate shelf life of several months can be ensured. However, the low reactivity has the consequence of unsatisfactory curing times on application as a thick-layer system, in particular in the case of relatively hard elastomers. In addition, the direct water/isocyanate competing reaction in the case of aldimines frequently results in undesired foaming of the elastomer.
The ob~ect of the invention was to develop a coating 212~860 ~ 3 _ o.z. 4737 composition to be processed as two components, based on aliphatic or cycloaliphatic polyi~ocyanate prepolymers and a suitable curing agent, which overcomes the outlined disadvantages, i.e. a coating composition of high reac- : -5 tivity, short curing time and broad applicability in :
various hardness ranges without foaming of the elastomer :
material due to water/isocyanate reaction.
Surprisingly, it has been found that a coating composi-tion comprising diketimines based on al~phatic or cyclo-aliphatic ketones and aliphatic or cycloaliphaticdiamines, aliphatic or aromatic carboxylic or sulphonic acids and aliphatic or cycloaliphatic polyisocyanate prepolymers satisfies this requirement. : ~:
The invention relates to a solvent-free or low-solvent coating composition to be processed as two components, for the preparation of PUR elastomers, comprising an isocyanate component A and a curing agent component B and auxiliaries and additive~ known in coating technology, which is characterized in that it contains ~ ~
': ' :
A) an aliphatic or cycloaliphatic polyi~ocyanate pre-polymer having an NC0 content of from 1 to 15 % by weight, B 1) a diketimine of the general formula ~ R2 Rl - (H ~ C )2 in which Rl is an alkylene radical having 2 to 20 carbon atoms, an alkylene radical having 4 to 100 carbon atoms containing oxygen and/or N-alkyl groups as bridging members, or a cycloalkylene radical having 5 to 20 carbon atoms, R2 and R3 are identical or different alkylene radicals having 1 to 8 carbon atoms, or R2 and R3, together with the carbon atom double-bonded to the 2120~0 _ 4 _ o.z. 4737 nitrogen atom, form a 5-membered or 6-membered ring, and B 2) an aromatic or aliphatic carboxylic or sulphonic acid.
Component A) of the coating composition according to the invention is an aliphatic or cycloaliphatic polyiso-cyanate prepolymer having an isocyanate content of from 1 to 15~, as obtained by the known addition reaction of excess aliphatic or cycloaliphatic diisocyanate compound~
with polyhydroxyl components. Suitable diisocyanate compounds are aliphatic diiqocyanates, such as hexa-methylene diisocyanate, 2-methylpentane diisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, preferably cycloaliphatic diisocyanates, such as 1,4-diisocyanatocyclohexane, or 2,4~- or 4,4~-diisocyanato-dicyclohexylmethane. Particular preference is given to 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (i~ophorone diisocyanate, IPDI).
These polyisocyanate prepolymers can also be blended with pure polyisocyanate~ of the abovementioned diisocyanates, as obtained, for example, by isocyanurate ring or biuret formation. The preferred diisocyanate here is hexamethyl-ene diisocyanate, particular preference being given to IPDI.
The polyisocyanate prepolymers having an NCO content of from 1 to 15~ to be employed according to the invention are prepared by the addition reaction of diisocyanate with the polyhydroxyl component, where an NCO/OH ratio!of from 1.5 : 1 to 5 : 1 is preferably maintained and the excess monomeric diisocyanate can also be removed by 30 distillation. -The reaction of diisocyanate and polyol component can be ~ carried out in a solvent, but especially carried out `~ without a solvent. The preparation is carried out at from 20 to 90C, optionally using the catalysts which are ~ ,' .~ .
~2~g~
_ 5 _ o.z. 4737 cu~tomary in urethane chemistry, such a~, for example, tertiary amine~, Sn salts or Zn ~alt~. The polyol com-ponents are preferably polyols having a molecular weight in the range from 500 to 6,000 g/mol and a mean functionality of from 2 to 3. ~he polyol components according to the invention have a low solvent content, with a non-volatile content of at least 90 % by weight, but are preferably solvent-free. Suitable polyol components are polyester-polyols, polyQther-polyols or polycarbonate polyols, also copolymers of these materials or mixtures of the polymers; preference i8 given to polyester-polyol~, particular preference to polyether-polyolæ.
Polyester-polyols are prepared by esterification or tran~esterification of dibasic aliphatic or aromatic, but preferably aliphatic carboxylic acids or esters or dihydric or polyhydric alcohols. Examples of suitable dicarboxylic acids are succinic acid, glutaric acid, adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, dodecanedioic acid, phthalic acid, iso-phthalic acid and terephthalic acid. Suitable dihydric or polyhydric alcohols are ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentane-diol, 2,2,4- and 2,4,4-trimethyl-1,6-hexanediol, decane-diol, neopentyl glycol and trimethylolpropane.
The reaction of the polyol component and the diisocyanatecan also be carried out using a low-molecular-weight chain extender, such as a diol having a molecular weight of from 60 to 200.
The functionality of the polyester-polyols is from 2 to 3, but is preferably 2. The molecular weight is between 500 and 3,000. Novel polyester-polyols are also poly-caprolactones which can be obtained by the addition reaction of caprolactone with difunctional or trifunctional alcohols, quch as, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol '~
~; ' ' . : ' ' "':,~ ' ' ' , ' ,',', ' .
