Low misting laminating adhesives
View Patent ↗The tendency of a two component laminating adhesive based on polyurethane chemistry to form a mist of fine droplets when applied at a high line speed may be reduced by including both a high functionality polyol and a lower functionality polymeric polyol in Component B which is combined and reacted with an isocyanate-functionalized polyurethane prepolymer in Component A.
1. A low-misting two component adhesive for bonding layers of a flexible packaging laminate consisting of two co-reactive components, Component A and Component B, wherein
Component A comprises an isocyanate-functionalized compound and optionally solvent, water, catalyst, curing agent, accelerator, plasticizer, stabilizer, antioxidant, light stabilizer, filler, dye, pigment, fragrance, preservative, or mixtures thereof, and
Component B consists of about 15% by weight to about 75% by weight (based on the total weight of Component B) of at least one high functionality polyol containing at least four hydroxyl groups per molecule, said high functionality polyol being selected from the group consisting of:
(i) a polyester polyol of the formula (HO) m (R 1 )—O—C(═O)—R 2 —C(═O)—O—(R 3 )(OH) n wherein —O—R 1 (OH) m and —O—R 3 (OH) n are each, independently, residues selected from trimethylolpropane, pentaerythritol and polyols where R 1 and R 3 are each, independently, linear, aliphatic cyclic, or aromatic hydrocarbyls; R 2 is selected from C 2 -C 20 hydrocarbyl radicals; each of m and n are at least one; and m+n is at least 4;
(ii) a polyester polyol of the formula (HO) q (R 4 )—O—C(═O)—R 5 —C(═O)—O—R 6 —O—C(═O)—R 7 —C(═O)—O—(R 8 )(OH) r wherein —O—R 4 (OH) m and —O—R 8 (OH) n are each, independently, selected from residues of trimethylolpropane, pentaerythritol and polyols where R 4 and R 8 are each, independently, linear, aliphatic cyclic, or aromatic hydrocarbyls; R 5 and R 7 are each, independently, C 2 -C 20 hydrocarbyl radicals; R 6 is a polyoxyalkylene radical, linear aliphatic, cycloaliphatic or aryl group, q and r are at least one and q+r is at least 4; and
(iii) a polyester polyol that is the reaction product of (a) at least one of ethylene glycol, diethylene glycol, 1,6-hexanediol and (b) a carboxylic acid containing four or more carboxylic acid groups per molecule; and
at least one lower functionality polymeric polyol compatible with the at least one high functionality polyol and selected from the group consisting of difunctional polymeric polyols; trifunctional polymeric polyols; difunctional polymeric polyols and at least one monomeric polyol having three hydroxyl groups per molecule; and trifunctional polymeric polyols and at least one monomeric polyol having three hydroxyl groups per molecule; and combinations thereof; said difunctional and trifunctional polymeric polyols being selected from at least one of:
(a) one or more polyester polyols obtained from reacting one or more dibasic acid or diester or anhydride thereof with one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1,6-hexanediol and polycaprolactone polyol; and
(b) one or more polyether polyols;
and optionally solvent, water, catalyst, curing agent, accelerator, plasticizer, stabilizer, antioxidant, light stabilizer, filler, dye, pigment, fragrance, preservative, or mixtures thereof;
wherein the at least one high functionality polyol is obtained by reacting a difunctional polyol and a dicarboxylic acid to form a carboxylic acid-functionalized diester and reacting the carboxylic acid-functionalized diester with a trifunctional polyol.
2. The two component laminating adhesive of claim 1 wherein said at least one lower functionality polymeric polyol is a polyester polyol.
