CA1282888C - Acrylourethane reaction product - Google Patents
Acrylourethane reaction productInfo
- Publication number
- CA1282888C CA1282888C CA000527201A CA527201A CA1282888C CA 1282888 C CA1282888 C CA 1282888C CA 000527201 A CA000527201 A CA 000527201A CA 527201 A CA527201 A CA 527201A CA 1282888 C CA1282888 C CA 1282888C
- Authority
- CA
- Canada
- Prior art keywords
- reaction product
- diol
- diisocyanate
- methacrylate
- molecular weight
- 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 - Lifetime
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- Polyurethanes Or Polyureas (AREA)
Abstract
TITLE
Acrylourethane Reaction Product ABSTRACT
The ungelled reaction product of an acrylic prepolymer, a diol and a diisocyanate, reacted in the presence of a small amount of a monoalcohol to prevent gelling, is an acrylo-urethane polymer which may be acid modified and is useful in high solids coating compositions.
Acrylourethane Reaction Product ABSTRACT
The ungelled reaction product of an acrylic prepolymer, a diol and a diisocyanate, reacted in the presence of a small amount of a monoalcohol to prevent gelling, is an acrylo-urethane polymer which may be acid modified and is useful in high solids coating compositions.
Description
TITLE
Acrylourethane Reaction Product ~ACKGRO~ND
The present invention concerns an acrylourethane polymer useful in high solids coating compositions.
Environmental and economic concerns often make it desirable to minimize the quantity of oryanic solvent released to the atmosphere in the application of paints, such as to automobiles, either in single color coats or in color coat/clear coat or other applications. One way to do this is to make a paint with higher solids content which contains less solvent to evaporate.
Several properties must be balanced and reconciled in developing such a paint.
It would be desirable to have polymers which can be used to make paints with relatively high solids content and low viscosity.
While acrylourethane coating compositions are known including U.S. Patents 4,304,706 (1981);
4,208,494 (1980); 4,208,49S (1980); 3,975,457 (1976);
and 3,919,351 (1975) all to Chang et al, it is difficult to find combinations and proportions of acrylic, diol and diisocyanate that will not gel on reaction. In U.S. Patent 4,208,495, Example 1 uses certain monoalcohols during the reaction to avoid gelling, however, the low level of hydroxyl ; ethyl acrylate such as 9% or less does not permit suitable curing at bake temperatures as low as might be desired.
~2~
SUMMARY OF THE INVENTION
The ungelled reaction product, by weight based on total polymer solids, of (a) 50-70% of an acrylic prepolymer having a number average molecular weight of 2,000-10,000 and an average of 5-15, hydroxyl groups per chain, said prepolymer comprising the following monomers in percent by weight based on the prepolymer: 40-60~ of one or more of butyl methacrylate or butyl acrylate, 10-30% lauryl methacrylate, 20-40% of one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate, and 0-30% o~
one or more of styrene, methyl methacrylate and ethyl methacrylate, (b) 20-35~ of at least one of a monomeric diol and an oligomeric diol having a number average molecular weight of 200-2,000, (c) 5-15% of an aliphatic or aromatic diisocyanate, and (d) 1.0-4.0~ of a monofunctional alcohol.
DETAILED DESCRIPTION
An acrylic prepolymer of number average molecular weight of2,000-10,000 (preferably 3,000-5,000) having an average of 5-15 hydroxyl groups per chain (preferably 6-12) is first pre-pared at temperatures of 130-160C. The monomer composition of he acrylic can he varied according to end use. Typical monomers are styrene, butyl acrylate, methyl methacrylate, n-butyl methacrylate, lauryl methacrylate, ethyl methacrylate and such hydroxy containing monomers as hydroxy ethyl acrylate or hydroxy propyl methacrylate. This acrylic prepolymer is prepared at Ç0-70% weight solids and is then co-reacted with various diols and diisocyanates in the presence of tin catalysts ~2~
and traces of monofunctional alcohols to provide for hydroxy-functional acrylourethanes. The mole ratio of diol to diisocyanate is about 1 to 1.