212~8~
` - 6 - O.Z. 4737 or trimethylolpropane.
The polyether-polyol~, which are preferred according to the invention, are prepared by polymerization of alkylene oxides, such as, for example, ethylene oxide, propylene oxide or tetrahydrofuran, using a difunctional or tri-functional initiator molecule containing active hydrogen atoms, such as, for example, water, ethylene glycol, propylene glycol, butanediol or trimethylolpropane.
It is also possible to employ copolymers of the said alkylene oxides or alternatively products of the reaction of the polyether polyols with lactones, such as, for example, caprolactone.
Polyether-polyols have a molecular weight of from 500 to 66,000 g/mol, preferably from 600 to 3,500 g/mol, and a functionality of from 2 to 3.
~he polycarbonate-diols which can be employed according to the invention are prepared by reacting low-molecular-weight diols with diaryl carbonates, such as, for example, diphenyl carbonate, dialkyl carbonates, such a~
for example, dimethyl carbonate, cyclic carbonates or phosgene. Suitable diols which may be mentioned are 1,3-propanediol, 1,4-butanediol, 3-methyl-1,5-pentane-diol, 1,6-hexanediol, 2,2,4- or 2,4,4-trimethylhexane-diol, diethylene glycol, triethylene glycol, tetra-ethylene glycol or mixtures of these diol components.
: .
Component B 1) of the coating composition accordingi tothe invention is an aliphatic or cycloaliphatic ketimine obtained by reacting an aliphatic or cycloaliphatic ketone with simultaneous removal of the water produced in the reaction mixture - for example by azeotropic distil-lation. The preparation is carried out with an at least equivalent ratio of amine and ketone groups, i.e. the NH2/C=0 ratio is at least 1 : 1, preferably from 1 : 1 to 1 : 3, in an inert solvent which i8 suitable for the 21~8~
_ 7 _ o.z. 4737 azeotropic removal of the water of reaction, for example toluene, benzene or heptane. If the ketone i8 also suitable as an entrainer, it is not necessary to use the abovementioned illustrative solvent~ if an NH2/C=O ratio of from 1 : 2 to 1 : 20 i8 used. In these cases, this variant is preferred. When all the water has been removed, excess ketone and optionally solvent are removed by distillation. If desired, the diketimine can be purified by distillation.
Suitable for the preparation of aliphatic or cyclo-aliphatic ketimines are diamines having 2 to 20 carbon atoms; examples of aliphatic diamines are 1,4-diamino-butane, 1~5-di~minopentane~ 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 2,2,4- and/or 2,4,4-trimethyl-1,6-di-aminohexane and 1,12-diaminododecane; examples of cyclo-aliphatic diamines are 4,4- and 2,4-diaminodicyclohexyl-methane, 3,3~-dimethyl-4,4~-diaminodicyclohexylmethane and l-amino-3,5,5-trimethyl-3-aminomethylcyclohexane (isophoronediamine). Preference is given to 1,6-di~mino-20 hexane, 2,4,4- and/or 2,4,4-trimethyl-1,6-diaminohexane, and particular preference is given to isophoronediamine.
Polyethylene oxide- and polypropylene oxide-based diamines, as are known under the name JEFPANINED, are also suitable for the preparation of relatively high-molecular-weight ketimines.
,.
The diketimines according to the invention are prepared using aliphatic or cycloaliphatic ketones having 3 to 15 carbon atoms. Examples of suitable aliphatic ketones are:
scetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, diethyl ketone, dii~opropyl ketone, methyl isobutyl ketone, methyl isoamyl ketone and diisobutyl ketone, and examples of cycloaliphatic ketones are cyclopentanone, cyclohexanone and 3,3,5-trimethyl-cyclohexanone. Preference is given to methyl isobutyl ketone.
,."., . . . , . " , . -,.. , ,.. - . .
2~2~86~
- 8 - O.Z. 4737 Component B 2 in the coating composition according to the invention is an aliphatic or aromatic carboxylic acid or sulphonic acid. Examples of aliphatic carboxylic acidq - are formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid and 2-ethyl-~ hexanoic acid, examples of aromatic carboxylic acid~ are benzoic acid and salicylic acid, and an example of a sulphonic acid is p-toluenesulphonic acid. Preference is given to 2-ethylhexanoic acid. From 0.05 to 3~ of com-ponent B 2)r based on the total binder of components A) and B), are particularly preferably employed. Under the catalytic action of the acids in the presence of mois-ture, the diketimines form amines, which then react with the isocyanate component.
In a less preferred embodiment, component A) can also be a partially silanized polyisocyanate prepolymer, as described, for example, in DE-A 37 23 936, or mixtures of fully silanized prepolymers, as described, for example, in German Patent 27 38 979 and DE A 36 29 237, with polyisocyanate prepolymers.
. :
A further, but less preferred embodiment comprises mixing component B) with other isocyanate-reactive compounds, -~ such as diols and polyols or diamines. The diamines are preferably the diamines already employed for the prepara- l~
25 tion of the ketimines, such as, for example, isophorone- j -diamine, 4,4'- and 2,4'-diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane.
