CA1334233C - Polyurethane adhesives containing organophosphites - Google Patents
Polyurethane adhesives containing organophosphitesInfo
- Publication number
- CA1334233C CA1334233C CA 530618 CA530618A CA1334233C CA 1334233 C CA1334233 C CA 1334233C CA 530618 CA530618 CA 530618 CA 530618 A CA530618 A CA 530618A CA 1334233 C CA1334233 C CA 1334233C
- Authority
- CA
- Canada
- Prior art keywords
- phosphite
- film laminating
- based film
- laminating adhesive
- polyurethane based
- 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 - Fee Related
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
A polyurethane based film laminating adhesive containing a prepolymer prepared by reacting MDI with a polyol in the presence of an organophosphite is provided.
The phosphite is present in an amount of about 0.1 to about 10% relative to the weight of said prepolymer. The prepolymer is characterized in having an isocyanate content of from about 1 to 25% by weight.
The phosphite is present in an amount of about 0.1 to about 10% relative to the weight of said prepolymer. The prepolymer is characterized in having an isocyanate content of from about 1 to 25% by weight.
Description
A POLYURETHANE BASED FILM LAMINATING ADHESIVE
FIELD OF THE INVENTION
The invention relates to adhesives and more particularly to polyurethane based adhesives.
SUMMARY OF THE INVENTION
A polyurethane based film laminating adhesive containing a prepolymer prepared by reacting MDI with a polyol in the presence of an organophosphite is provided.
The phosphite is present in an amount of about 0.1 to about 10% relative to the weight of said prepolymer. The prepolymer is characterized in having an isocyanate content of from about 1 to 25% by weight.
BACKGROUND OF THE INVENTION
The automotive industry has progressed from using mechanical fasteners and welds on steel panels to adhesively bonding reinforced composite materials. The volume composites used and the need to bond them, particularly in the area of exterior body panels has increased dramatically in recent years.
The food packaging industry uses a large volume of laminated films in packaging foods. In recent years there has been a trend mandated by government regulations to limit the amount of solvent in the adhesives. Solvent free and high solids (higher than 60%) systems~are therefore of interest. U.S. Patent 2,915,496 discloses certain polyurethane compositions which are resistant to aging and weathering. Organic phosphites are disclosed an antioxidants. In Example II, at column 7 there is disclosed the preparation of TDI based cellular foamed polyurethane in the presence of a phosphite. U.S. Patent 4,000,104 discloses urethane compositions which are prepared from difunctional polyols and polyisocyanates having a ~ l ,.. ~,~
t -2- l 334233 functionality of at least about 2.5, a liquid modifier and a catalyst.
Among the modifiers, there are listed organophosphites which are said to function in moderating the reaction exotherm between the remaining components without substantial reaction therewith. Example 3 ( at 5 column 9) and Example 26 (at column 15) of the patent demonstrate the use of such a modifier.
DETAILED DESCRIPTION OF THE INVENTION
The adhesives of the invention include both 100% solids or high (at least 60%) solids polyurethane systems and they are suitable 10 both as film laminating and as structural adhesives. The adhesive comprises a prepolymer prepared from MDI and a polyol - a polyhydric alcohol containing 2 or more hydroxyl compounds - and includes an added 0.1 to about 10, preferably 0.3 to about 5, percent by weight of an organophosphite. The NCO content is about 1-25%, preferably 3 to 15 15%. The adhesive may also comprise a solvent in an amount of at most 40% by weight of the system.
Among the polyols suitable in the practice of the invention, the preferred ones are: polyester polyols, polyether polyols and polycarbonate polyols, all of which are well recognized in the art. These 20 and other suitable polyols may be prepared by known methods and are also readily available in commerce.
MDI in the present context refers to 4,4'-diphenylmethanediisocyanate, 2,4'-diphenylmethanediisocyanate, 2,2'-diphenylmethanediisocyanate and mixtures thereof. Preferably the MDI
25 is 4,4'-diphenylmethanediisocyanate. MDI is well recognized in the art and is readily available in commerce.
The organophosphite suitable in the invention is generally any organic compound which contains the radical PO~3. Included among the suitable organophosphites are:
Mo-2828 P~' (TO~ P 1 334233 where T is a hydrogen, alkyl, aryl or alkaryl group with the pro~ision that no more than two of the T groups are hydrogen atoms. Other suitable organ~phosphites conform 5 to (Z-Ar-O tP
where Ar is an aromatic nucleus, including naphthyl, phenyl and diphenyl and Z is an alkyl radical having at least 4 carbon atoms, preferably C6-C12 alkyl. Other 10 suitable phosphites include mono and di(nonylphenyl) phosphite, triethylphosphite, tris(2-ethylhexyl) phosphite, triisopropylphosphite, tris(dipropylene-glycol)phosphite, tris(nonylphenyl)phosphite, tristearylphosphite and tris(2-tolyl)pho~phite. The 15 preferred species are: tri(mixed mono and dinonylphenyl)phosphite, tris(nonylphenyl phosphite), tris(2-ethylhexyl)phosphite and tristearylphosphite.