Monofunctional alcohol is present during the polymerization reaction at level~ of 1.0-4.0~ on total polymer solids with a preferred level of 2.5%. This alcohol is present to prevent gellation since the mole ratio of diol to diisocyanate inherently leads to a gelling network.
The amount of hydroxyl extension can be varied from 5 to 50% of the existent acrylic hydroxyl groups with a preferred limit of 10-30~.
The range of 20-40~ of hydroxy ethyl acrylate or related monomers permits curing in the range of lS 110~132C, preferably 121C, for about 30 min.
The diol portion can be cDmprised of monomeric diols such as neopentyl glycol, ethylene glycol, cyclohexanedimethanol, 1,6-hexane diol, 1,4-butane diol or any other suitable diol having from 2-10 carbons. The diol portion can also be of an oligomeric ester-diol type such as poly-caprolactone diol or any polyester diols having number average molecular weights in the xange of 200-2,000 wi h those of Mn 500-11500 heing preferred.
The diisocyanate can be either aliphatic or aromatic in nature such as isophorone diiso-cyanate, bis-cyclohexylmethylene-4,4l-diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate and toluene diisocyanate.
The acid content of the acrylourethanes can be controlled either by post reaction with various anhydrides such as o-phthalic, succinic, ~x~
glutaric or trimellitic anhydrides to acid numbers of 10 or greater (15-25 preferred) or by carrying the chain extension out in the presence of such extending diols as dimethylolproionic acid.
Acrylourethanes prepared by the methods described in the examples can be formulated into high solids flexible coating which provide for coatings exhibiting excellent low temperature flexibility, good mar resistance and toughness under normal conditions.
EXAMPLES
In the following examples,parts, percentages and proportions are by weight except where indicated otherwise.
Example la - Acrylic Prepol~mer 50~ butyl methacrylate 20~ lauryl methacrylate 30~ hydroxy ethylacrylate To a 5-liter flask equipped with electric heating mantle, mechanical stirrer, batch and vapor thermometers, water cooled condenser, nitrogen purge and addition funnels are added 100 grams of xylene and 900 grams of aromatic hydrocarbon (bp.
160-170-C). The solvent is heated to reflux at batch temperature of 150-160C.
A mixture of 1200 g n-butyl methacxylate, 400 g lauryl methacrvlate and 720 g hydroxyethyl acrylate is added to the flask over a 4-hour period. A solution of 38 grams of a 70% solution of t-butyl peracetate and 3D grams of xylene is added concomitantly with the monomer mix over 4 hours and twenty minutes. The batch is kept at reflux duxing the additions and for twenty minutes beyond the initiator feed at 150-160C. The resultant acrylic resin has the following characteristics:
Theoretical Acid No; 1-5 mg ~OH at 100 weight solids Theoretical Hydroxyl No.: 140-lS0 mg KOH .
at 100% weight solids Glass transition temperatures (Tg) -36C as measured by differential scanning calorimetry (DSC~
Wt. Solids: 67-69~ (determined with heating at 110C for 1 hr) Gar~ner-Holdt viscosity = T-V Q 25C
GPC (gel permeation chromatography) molecular weight distribution:
number average Mn - 3570 ; weight average Mw = 7520 Z average Mz = 13200 polydispersity d = 2.10 Example lb - AcrYlourethane Resin To a 12-liter flask equipped with electric heating mantle, mechanical stirrer, batch and vapor thermometers, nitrogen purge, water cooled con-~: denser and addition funnel are added 6710.60 q ~f acrylic prepolymer from Example la, 1~32.2 g CAPA-210 polycaprolactone diol, 175.4 g n~butyl : alcohol, 0.4 g of dibutyl tin dilaurate, and 1066.3 g of methyl ethyl ketone.
The mixture is heated to reflux at temperatures of 105-115C and then ~80 g of Desmodur-W* diisocyanate and added over 30 minutes.