Just before application, components A) and B) are mixed.
In an embodiment which is preferred according to the invention, such amounts of components A) and B) are mixed 80 that the ratio between NC0 and latent amine groups is from 1.4 s 1 to 1 : 1, particularly preferably from 1.1 : 1 to 1 : 1.
Small amounts of solvents, preferably a maximum of 10%, particularly preferably a maximum of 5%, can be added to 2~208~
_ g _ O.Z. 4737 the mixture in order to reduce the viscosity.
Furthermore, additives which are customary in coatinq technology, such as pigments, fillers, dyes, plasti-cizers, thickeners, adhe~ion promoters, W absorbers, oxidation stabilizers, HALS ~tabilizers and customary catalysts of urethane chemistry, such a~, for example, tertiary amines, may furthermore be added to the coating composition according to the invention.
~ he ratio between the total amounts by weight of the non-volatile constituents of components A) and B) and the total amounts by weight of the ~olvents present in these component~ i8 preferably in the range from 90 : 10 to 100 : 0.
In the examples below, parts are by weight.
ExamDle 1 Dilcetimi ne 158 parts by weight of a mixture of 2,2,4- and 2,4,4-trimethyl-1,6-diaminohexane are mixed with 400 parts by weight of methyl isobutyl ketone, and the mixture is warmed to a maximum of 130C on a water separator. After about 8 hours, 36 parts by weight of water have separated off. The exces~ ketone i8 removed by distillation under reduced pressure. The amine equivalent of the liquid, yellowish residue, determined by titration, is 162 g/eq.
~xam~le 2 Diketimine 2 170 part6 by weight of 1-amino-3,5,5-trimethyl-3-amino-methylcyclohexane (isophoronediamine) are mixed with 400 parts by weight of methyl isobutyl ketone, and reacted and worked up analogously to diketimine 1 (36 parts by weight of water separated off). The residue obtained is a yellowish liquid having an amine equivalent weight of 167 g/eq.
2l2o8~
- 10 - O.Z. 4737 Exam~le 3 Diketimine 3 116 parts by weight of 2-methyl-1,5-diaminopentane are reacted with 400 parts by weight of methyl isobutyl ketone analogously to diketimine 1 and diketimine 2 and worked up after 36 parts by weight of water have ~epa-rated off. Equivalent weight of the yellowish residue:
141 g/eq.
Example 4 - comparison Dialdimine 1 170 parts by weight of isophorodiamine are mixed with 200 parts by weight of isobutyraldehyde and 200 g of toluene at room temperature, and the mixture is left to react for 1 hour and subsequently heated at a maximum of 130C on a water separator. After 6 hours, 36 parts by weight of water have separated off. The toluene and the excess isobutyraldehyde are removed by distillation under reduced pressure. The equivalent weight was measuredi at 140 g/eq.
Exam~le 5 Polyisocyanaite prepolymer 1 1,~50 parts by weight of a trimathylolpropane-initiated copolymer of ethylene oxide and propylene oxide having a molecular weight of about 3,500 g/mol are mixed with 333 parts by weight of isophorone diisocyanate and 2 g of dibutyltin dilaurate (DBTL), and the mixture is stirred at 50C for 5 hours. After cooling, a polyisocyanate prepolymer containing 2.8% of NC0 and having a viscosity of 13,000 mPa-s at 25C i8 obtained.
Exam~le 6 Polyisocyanate prepolymer 2 1 part by weight of DBTL and 406 g of isophoronediiso-2~208~0 - 11 - O.Z. 4737 cyanate are added to 593 psrts by weight of a polytetra-hydrofuran diol having a molecular weight of about 650 g/mol. The mixture is stirred at 50C for 5 hour~.
After cooling, a polyisocyanate prepolymer containing 7.3% of NCO and having a viscosity of 23,000 mPa.~ at 25 C is obtained.
Exam~les 7 to 11 and Com~arative Exam~les 12 and_l3 In Examples 7 to 11, the polyisocyanate prepolymers 1 and 2 or mixtures of these products are cured by mean~ of a mixture of the diketimines 1 to 3 with 0.5~ of 2-ethyl-hexanoic acid (based on the total formulation) in the NCO:latent NH2 ratio of 1.05 : 1.
In Comparative Examples 12 and 13, a reaction with a diketimine without addition of 2-ethylhexanoic acid or curing by means of the dialdimine 1 from ~xample 4 and addition of 2-ethylhexanoic acid is described.
The solvent free two-component systems are applied in a coating thickness of 6 mm, and the progres3 of curing at 23C and 5C is monitored from the Shore Hardness.
~ , ~
2~2~8~0 ,~ = = = = = = =
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1'' 1'' ~
.,~. ~ ; . , ; , .. ~ '~. :. , . . :: . ' i''.' ' "'. ' '` it . ; i . ' - 'i: ~ " '
The pre~ent invention relates to a solvent-free or low~
solvent coating compo~ition to be procecsed as two component~, and to the use thereof for the preparation of elastomers.