3. A low-misting two component adhesive for bonding layers of a flexible packaging laminate consisting of two co-reactive components, Component A and Component B, wherein
Component A comprises an isocyanate-functionalized compound and optionally solvent, water, catalyst, curing agent, accelerator, plasticizer, stabilizer, antioxidant, light stabilizer, filler, dye, pigment, fragrance, preservative, or mixtures thereof, and
Component B consists of about 15% by weight to about 75% by weight (based on the total weight of Component B) of at least one high functionality polyol containing at least four hydroxyl groups per molecule, said high functionality polyol being selected from the group consisting of:
(i) a polyester polyol of the formula (HO) m (R 1 )—O—C(═O)—R 2 —C(═O)—O—(R 3 )(OH) n wherein —O—R′(OH) m and —O—R 3 (OH) n are each, independently, residues selected trimethylolpropane, pentaerythritol and polyols where R 1 and R 3 are each, independently, linear, aliphatic cyclic, or aromatic hydrocarbyls; R 2 is selected from C 2 -C 20 hydrocarbyl radicals; each of m and n are at least one and m+n is at least 4;
(ii) a polyester polyol of the formula (HO) q (R 4 )—O—C(═O)—R 5 —C(═O)—O—R 6 —O—C(═O)—R 7 —C(═O)—O—(R 8 )(OH) r wherein —O—R 4 (OH) m and —O—R 8 (OH) n are each, independently, selected from residues of trimethylolpropane, pentaerythritol and polyols where R 4 and R 8 are each, independently, linear, aliphatic cyclic, or aromatic hydrocarbyls; R 5 and R 7 are each, independently, C 2 -C 20 hydrocarbyl radicals; R 6 is a polyoxyalkylene radical, linear aliphatic, cycloaliphatic or aryl group, q and r are at least one and q+r is at least 4; and
(iii) a polyester polyol that is the reaction product of (a) at least one of ethylene glycol, diethylene glycol, 1,6-hexanediol and (b) a carboxylic acid containing four or more carboxylic acid groups per molecule; and
at least one lower functionality polymeric polyol compatible with the at least one high functionality polyol and selected from the group consisting of difunctional polymeric polyols; trifunctional polymeric polyols; difunctional polymeric polyols and at least one monomeric polyol having three hydroxyl groups per molecule; and trifunctional polymeric polyols and at least one monomeric polyol having three hydroxyl groups per molecule; and combinations thereof;
said at least one lower functionality polymeric polyol is a polyether polyol and
optionally solvent, water, catalyst, curing agent, accelerator, plasticizer, stabilizer, antioxidant, light stabilizer, filler, dye, pigment, fragrance, preservative, or mixtures thereof.
4. A low-misting two component adhesive for bonding layers of a flexible packaging laminate consisting of two co-reactive components, Component A and Component B, wherein
Component A comprises an isocyanate-functionalized compound and optionally solvent, water, catalyst, curing agent, accelerator, plasticizer, stabilizer, antioxidant, light stabilizer, filler, dye, pigment, fragrance, preservative, or mixtures thereof, and
Component B consists of about 15% by weight to about 75% by weight (based on the total weight of Component B) of at least one high functionality polyol containing at least four hydroxyl groups per molecule, said high functionality polyol being selected from the group consisting of:
(i) a polyester polyol of the formula (HO) m (R 1 )—O—C(═O)—R 2 —C(═O)—O—(R 3 )(OH) n wherein —O—R 1 (OH) m and —O—R 3 (OH) n are each, independently, residues selected trimethylolpropane, pentaerythritol and polyols where R 1 and R 3 are each, independently, linear, aliphatic cyclic, or aromatic hydrocarbyls; R 2 is selected from C 2 -C 20 hydrocarbyl radicals; each of m and n are at least one and m+n is at least 4;
(ii) a polyester polyol of the formula (HO) q (R 4 )—O—C(═O)—R 5 —C(═O)—O—R 6 —O—C(═O)—R 7 —C(═O)—O—(R 8 )(OH) r wherein —O—R 4 (OH) m and —O—R 8 (OH) n are each, independently, selected from residues of trimethylolpropane, pentaerythritol and polyols where R 4 and R 8 are each, independently, linear, aliphatic cyclic, or aromatic hydrocarbyls; R 5 and R 7 are each, independently, C 2 -C 20 hydrocarbyl radicals; R 6 is a polyoxyalkylene radical, linear aliphatic, cycloaliphatic or aryl group, q and r are at least one and q+r is at least 4; and
(iii) a polyester polyol that is the reaction product of (a) at least one of ethylene glycol, diethylene glycol, 1,6-hexanediol and (b) a carboxylic acid containing four or more carboxylic acid groups per molecule; and
at least one lower functionality polymeric polyol compatible with the at least one high functionality polyol and selected from the group consisting of difunctional polymeric polyols; trifunctional polymeric polyols; difunctional polymeric polyols and at least one monomeric polyol having three hydroxyl groups per molecule; and trifunctional polymeric polyols and at least one monomeric polyol having three hydroxyl groups per molecule; and combinations thereof; said difunctional and trifunctional polymeric polyols being selected from at least one of:
(a) one or more polyester polyols obtained from reacting one or more dibasic acid or diester or anhydride thereof with one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1,6-hexanediol and polycaprolactone polyol; and
(b) one or more polyether polyols;
and optionally solvent, water, catalyst, curing agent, accelerator, plasticizer, stabilizer, antioxidant, light stabilizer, filler, dye, pigment, fragrance, preservative, or mixtures thereof;
wherein Component B contains at least one monomeric polyol having three hydroxyl groups per molecule.