The mixture is then heated ~t reflux for 3 hours at 105-115~C at which point thc isocyanate is completely consumed as monitored by infrared. The : 35 resultant resin has the following characteristics:
* denotes txade mark 1~8~ B
at 105~115C at which point the isocyanate is completely consumed as monitored by infrared. The resultant resin has the following characteristics:
Acid NoO: 1-5 mg KOH
Hydroxyl No.: 110-120 mg KOH
~ Wt. Solids = 67-69% (110C for 1 hr) Gardner-Holdt viscosity: O-Q at 25C
Tg for the two polymer components: -48C
and -4C (DSC) GPC Mol Wt.
Mn = 3720 Mw = 21700 Mz = 84100 d = 5.83 Example 2 - Acid Modified Acrylourethane The acrylourethane from Example lb can be post reacted with trimellitic anhydride in the following manner.
Upon completion of the chain extension reaction, the batch is allowed to cool to 80C
or less to provide for safe solids addition. A
total of 218.15 g of trimellitic anhydride is added and the mixture is then heated a reflux at 105-115C for 30 minutes or until the acid number is 15-22 mg KOH. The characteristics of the resin are:
Acid No~: lS 20 mg XOH
Hydroxyl No.: 100-110 mg KOH
% Wt. Solids: 69-71 (110~C ~or 1 hr) ~ardner-Holdt viscosity: S-U at 25C
Tg: -45C and -4C as measured by DSC
GPC Mol Wt, same as Example lb :
~Z8Z~
E:cample 3 - Coatings from Acrylourethanes Polymers of the present invention have been formulated into various high solids flexible enamels. A typical coating composition for an unpigmented clear flexible ~namel is as follows:
60 parts solid acrylourethane resin of Example lb 40 parts Resimene*755 melamine-formaldehyde crosslinking resin made by Monsanto 2 parts on binder of Tinuvin*328 ultraviolet absorber made by Ciba Geigy 1 part on binder of Tinuvin 079 hindered amine light stabilizer made by Ciba Geigy 1.2 parts on binder dodecyl benzene sulfonic acid.
: The clear coating is diluted to 60% weight solids with a 1/1 blend of xylene and methyl amyl ketone to a viscosi~y of 35-40 seconds #2 ~isher cup.
The clear coating is then spray applied to primed RIM
sub trate to give a dry film build of 50 ~m + 2.5 ~m of (2.0 mils - 0.1 mils) at a bake of 250F for 30 minu~es.
~: ~his clear coating exhibits excellent low temperature flexibility as tested by ~ bend test over a 1.27 cm 11/2 inch) cylindrical mandrel at : -20F. The hardness is measured at 2.0-3.0 Knoops by Tukon hardness, and the clear co2ting has excellent humidity resistance and adhesion after ~ 30 exposure to 96 hours at lOO~F and 100% relative : humidity.
* denotes trade mark
Acrylourethane Reaction Product ~ACKGRO~ND
The present invention concerns an acrylourethane polymer useful in high solids coating compositions.
Environmental and economic concerns often make it desirable to minimize the quantity of oryanic solvent released to the atmosphere in the application of paints, such as to automobiles, either in single color coats or in color coat/clear coat or other applications. One way to do this is to make a paint with higher solids content which contains less solvent to evaporate.
Several properties must be balanced and reconciled in developing such a paint.
It would be desirable to have polymers which can be used to make paints with relatively high solids content and low viscosity.
While acrylourethane coating compositions are known including U.S. Patents 4,304,706 (1981);
4,208,494 (1980); 4,208,49S (1980); 3,975,457 (1976);
and 3,919,351 (1975) all to Chang et al, it is difficult to find combinations and proportions of acrylic, diol and diisocyanate that will not gel on reaction. In U.S. Patent 4,208,495, Example 1 uses certain monoalcohols during the reaction to avoid gelling, however, the low level of hydroxyl ; ethyl acrylate such as 9% or less does not permit suitable curing at bake temperatures as low as might be desired.
~2~
SUMMARY OF THE INVENTION
The ungelled reaction product, by weight based on total polymer solids, of (a) 50-70% of an acrylic prepolymer having a number average molecular weight of 2,000-10,000 and an average of 5-15, hydroxyl groups per chain, said prepolymer comprising the following monomers in percent by weight based on the prepolymer: 40-60~ of one or more of butyl methacrylate or butyl acrylate, 10-30% lauryl methacrylate, 20-40% of one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate, and 0-30% o~
one or more of styrene, methyl methacrylate and ethyl methacrylate, (b) 20-35~ of at least one of a monomeric diol and an oligomeric diol having a number average molecular weight of 200-2,000, (c) 5-15% of an aliphatic or aromatic diisocyanate, and (d) 1.0-4.0~ of a monofunctional alcohol.