Due to their excellent hardness/elasticity ratio, excellent light stability and good processing properties, low-solvent or solvent-free polyisocyanate prepolymers based on aliphatic or cycloaliphatic diisocyanates are widely used in the area of thick-layer application, for example as grouts, roof and floor coatings or window putties.
In order to achieve uniform and complete curing over the entire layer thickness, inert aromatic diamines, for example 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine (DETDA 80), are added to the pre-polymers shortly before processing when the latter are used as two components. Due to their reduced reactivity towards aliphatic and cycloaliphatic isocyanate groups, an acceptable balance is obtained between processing time and curing time. Disadvantages of this class of curing agent which may be mentioned are the intense inherent colour of the curing agents, the high su~ceptibility toward yellowing of the cured elastomers and the fre-quently high toxicity of the aromatic diamines.
Aliphatic or cycloaliphatic diamines, which are regarded as being more favourable as the curing agent component with respect to their toxicity and the weathering stability of the cured materials, are generally too reactive towards isocyanates to ensure an adequate processing time.
::,. . .
2~ 2~860 According to EP-A 359 456, blocked aliphatic or cyclo-aliphatic diamines in the form of, for example, ketimine~
or aldimines are used, due to their reduced reactivity, in RIM technology a~ curing agents for aromatic polyiso-cyanates.
Compared to aliphatic or cycloaliphatic polyisocyanates, these compounds are frequently so stable that they are used in the area of paint technology in one-component, solvent-containing paint systems with a long shelf life which react with moisture, i.e. via hydrolysis of the ketimine or aldimine, in the application of thin coatings (DE-A 15 20 139, US Patent 3,523,925, US
Patent 3,493,543, US Patent 3,535,353, see also Becker/Braun, ~unætstoffhandbuch tPlastics Handbook], Vol. 7: Polyurethane, Hanser-Verlag, 1983, pp. 427 ff.).
Latent amines of this type are also employed as curing agents for isocyanate prepolymers in combination with moisture in the area of low-solvent or solvent-free one-component systems for very flexible, highly elastic elastomer materials, including in the form of certain aldimines having steric hindrance which promotes the shelf life, for example in accordance with DE-A
33 06 373. However, the reactivity in said D~-A must be increased by addition of acids.
All one-component systems based on ketimines and aldimines as latent curing agents and polyisocyanate prepolymers have low basic reactivity 80 that an adequate shelf life of several months can be ensured. However, the low reactivity has the consequence of unsatisfactory curing times on application as a thick-layer system, in particular in the case of relatively hard elastomers. In addition, the direct water/isocyanate competing reaction in the case of aldimines frequently results in undesired foaming of the elastomer.
The ob~ect of the invention was to develop a coating 212~860 ~ 3 _ o.z. 4737 composition to be processed as two components, based on aliphatic or cycloaliphatic polyi~ocyanate prepolymers and a suitable curing agent, which overcomes the outlined disadvantages, i.e. a coating composition of high reac- : -5 tivity, short curing time and broad applicability in :
various hardness ranges without foaming of the elastomer :
material due to water/isocyanate reaction.
Surprisingly, it has been found that a coating composi-tion comprising diketimines based on al~phatic or cyclo-aliphatic ketones and aliphatic or cycloaliphaticdiamines, aliphatic or aromatic carboxylic or sulphonic acids and aliphatic or cycloaliphatic polyisocyanate prepolymers satisfies this requirement. : ~:
The invention relates to a solvent-free or low-solvent coating composition to be processed as two components, for the preparation of PUR elastomers, comprising an isocyanate component A and a curing agent component B and auxiliaries and additive~ known in coating technology, which is characterized in that it contains ~ ~
': ' :
A) an aliphatic or cycloaliphatic polyi~ocyanate pre-polymer having an NC0 content of from 1 to 15 % by weight, B 1) a diketimine of the general formula ~ R2 Rl - (H ~ C )2 in which Rl is an alkylene radical having 2 to 20 carbon atoms, an alkylene radical having 4 to 100 carbon atoms containing oxygen and/or N-alkyl groups as bridging members, or a cycloalkylene radical having 5 to 20 carbon atoms, R2 and R3 are identical or different alkylene radicals having 1 to 8 carbon atoms, or R2 and R3, together with the carbon atom double-bonded to the 2120~0 _ 4 _ o.z. 4737 nitrogen atom, form a 5-membered or 6-membered ring, and B 2) an aromatic or aliphatic carboxylic or sulphonic acid.
Component A) of the coating composition according to the invention is an aliphatic or cycloaliphatic polyiso-cyanate prepolymer having an isocyanate content of from 1 to 15~, as obtained by the known addition reaction of excess aliphatic or cycloaliphatic diisocyanate compound~
with polyhydroxyl components. Suitable diisocyanate compounds are aliphatic diiqocyanates, such as hexa-methylene diisocyanate, 2-methylpentane diisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, preferably cycloaliphatic diisocyanates, such as 1,4-diisocyanatocyclohexane, or 2,4~- or 4,4~-diisocyanato-dicyclohexylmethane. Particular preference is given to 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (i~ophorone diisocyanate, IPDI).