5. The two component laminating adhesive of claim 4 wherein the at least one high functionality polyol is obtained by reacting a trifunctional polyol and a dicarboxylic acid or diester or anhydride thereof.
6. The two component laminating adhesive of claim 4 wherein the at least one high functionality polyol is obtained by reacting (a) at least one trifunctional polyol selected from the group consisting of glycerin, trimethylolpropane, trimethylolethane, 1,2,4-butanetriol, and trifunctional polyether polyols and (b) at least one C 4 -C 18 dicarboxylic acid or diester or anhydride thereof, wherein said at least one trifunctional polyol is in molar excess relative to the at least one C 4 -C 18 dicarboxylic acid or diester or anhydride thereof.
7. The two component laminating adhesive of claim 4 wherein the at least one high functionality polyol is obtained by reacting (a) glycerin with (b) at least one C 4 -C 8 linear saturated aliphatic dicarboxylic acid, wherein the molar ratio (a):(b) is about 2:1.
8. The two component laminating adhesive of claim 4 , wherein the at least one high functionality polyol has a structure as follows:
(HO) m (R 1 )—O—C(═O)—R 2 —C(═O)—O—(R 3 )(OH) n
wherein —O—R 1 (OH) m and —O—R 3 (OH) n are each, independently, selected from residues of trimethylolpropane, pentaerythritol and polyols where R 1 and R 3 are each, independently, C 2 -C 20 linear, aliphatic cyclic, or aromatic hydrocarbyls; R 2 is selected from C 2 -C 20 hydrocarbyl radicals; each of m and n are at least one; and m+n is at least 4.
9. A low-misting two component adhesive for bonding layers of a flexible packaging laminate consisting of two co-reactive components, Component A and Component B, wherein
Component A comprises an isocyanate-functionalized compound and optionally solvent, water, catalyst, curing agent, accelerator, plasticizer, stabilizer, antioxidant, light stabilizer, filler, dye, pigment, fragrance, preservative, or mixtures thereof, and
Component B consists of about 15% by weight to about 75% by weight (based on the total weight of Component B) of at least one high functionality polyol containing at least four hydroxyl groups per molecule, wherein the at least one high functionality polyol has a structure as follows:
(HO) q (R 4 )—O—C(═O)—R 5 —C(═O)—O—R 6 —O—C(═O)—R 7 —C(═O)—O—(R 8 )(OH) r
wherein —O—R 4 (OH) m and —O—R 8 (OH) n are each, independently, selected from residues of trimethylolpropane, pentaerythritol and polyols where R 4 and R 8 are each, independently, C 2 -C 20 linear, aliphatic cyclic, or aromatic hydrocarbyls; R 5 and R 7 are each, independently, C 2 -C 20 hydrocarbyl radicals; R 6 is a polyoxyalkylene radical, linear aliphatic, cycloaliphatic or aryl group, q and r are at least one and q+r is at least 4; and
at least one lower functionality polymeric polyol compatible with the at least one high functionality polyol and selected from the group consisting of difunctional polymeric polyols; trifunctional polymeric polyols; difunctional polymeric polyols and at least one monomeric polyol having three hydroxyl groups per molecule; and trifunctional polymeric polyols and at least one monomeric polyol having three hydroxyl groups per molecule; and combinations thereof said difunctional and trifunctional polymeric polyols being selected from at least one of:
(a) one or more polyester polyols obtained from reacting one or more dibasic acid or diester or anhydride thereof with one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1,6-hexanediol and polycaprolactone polyol; and
(b) one or more polyether polyols;
and optionally solvent, water, catalyst, curing agent, accelerator, plasticizer, stabilizer, antioxidant, light stabilizer, filler, dye, pigment, fragrance, preservative, or mixtures thereof.