DETAILED DESCRIPTION
An acrylic prepolymer of number average molecular weight of2,000-10,000 (preferably 3,000-5,000) having an average of 5-15 hydroxyl groups per chain (preferably 6-12) is first pre-pared at temperatures of 130-160C. The monomer composition of he acrylic can he varied according to end use. Typical monomers are styrene, butyl acrylate, methyl methacrylate, n-butyl methacrylate, lauryl methacrylate, ethyl methacrylate and such hydroxy containing monomers as hydroxy ethyl acrylate or hydroxy propyl methacrylate. This acrylic prepolymer is prepared at Ç0-70% weight solids and is then co-reacted with various diols and diisocyanates in the presence of tin catalysts ~2~
and traces of monofunctional alcohols to provide for hydroxy-functional acrylourethanes. The mole ratio of diol to diisocyanate is about 1 to 1.
Monofunctional alcohol is present during the polymerization reaction at level~ of 1.0-4.0~ on total polymer solids with a preferred level of 2.5%. This alcohol is present to prevent gellation since the mole ratio of diol to diisocyanate inherently leads to a gelling network.
The amount of hydroxyl extension can be varied from 5 to 50% of the existent acrylic hydroxyl groups with a preferred limit of 10-30~.
The range of 20-40~ of hydroxy ethyl acrylate or related monomers permits curing in the range of lS 110~132C, preferably 121C, for about 30 min.
The diol portion can be cDmprised of monomeric diols such as neopentyl glycol, ethylene glycol, cyclohexanedimethanol, 1,6-hexane diol, 1,4-butane diol or any other suitable diol having from 2-10 carbons. The diol portion can also be of an oligomeric ester-diol type such as poly-caprolactone diol or any polyester diols having number average molecular weights in the xange of 200-2,000 wi h those of Mn 500-11500 heing preferred.
The diisocyanate can be either aliphatic or aromatic in nature such as isophorone diiso-cyanate, bis-cyclohexylmethylene-4,4l-diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate and toluene diisocyanate.
The acid content of the acrylourethanes can be controlled either by post reaction with various anhydrides such as o-phthalic, succinic, ~x~
glutaric or trimellitic anhydrides to acid numbers of 10 or greater (15-25 preferred) or by carrying the chain extension out in the presence of such extending diols as dimethylolproionic acid.
Acrylourethanes prepared by the methods described in the examples can be formulated into high solids flexible coating which provide for coatings exhibiting excellent low temperature flexibility, good mar resistance and toughness under normal conditions.
EXAMPLES
In the following examples,parts, percentages and proportions are by weight except where indicated otherwise.
Example la - Acrylic Prepol~mer 50~ butyl methacrylate 20~ lauryl methacrylate 30~ hydroxy ethylacrylate To a 5-liter flask equipped with electric heating mantle, mechanical stirrer, batch and vapor thermometers, water cooled condenser, nitrogen purge and addition funnels are added 100 grams of xylene and 900 grams of aromatic hydrocarbon (bp.
160-170-C). The solvent is heated to reflux at batch temperature of 150-160C.
A mixture of 1200 g n-butyl methacxylate, 400 g lauryl methacrvlate and 720 g hydroxyethyl acrylate is added to the flask over a 4-hour period. A solution of 38 grams of a 70% solution of t-butyl peracetate and 3D grams of xylene is added concomitantly with the monomer mix over 4 hours and twenty minutes. The batch is kept at reflux duxing the additions and for twenty minutes beyond the initiator feed at 150-160C. The resultant acrylic resin has the following characteristics:
Theoretical Acid No; 1-5 mg ~OH at 100 weight solids Theoretical Hydroxyl No.: 140-lS0 mg KOH .