These polyisocyanate prepolymers can also be blended with pure polyisocyanate~ of the abovementioned diisocyanates, as obtained, for example, by isocyanurate ring or biuret formation. The preferred diisocyanate here is hexamethyl-ene diisocyanate, particular preference being given to IPDI.
The polyisocyanate prepolymers having an NCO content of from 1 to 15~ to be employed according to the invention are prepared by the addition reaction of diisocyanate with the polyhydroxyl component, where an NCO/OH ratio!of from 1.5 : 1 to 5 : 1 is preferably maintained and the excess monomeric diisocyanate can also be removed by 30 distillation. -The reaction of diisocyanate and polyol component can be ~ carried out in a solvent, but especially carried out `~ without a solvent. The preparation is carried out at from 20 to 90C, optionally using the catalysts which are ~ ,' .~ .
~2~g~
_ 5 _ o.z. 4737 cu~tomary in urethane chemistry, such a~, for example, tertiary amine~, Sn salts or Zn ~alt~. The polyol com-ponents are preferably polyols having a molecular weight in the range from 500 to 6,000 g/mol and a mean functionality of from 2 to 3. ~he polyol components according to the invention have a low solvent content, with a non-volatile content of at least 90 % by weight, but are preferably solvent-free. Suitable polyol components are polyester-polyols, polyQther-polyols or polycarbonate polyols, also copolymers of these materials or mixtures of the polymers; preference i8 given to polyester-polyol~, particular preference to polyether-polyolæ.
Polyester-polyols are prepared by esterification or tran~esterification of dibasic aliphatic or aromatic, but preferably aliphatic carboxylic acids or esters or dihydric or polyhydric alcohols. Examples of suitable dicarboxylic acids are succinic acid, glutaric acid, adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, dodecanedioic acid, phthalic acid, iso-phthalic acid and terephthalic acid. Suitable dihydric or polyhydric alcohols are ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentane-diol, 2,2,4- and 2,4,4-trimethyl-1,6-hexanediol, decane-diol, neopentyl glycol and trimethylolpropane.
The reaction of the polyol component and the diisocyanatecan also be carried out using a low-molecular-weight chain extender, such as a diol having a molecular weight of from 60 to 200.
The functionality of the polyester-polyols is from 2 to 3, but is preferably 2. The molecular weight is between 500 and 3,000. Novel polyester-polyols are also poly-caprolactones which can be obtained by the addition reaction of caprolactone with difunctional or trifunctional alcohols, quch as, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol '~
~; ' ' . : ' ' "':,~ ' ' ' , ' ,',', ' .
212~8~
` - 6 - O.Z. 4737 or trimethylolpropane.
The polyether-polyol~, which are preferred according to the invention, are prepared by polymerization of alkylene oxides, such as, for example, ethylene oxide, propylene oxide or tetrahydrofuran, using a difunctional or tri-functional initiator molecule containing active hydrogen atoms, such as, for example, water, ethylene glycol, propylene glycol, butanediol or trimethylolpropane.
It is also possible to employ copolymers of the said alkylene oxides or alternatively products of the reaction of the polyether polyols with lactones, such as, for example, caprolactone.
Polyether-polyols have a molecular weight of from 500 to 66,000 g/mol, preferably from 600 to 3,500 g/mol, and a functionality of from 2 to 3.
~he polycarbonate-diols which can be employed according to the invention are prepared by reacting low-molecular-weight diols with diaryl carbonates, such as, for example, diphenyl carbonate, dialkyl carbonates, such a~
for example, dimethyl carbonate, cyclic carbonates or phosgene. Suitable diols which may be mentioned are 1,3-propanediol, 1,4-butanediol, 3-methyl-1,5-pentane-diol, 1,6-hexanediol, 2,2,4- or 2,4,4-trimethylhexane-diol, diethylene glycol, triethylene glycol, tetra-ethylene glycol or mixtures of these diol components.
: .
Component B 1) of the coating composition accordingi tothe invention is an aliphatic or cycloaliphatic ketimine obtained by reacting an aliphatic or cycloaliphatic ketone with simultaneous removal of the water produced in the reaction mixture - for example by azeotropic distil-lation. The preparation is carried out with an at least equivalent ratio of amine and ketone groups, i.e. the NH2/C=0 ratio is at least 1 : 1, preferably from 1 : 1 to 1 : 3, in an inert solvent which i8 suitable for the 21~8~
_ 7 _ o.z. 4737 azeotropic removal of the water of reaction, for example toluene, benzene or heptane. If the ketone i8 also suitable as an entrainer, it is not necessary to use the abovementioned illustrative solvent~ if an NH2/C=O ratio of from 1 : 2 to 1 : 20 i8 used. In these cases, this variant is preferred. When all the water has been removed, excess ketone and optionally solvent are removed by distillation. If desired, the diketimine can be purified by distillation.
Suitable for the preparation of aliphatic or cyclo-aliphatic ketimines are diamines having 2 to 20 carbon atoms; examples of aliphatic diamines are 1,4-diamino-butane, 1~5-di~minopentane~ 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 2,2,4- and/or 2,4,4-trimethyl-1,6-di-aminohexane and 1,12-diaminododecane; examples of cyclo-aliphatic diamines are 4,4- and 2,4-diaminodicyclohexyl-methane, 3,3~-dimethyl-4,4~-diaminodicyclohexylmethane and l-amino-3,5,5-trimethyl-3-aminomethylcyclohexane (isophoronediamine). Preference is given to 1,6-di~mino-20 hexane, 2,4,4- and/or 2,4,4-trimethyl-1,6-diaminohexane, and particular preference is given to isophoronediamine.