10. A laminate comprised of at least one polymeric film and the two component laminating adhesive of claim 4 in cured form.
11. The laminate of claim 10 comprised of at least two polymeric films, wherein the two component laminating adhesive is located between two of said polymeric films and adheres said polymeric films to each other.
12. The laminate of claim 10 wherein at least one polymeric film is comprised of a thermoplastic selected from the group consisting of polyethylene terephthalate, polyethylene, polypropylene, and polyvinylidene chloride.
13. The laminate of claim 10 additionally comprising a metal foil, wherein the laminating adhesive is located between the metal foil and at least one polymeric film.
14. A method of making a flexible film laminate, said method comprising a) combining Component A and Component B of the two component laminating adhesive of claim 4 to form an adhesive mixture, b) joining a first flexible film and a second flexible film using the adhesive mixture interposed between the first flexible film and the second flexible film, and c) curing the adhesive mixture.
15. The two component laminating adhesive of claim 1 , wherein Component A has a viscosity not greater than 10,000 cps at 25 degrees C.
16. The two component laminating adhesive of claim 1 , wherein Component A has a viscosity not greater than 3,500 cps at 25 degrees C.
17. A low-misting two component adhesive for bonding layers of a flexible packaging laminate consisting of two co-reactive components, Component A and Component B, wherein
Component A comprises an isocyanate-functionalized compound and optionally solvent, water, catalyst, curing agent, accelerator, plasticizer, stabilizer, antioxidant, light stabilizer, filler, dye, pigment, fragrance, preservative, or mixtures thereof, and
Component B consists of
about 15% by weight to about 75% by weight (based on the total weight of Component B) of at least one high functionality polyol containing at least four hydroxyl groups per molecule, wherein the at least one high functionality polyol is obtained by reacting a difunctional polyol and a dicarboxylic acid to form a carboxylic acid-functionalized diester and reacting the carboxylic acid-functionalized diester with a trifunctional polyol; and
at least one lower functionality polymeric polyol compatible with the at least one high functionality polyol and selected from the group consisting of difunctional polymeric polyols; trifunctional polymeric polyols; difunctional polymeric polyols and at least one monomeric polyol having three hydroxyl groups per molecule; and trifunctional polymeric polyols and at least one monomeric polyol having three hydroxyl groups per molecule; and combinations thereof; said difunctional and trifunctional polymeric polyols being selected from at least one of:
(a) one or more polyester polyols obtained from reacting one or more dibasic acid or diester or anhydride thereof with one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1,6-hexanediol and polycaprolactone polyol; and
(b) one or more polyether polyols;
and optionally solvent, water, catalyst, curing agent, accelerator, plasticizer, stabilizer, antioxidant, light stabilizer, filler, dye, pigment, fragrance, preservative, or mixtures thereof.
18. The two component laminating adhesive of claim 17 , wherein the at least one high functionality polyol is obtained by reacting at least one difunctional polyether polyol and at least one C 4 -C 18 dicarboxylic acid to form a carboxylic acid-functionalized polyether and reacting the carboxylic acid-functionalized polyether with at least one trifunctional polyol selected from the group consisting of glycerin, trimethylolpropane, trimethylolethane, 1,2,4-butanetriol, and trifunctional polyether polyols.
19. The two component laminating adhesive of claim 17 , wherein the at least one high functionality polyol is obtained by reacting at least one difunctional polypropylene glycol and at least one C 4 -C 8 saturated aliphatic dicarboxylic acid at a molar ratio of about 1:2 to form a carboxylic acid-functionalized polypropylene glycol and reacting the carboxylic acid-functionalized polypropylene glycol with glycerin at a molar ratio of about 1:2.