at 100% weight solids Glass transition temperatures (Tg) -36C as measured by differential scanning calorimetry (DSC~
Wt. Solids: 67-69~ (determined with heating at 110C for 1 hr) Gar~ner-Holdt viscosity = T-V Q 25C
GPC (gel permeation chromatography) molecular weight distribution:
number average Mn - 3570 ; weight average Mw = 7520 Z average Mz = 13200 polydispersity d = 2.10 Example lb - AcrYlourethane Resin To a 12-liter flask equipped with electric heating mantle, mechanical stirrer, batch and vapor thermometers, nitrogen purge, water cooled con-~: denser and addition funnel are added 6710.60 q ~f acrylic prepolymer from Example la, 1~32.2 g CAPA-210 polycaprolactone diol, 175.4 g n~butyl : alcohol, 0.4 g of dibutyl tin dilaurate, and 1066.3 g of methyl ethyl ketone.
The mixture is heated to reflux at temperatures of 105-115C and then ~80 g of Desmodur-W* diisocyanate and added over 30 minutes.
The mixture is then heated ~t reflux for 3 hours at 105-115~C at which point thc isocyanate is completely consumed as monitored by infrared. The : 35 resultant resin has the following characteristics:
* denotes txade mark 1~8~ B
at 105~115C at which point the isocyanate is completely consumed as monitored by infrared. The resultant resin has the following characteristics:
Acid NoO: 1-5 mg KOH
Hydroxyl No.: 110-120 mg KOH
~ Wt. Solids = 67-69% (110C for 1 hr) Gardner-Holdt viscosity: O-Q at 25C
Tg for the two polymer components: -48C
and -4C (DSC) GPC Mol Wt.
Mn = 3720 Mw = 21700 Mz = 84100 d = 5.83 Example 2 - Acid Modified Acrylourethane The acrylourethane from Example lb can be post reacted with trimellitic anhydride in the following manner.
Upon completion of the chain extension reaction, the batch is allowed to cool to 80C
or less to provide for safe solids addition. A
total of 218.15 g of trimellitic anhydride is added and the mixture is then heated a reflux at 105-115C for 30 minutes or until the acid number is 15-22 mg KOH. The characteristics of the resin are:
Acid No~: lS 20 mg XOH
Hydroxyl No.: 100-110 mg KOH
% Wt. Solids: 69-71 (110~C ~or 1 hr) ~ardner-Holdt viscosity: S-U at 25C
Tg: -45C and -4C as measured by DSC
GPC Mol Wt, same as Example lb :
~Z8Z~
E:cample 3 - Coatings from Acrylourethanes Polymers of the present invention have been formulated into various high solids flexible enamels. A typical coating composition for an unpigmented clear flexible ~namel is as follows:
60 parts solid acrylourethane resin of Example lb 40 parts Resimene*755 melamine-formaldehyde crosslinking resin made by Monsanto 2 parts on binder of Tinuvin*328 ultraviolet absorber made by Ciba Geigy 1 part on binder of Tinuvin 079 hindered amine light stabilizer made by Ciba Geigy 1.2 parts on binder dodecyl benzene sulfonic acid.
: The clear coating is diluted to 60% weight solids with a 1/1 blend of xylene and methyl amyl ketone to a viscosi~y of 35-40 seconds #2 ~isher cup.
The clear coating is then spray applied to primed RIM
sub trate to give a dry film build of 50 ~m + 2.5 ~m of (2.0 mils - 0.1 mils) at a bake of 250F for 30 minu~es.
~: ~his clear coating exhibits excellent low temperature flexibility as tested by ~ bend test over a 1.27 cm 11/2 inch) cylindrical mandrel at : -20F. The hardness is measured at 2.0-3.0 Knoops by Tukon hardness, and the clear co2ting has excellent humidity resistance and adhesion after ~ 30 exposure to 96 hours at lOO~F and 100% relative : humidity.