Polyethylene oxide- and polypropylene oxide-based diamines, as are known under the name JEFPANINED, are also suitable for the preparation of relatively high-molecular-weight ketimines.
,.
The diketimines according to the invention are prepared using aliphatic or cycloaliphatic ketones having 3 to 15 carbon atoms. Examples of suitable aliphatic ketones are:
scetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, diethyl ketone, dii~opropyl ketone, methyl isobutyl ketone, methyl isoamyl ketone and diisobutyl ketone, and examples of cycloaliphatic ketones are cyclopentanone, cyclohexanone and 3,3,5-trimethyl-cyclohexanone. Preference is given to methyl isobutyl ketone.
,."., . . . , . " , . -,.. , ,.. - . .
2~2~86~
- 8 - O.Z. 4737 Component B 2 in the coating composition according to the invention is an aliphatic or aromatic carboxylic acid or sulphonic acid. Examples of aliphatic carboxylic acidq - are formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid and 2-ethyl-~ hexanoic acid, examples of aromatic carboxylic acid~ are benzoic acid and salicylic acid, and an example of a sulphonic acid is p-toluenesulphonic acid. Preference is given to 2-ethylhexanoic acid. From 0.05 to 3~ of com-ponent B 2)r based on the total binder of components A) and B), are particularly preferably employed. Under the catalytic action of the acids in the presence of mois-ture, the diketimines form amines, which then react with the isocyanate component.
In a less preferred embodiment, component A) can also be a partially silanized polyisocyanate prepolymer, as described, for example, in DE-A 37 23 936, or mixtures of fully silanized prepolymers, as described, for example, in German Patent 27 38 979 and DE A 36 29 237, with polyisocyanate prepolymers.
. :
A further, but less preferred embodiment comprises mixing component B) with other isocyanate-reactive compounds, -~ such as diols and polyols or diamines. The diamines are preferably the diamines already employed for the prepara- l~
25 tion of the ketimines, such as, for example, isophorone- j -diamine, 4,4'- and 2,4'-diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane.
Just before application, components A) and B) are mixed.
In an embodiment which is preferred according to the invention, such amounts of components A) and B) are mixed 80 that the ratio between NC0 and latent amine groups is from 1.4 s 1 to 1 : 1, particularly preferably from 1.1 : 1 to 1 : 1.
Small amounts of solvents, preferably a maximum of 10%, particularly preferably a maximum of 5%, can be added to 2~208~
_ g _ O.Z. 4737 the mixture in order to reduce the viscosity.
Furthermore, additives which are customary in coatinq technology, such as pigments, fillers, dyes, plasti-cizers, thickeners, adhe~ion promoters, W absorbers, oxidation stabilizers, HALS ~tabilizers and customary catalysts of urethane chemistry, such a~, for example, tertiary amines, may furthermore be added to the coating composition according to the invention.
~ he ratio between the total amounts by weight of the non-volatile constituents of components A) and B) and the total amounts by weight of the ~olvents present in these component~ i8 preferably in the range from 90 : 10 to 100 : 0.
In the examples below, parts are by weight.
ExamDle 1 Dilcetimi ne 158 parts by weight of a mixture of 2,2,4- and 2,4,4-trimethyl-1,6-diaminohexane are mixed with 400 parts by weight of methyl isobutyl ketone, and the mixture is warmed to a maximum of 130C on a water separator. After about 8 hours, 36 parts by weight of water have separated off. The exces~ ketone i8 removed by distillation under reduced pressure. The amine equivalent of the liquid, yellowish residue, determined by titration, is 162 g/eq.
~xam~le 2 Diketimine 2 170 part6 by weight of 1-amino-3,5,5-trimethyl-3-amino-methylcyclohexane (isophoronediamine) are mixed with 400 parts by weight of methyl isobutyl ketone, and reacted and worked up analogously to diketimine 1 (36 parts by weight of water separated off). The residue obtained is a yellowish liquid having an amine equivalent weight of 167 g/eq.
2l2o8~
- 10 - O.Z. 4737 Exam~le 3 Diketimine 3 116 parts by weight of 2-methyl-1,5-diaminopentane are reacted with 400 parts by weight of methyl isobutyl ketone analogously to diketimine 1 and diketimine 2 and worked up after 36 parts by weight of water have ~epa-rated off. Equivalent weight of the yellowish residue:
141 g/eq.
Example 4 - comparison Dialdimine 1 170 parts by weight of isophorodiamine are mixed with 200 parts by weight of isobutyraldehyde and 200 g of toluene at room temperature, and the mixture is left to react for 1 hour and subsequently heated at a maximum of 130C on a water separator. After 6 hours, 36 parts by weight of water have separated off. The toluene and the excess isobutyraldehyde are removed by distillation under reduced pressure. The equivalent weight was measuredi at 140 g/eq.