The adhesive of the invention in both the solvent-free embodiment and high solids embod~ment 20 exhibit an improved level of adhesion. Additionally, it was noted that adding the phosphites accelerates the rate of cure in a film laminate combination of polypropylene to polyethylene.
EXPERIMENTAL
The adhesive used in demonstrating the invention were all based on propylene-oxide-tipped propylene glycol and methylene di-para-phenylene isocyanate (MDI). In preparing the phosphite-modified systems the MDI (Monduf M from Mobay Corporation) was 30 heated to 70C under nitrogen in a 3-neck flask equipped with a mechanical stirrer and an equalizing addition funnel. A mixture of the phosphite and glycol was added over a 15-120 minute period and the resulting prepolymer held at about 70C for about two hours. The resulting 35 prepolymer was cooled and then stored in a sealed, dry Mo-2828 *- Trademark _4_ 1 334233 jar under a nitrogen pad. In carrying out the experiments, the relative amounts of the components were typically about 125.15 gm (1 equivalent) of MDI, 297 gms (0.297 equivalents) of a polyol (~ 3600 from Mobay 5 Corporation) and about 1 Z relative tO the weight of the MDI and polyol, of the indicated phosphite.
Adhesive testing: the viscosities of the systems were measured at about 23C using a Brookfield viscometer (RVT or LVTD). Coating weights used in film 10 laminations were between 1.0 and 1.5 lbs/ream. Peel strength was determined using a Scott Tester at a cross-head speed of 12 inches/min after aging (24 hours or 1 week) at room temperature. The adhesives failure mode was determined as one of: adhesive failure, 15 cohesive failure and/or substrate failure. The testing of the prepolymers was performed on various laminations as follows: polypropylene (PP) to Mylar~-and polypropylene to polyethylene (PE).
Peel Stren~th (4) pli Phosphite Viscosity NCO
added mPa.s Z 1 day 1 week --- 6,725 6.90 0 2(3)(C) 0 4(3)(A) 0.3 0.5 Polygard HR(l) 6,730 6.79 0.2(C) 0.9 0.7(C) 0.7 Poly~d HR/ 7,725 6.68 0.9 0.8 T-12 0.8 0.8 30 Triethylphos- 17,300 6.96 0.6 0.8 phite 0.6(A) 0.7 Tris(2-ethyl- 9,100 6.90 0.8 0.8 hexyl)phosphite 0.8 0.8 Triisopropyl- 150,150 6.80 0.6 0.8 35 phosphite 0.6 0.9 Tris(dipropy- 114,700 5.04 0.8 0.8 leneglycol) 0.6(A) 0.5(A) phosphite Mo-2828 * - Trademark , t----_5 1 334233 Peel Stren~th (4) pli Phosphite Viscosity NC0 added mPa.s Z 1 dav 1 week 5 Tris(nonvl- 8,600 6.98 0.8 0.8 phenyl)phos- 0.6 0.8 phite Tristearyl- 8,160 6.77 0.8 0.8 Phosphite 0.6 0.8 10 Tris(2-tolyl)- 9,000 7.20 0.5(A) 0.7 phosphite 0.6(A) 0.7 (5) 10,000 7.65 0.2(A) 0.3(A) 0.5(A) 0.4(A) (6) 8,484 7.52 0.2(A) 0.2(A) 0.8 0.6 (1) Tri(mixed mono and dinonylphenyl) phosphite with 1 triisopropanol.~ine (2) Tin Catalyst (3) The indicated peel strength values are listed first for a Mylar7PP laminate and second for a PE/PP
laminate (4) Except where noted a failure in the propylene substrate was observed. (A) indicates failure in the adhesion to polypropylene. (C) indicates cohesive failure (5) Multiflex*N - isocyanate terminated MDI prepolymer (6) Multiflex~NM-35 - isocyanate terminated MDI
prepolymer The peel strength of the phosphite modified 30 adhesives of the invention compare favorably with commercial, solvent.free, products .(Peter Cooper adhesives Multiflex N and MultifleY~NM-35) as is noted in the table.
The adhesive of the invention is suitable for 35 use 8S a film laminating adhesive or as a structural adhesive. Among the film laminating systems where the adhesive of the invention is suitable mention is made of combinations of propylene, aluminum, polyethylene and Mo-2828 -. `, * - Trademark polyester films (for instance Mylar). The structural components for which the adhesive of the invention is suitable include combinations of stainless steel, aluminum, SMC, RIM and reinforced RIM.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the 10 spirit and scope of the invention except as it may be limited by the claims.