* denotes trade mark
Claims (13)
1. The ungelled reaction product, by weight based on total polymer solids, of (a) 0-70% of an acrylic prepolymer having a number average molecular weight of 2,000-10,000 and an average of 5-15, hydroxyl groups per chain said prepolymer comprising thy following monomers in percent by weight based on the prepolymer:
40-60% of one or more of butyl methacrylate or butyl acrylate 10-30% lauyl methacrylate 20 40% of one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxy-propyl methacrylate, and 0-30% of one or more of styrene, methyl methacrylate and ethylmethacrylate (b) 20 35% of at least one of a monomeric diol and an oligomeric diol having a number average molecular weight of 200-2,000, (c) 5-15% of an aliphatic or aromatic diisocyanate, and (d) 1.0-4.0% of a monofunctional alcohol said reaction being performed by first forming the acrylic prepolymer of (a) then mixing with (a) the diol of (b) and the alcohol of (d), then mixing therewith the diisocyanate of (c).
40-60% of one or more of butyl methacrylate or butyl acrylate 10-30% lauyl methacrylate 20 40% of one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxy-propyl methacrylate, and 0-30% of one or more of styrene, methyl methacrylate and ethylmethacrylate (b) 20 35% of at least one of a monomeric diol and an oligomeric diol having a number average molecular weight of 200-2,000, (c) 5-15% of an aliphatic or aromatic diisocyanate, and (d) 1.0-4.0% of a monofunctional alcohol said reaction being performed by first forming the acrylic prepolymer of (a) then mixing with (a) the diol of (b) and the alcohol of (d), then mixing therewith the diisocyanate of (c).
2. The reaction product of claim 1 in which 5-50% of the hydroxyl groups on the acrylic prepolymer have reacted with diol or diisocyanate
3. The reaction product of claim 2 in which 10-30% of the hydroxyl groups have so reacted.
4. The reaction product of claim 2 which has been further reacted with enough of an anhydride to give an acid number of at least 10.
5. The reaction product of claim 4 in which the acid number is 15-25.
6. The reaction product of claim 5 in which the anhydride is at least one selected from o-phthalic, succinic, glutaric and trimellitic anhydrides.
7. The reaction product of claim 5 in which the anhydride is trimellitic anhydride.
8. The reaction product of claim 2 in which the diol is dimethylolpropionic acid and the acid number of the reaction product is at least 10.
9. The reaction product o claim B in which the acid number is 15-25.
10. The reaction product of claim 3 in which (a) the acrylic prepolymer has a number average molecular weight of 3,000-5,000 and an average of 6-12 hydroxyl groups per chain.
(b) the diol is either monomeric or an oligomer having a number average molecular weight of 500-1,590.
(d) he monofunctional alcohol is present in the range of about 2.0-3.0%.
(b) the diol is either monomeric or an oligomer having a number average molecular weight of 500-1,590.
(d) he monofunctional alcohol is present in the range of about 2.0-3.0%.
11. The reaction product of claim 10 in which (b) the diol is one or more of neopentyl glycol, ethylene glycol, cyclohexanedimethanol, 1,6 hexane diol; 1,4-butane diol, dimethylol propionic acid, or other diol having 2-10 carbon atoms, or a polyester diol oligomer including polycaprolactone diol, (c) the diisocyanate is one or more of 4,4'-methylene bis(cyclohexyl isocyanate), hexa-methylene diisocyanate, trimethylhexamethylene diisocyanate, and toluene diisocyanate,
12. The reaction product of claim 10 in which (b) the diol a polycaprolactone diol having a number average molecular weight of about 1,000 and (c) the monofunctional alcohol is n-butyl alcohol, present in an amount of about 2.5%.
13. A coating composition comprising the reaction product of claim 1 and a crosslinking resin in an organic solvent media.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000527201A CA1282888C (en) | 1987-01-13 | 1987-01-13 | Acrylourethane reaction product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000527201A CA1282888C (en) | 1987-01-13 | 1987-01-13 | Acrylourethane reaction product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1282888C true CA1282888C (en) | 1991-04-09 |
Family
ID=4134741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000527201A Expired - Lifetime CA1282888C (en) | 1987-01-13 | 1987-01-13 | Acrylourethane reaction product |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1282888C (en) |
-
1987
- 1987-01-13 CA CA000527201A patent/CA1282888C/en not_active Expired - Lifetime
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