Exam~le 5 Polyisocyanaite prepolymer 1 1,~50 parts by weight of a trimathylolpropane-initiated copolymer of ethylene oxide and propylene oxide having a molecular weight of about 3,500 g/mol are mixed with 333 parts by weight of isophorone diisocyanate and 2 g of dibutyltin dilaurate (DBTL), and the mixture is stirred at 50C for 5 hours. After cooling, a polyisocyanate prepolymer containing 2.8% of NC0 and having a viscosity of 13,000 mPa-s at 25C i8 obtained.
Exam~le 6 Polyisocyanate prepolymer 2 1 part by weight of DBTL and 406 g of isophoronediiso-2~208~0 - 11 - O.Z. 4737 cyanate are added to 593 psrts by weight of a polytetra-hydrofuran diol having a molecular weight of about 650 g/mol. The mixture is stirred at 50C for 5 hour~.
After cooling, a polyisocyanate prepolymer containing 7.3% of NCO and having a viscosity of 23,000 mPa.~ at 25 C is obtained.
Exam~les 7 to 11 and Com~arative Exam~les 12 and_l3 In Examples 7 to 11, the polyisocyanate prepolymers 1 and 2 or mixtures of these products are cured by mean~ of a mixture of the diketimines 1 to 3 with 0.5~ of 2-ethyl-hexanoic acid (based on the total formulation) in the NCO:latent NH2 ratio of 1.05 : 1.
In Comparative Examples 12 and 13, a reaction with a diketimine without addition of 2-ethylhexanoic acid or curing by means of the dialdimine 1 from ~xample 4 and addition of 2-ethylhexanoic acid is described.
The solvent free two-component systems are applied in a coating thickness of 6 mm, and the progres3 of curing at 23C and 5C is monitored from the Shore Hardness.
~ , ~
2~2~8~0 ,~ = = = = = = =
. ~ ~ ~ ~ u7 ~n I
o ~,~ l l l l l l ,~~ ol U~ U. o - , ~-N j ~ ~
~ ~ , 1~ N ¦
O
I _ _ _ _ _ _ _ ?~: ;' - i , ,- ., r~:.: ~ .. . : ~ ,, ' ~ ~ ; : , '.... . ~ ' . : .
21208~
~ _ I ~
O I X~r~ XXXXX XXX X X
~ I 11 ~ XXX~C XXXX~ I - :
~ I
~ x-tu~ x~r I
~ _ I
' ':
~o ~s~ I ~ g :.
:~
A ~ ~R ~ X ~ ~ ""
V ~ I . ~ .
Sl ~~ ~ r %~ _ ~a ' ~ I _ ' ::
~t'` x~ x~D$~
V ~ ~; < ~ I <~ o~ - ~
.~ ~ ~ r ulc '~
1'' 1'' ~
.,~. ~ ; . , ; , .. ~ '~. :. , . . :: . ' i''.' ' "'. ' '` it . ; i . ' - 'i: ~ " '
Claims (9)
1. A solvent-free or low-solvent coating composition to be processed as two components, said composition comprising an isocyanate component A and a curing agent component B, wherein A) is an aliphatic or cycloaliphatic polyisocyanate prepolymer having an NCO content of from about 1 to about 15% by weight, B 1) is a diketimine of the general formula I
) 2 in which R1 is an alkylene radical having 2 to 20 carbon atoms, an alkylene radical having 4 to 100 carbon atoms and containing oxygen and/or N-alkyl groups as bridging members, or a cyclo-alkylene radical having 5 to 20 carbon atoms, R2 and R3 are identical or different alkylene radicals having 1 to 8 carbon atoms, or R2 and R3, together with the carbon atom double-bonded to the nitrogen atom, form a 5-membered or 6-membered ring, and B 2) is an aromatic or aliphatic carboxylic or sulphonic acid.
) 2 in which R1 is an alkylene radical having 2 to 20 carbon atoms, an alkylene radical having 4 to 100 carbon atoms and containing oxygen and/or N-alkyl groups as bridging members, or a cyclo-alkylene radical having 5 to 20 carbon atoms, R2 and R3 are identical or different alkylene radicals having 1 to 8 carbon atoms, or R2 and R3, together with the carbon atom double-bonded to the nitrogen atom, form a 5-membered or 6-membered ring, and B 2) is an aromatic or aliphatic carboxylic or sulphonic acid.
2. A coating composition according to claim 1, wherein the polyisocyanate prepolymer is based on cycloaliphatic diisocyanantes and polyols having a molecular weight in the range from about 500 to about 6,000 g/mol and a mean functionality of from 2 to 3.
3. A coating composition according to claim 1, wherein the polyisocyanate prepolymer is based on 1-isocyanato-3,5,5-trimethyl-3-isocyanatomethyl-cyclohexane.
4. A coating composition according to claim 1, wherein in the formula I R1 is a radical formed by removal of the amino groups from 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 2,2,4- and/or 2,4,4-trimethyl-1,6-diaminohexane, 1-amino-3,5,5-trimethyl-3-aminomethyl-cyclohexane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane or 4,4'-diaminodicyclohexylmethane.
5. A coating composition according to claim 1, wherein in the formula I radicals R1 and R2 are methyl, ethyl, isopropyl or 2-methylpropyl groups.
6. A coating composition according to claim 1, wherein component B2) is 2-ethylhexanoic acid, benzoic acid, salicylic acid or p-toluenesulphonic acid.
7. A coating composition according to claim 1, wherein the relative amount by weight of component B2) is 0.05 to 3%, based on the total weight of components A) and B).
8. A coating composition according to claim 1, wherein the equivalent ratio between the NCO groups of polymer component A) and the latent amino groups of component B) is from about 1.4 : 1 to about 1: 1.
9. A coating composition according to claim 1, wherein the ratio between the total amount by weight of the non-volatile constituents of components A) and B) and the total amount by weight of the solvents present in these components is from about 90 : 10 to about 100 : 0.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4311923.9 | 1993-04-10 | ||
| DE19934311923 DE4311923A1 (en) | 1993-04-10 | 1993-04-10 | Two-component coating composition for the production of PUR elastomers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2120860A1 true CA2120860A1 (en) | 1994-10-11 |
Family
ID=6485292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2120860 Abandoned CA2120860A1 (en) | 1993-04-10 | 1994-04-08 | Coating composition to be processed as two components, for the preparation of pur elastomers |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0620237A3 (en) |
| JP (1) | JPH0776670A (en) |
| CA (1) | CA2120860A1 (en) |
| DE (1) | DE4311923A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955199A (en) * | 1997-09-26 | 1999-09-21 | Ashland Inc. | Imine-containing curative for two component polyurethane structural adhesives |
| US20100130674A1 (en) * | 2007-03-28 | 2010-05-27 | Sika Technology Ag | Method for the production of polyurethane compositions with a low isocyanate monomer content |
| US8324340B2 (en) | 2006-10-31 | 2012-12-04 | Sika Technology Ag | Polyurethane composition with good initial strength |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100273932A1 (en) * | 2007-10-22 | 2010-10-28 | Base Se | Polyisocyanate containing urethane groups |
| EP2593490B1 (en) | 2010-07-13 | 2015-09-09 | Basf Se | High-functionality polyisocyanates having urethane groups |
| US9550857B2 (en) | 2010-07-13 | 2017-01-24 | Basf Se | High-functionality polyisocyanates containing urethane groups |
| US8580887B2 (en) | 2010-07-30 | 2013-11-12 | Basf Se | High-functionality polyisocyanates containing urethane groups |
| CN103140530A (en) | 2010-07-30 | 2013-06-05 | 巴斯夫欧洲公司 | High-functionality polyisocyanates having urethane groups |
| CN104140754B (en) * | 2013-05-10 | 2016-08-10 | 北京碧海舟腐蚀防护工业股份有限公司 | Unmaned platform and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3645907A (en) * | 1969-08-25 | 1972-02-29 | Goodyear Tire & Rubber | Composition prepared by treating diamine-ketone mixtures with calcium carbide |
| DE2651479C2 (en) * | 1976-11-11 | 1986-03-20 | Schering AG, 1000 Berlin und 4709 Bergkamen | Elastic adhesive |
| DE3306373A1 (en) * | 1983-02-24 | 1984-08-30 | Basf Ag, 6700 Ludwigshafen | Moisture-curing, storage-stable single-component polyurethane system |
| DE3701547A1 (en) * | 1987-01-21 | 1988-08-04 | Basf Lacke & Farben | POLYETHERURETHANE, METHOD FOR THE PRODUCTION THEREOF, LEVELING AGENTS AND USE OF POLYETHERURETHANE |
| DE3703973A1 (en) * | 1987-02-10 | 1988-08-18 | Bayer Ag | PROCESS FOR THE PREPARATION OF PRE-POLYMERS HAVING ISOCYANATE GROUPS, THE PRE-POLYMERS PREPARED THEREOF AND THEIR USE |
| US5130402A (en) * | 1988-07-01 | 1992-07-14 | Sanyo Chemical Industries, Ltd. | Coating composition and plastisol composition, and articles coated therewith |
-
1993
- 1993-04-10 DE DE19934311923 patent/DE4311923A1/en not_active Withdrawn
-
1994
- 1994-02-11 EP EP94102104A patent/EP0620237A3/en not_active Withdrawn
- 1994-04-08 CA CA 2120860 patent/CA2120860A1/en not_active Abandoned
- 1994-04-08 JP JP6071030A patent/JPH0776670A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955199A (en) * | 1997-09-26 | 1999-09-21 | Ashland Inc. | Imine-containing curative for two component polyurethane structural adhesives |
| US8324340B2 (en) | 2006-10-31 | 2012-12-04 | Sika Technology Ag | Polyurethane composition with good initial strength |
| US20100130674A1 (en) * | 2007-03-28 | 2010-05-27 | Sika Technology Ag | Method for the production of polyurethane compositions with a low isocyanate monomer content |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0620237A2 (en) | 1994-10-19 |
| EP0620237A3 (en) | 1995-01-25 |
| JPH0776670A (en) | 1995-03-20 |
| DE4311923A1 (en) | 1994-10-13 |
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