Mo-2828
FIELD OF THE INVENTION
The invention relates to adhesives and more particularly to polyurethane based adhesives.
SUMMARY OF THE INVENTION
A polyurethane based film laminating adhesive containing a prepolymer prepared by reacting MDI with a polyol in the presence of an organophosphite is provided.
The phosphite is present in an amount of about 0.1 to about 10% relative to the weight of said prepolymer. The prepolymer is characterized in having an isocyanate content of from about 1 to 25% by weight.
BACKGROUND OF THE INVENTION
The automotive industry has progressed from using mechanical fasteners and welds on steel panels to adhesively bonding reinforced composite materials. The volume composites used and the need to bond them, particularly in the area of exterior body panels has increased dramatically in recent years.
The food packaging industry uses a large volume of laminated films in packaging foods. In recent years there has been a trend mandated by government regulations to limit the amount of solvent in the adhesives. Solvent free and high solids (higher than 60%) systems~are therefore of interest. U.S. Patent 2,915,496 discloses certain polyurethane compositions which are resistant to aging and weathering. Organic phosphites are disclosed an antioxidants. In Example II, at column 7 there is disclosed the preparation of TDI based cellular foamed polyurethane in the presence of a phosphite. U.S. Patent 4,000,104 discloses urethane compositions which are prepared from difunctional polyols and polyisocyanates having a ~ l ,.. ~,~
t -2- l 334233 functionality of at least about 2.5, a liquid modifier and a catalyst.
Among the modifiers, there are listed organophosphites which are said to function in moderating the reaction exotherm between the remaining components without substantial reaction therewith. Example 3 ( at 5 column 9) and Example 26 (at column 15) of the patent demonstrate the use of such a modifier.
DETAILED DESCRIPTION OF THE INVENTION
The adhesives of the invention include both 100% solids or high (at least 60%) solids polyurethane systems and they are suitable 10 both as film laminating and as structural adhesives. The adhesive comprises a prepolymer prepared from MDI and a polyol - a polyhydric alcohol containing 2 or more hydroxyl compounds - and includes an added 0.1 to about 10, preferably 0.3 to about 5, percent by weight of an organophosphite. The NCO content is about 1-25%, preferably 3 to 15 15%. The adhesive may also comprise a solvent in an amount of at most 40% by weight of the system.
Among the polyols suitable in the practice of the invention, the preferred ones are: polyester polyols, polyether polyols and polycarbonate polyols, all of which are well recognized in the art. These 20 and other suitable polyols may be prepared by known methods and are also readily available in commerce.
MDI in the present context refers to 4,4'-diphenylmethanediisocyanate, 2,4'-diphenylmethanediisocyanate, 2,2'-diphenylmethanediisocyanate and mixtures thereof. Preferably the MDI
25 is 4,4'-diphenylmethanediisocyanate. MDI is well recognized in the art and is readily available in commerce.
The organophosphite suitable in the invention is generally any organic compound which contains the radical PO~3. Included among the suitable organophosphites are:
Mo-2828 P~' (TO~ P 1 334233 where T is a hydrogen, alkyl, aryl or alkaryl group with the pro~ision that no more than two of the T groups are hydrogen atoms. Other suitable organ~phosphites conform 5 to (Z-Ar-O tP
where Ar is an aromatic nucleus, including naphthyl, phenyl and diphenyl and Z is an alkyl radical having at least 4 carbon atoms, preferably C6-C12 alkyl. Other 10 suitable phosphites include mono and di(nonylphenyl) phosphite, triethylphosphite, tris(2-ethylhexyl) phosphite, triisopropylphosphite, tris(dipropylene-glycol)phosphite, tris(nonylphenyl)phosphite, tristearylphosphite and tris(2-tolyl)pho~phite. The 15 preferred species are: tri(mixed mono and dinonylphenyl)phosphite, tris(nonylphenyl phosphite), tris(2-ethylhexyl)phosphite and tristearylphosphite.
The adhesive of the invention in both the solvent-free embodiment and high solids embod~ment 20 exhibit an improved level of adhesion. Additionally, it was noted that adding the phosphites accelerates the rate of cure in a film laminate combination of polypropylene to polyethylene.
EXPERIMENTAL
The adhesive used in demonstrating the invention were all based on propylene-oxide-tipped propylene glycol and methylene di-para-phenylene isocyanate (MDI). In preparing the phosphite-modified systems the MDI (Monduf M from Mobay Corporation) was 30 heated to 70C under nitrogen in a 3-neck flask equipped with a mechanical stirrer and an equalizing addition funnel. A mixture of the phosphite and glycol was added over a 15-120 minute period and the resulting prepolymer held at about 70C for about two hours. The resulting 35 prepolymer was cooled and then stored in a sealed, dry Mo-2828 *- Trademark _4_ 1 334233 jar under a nitrogen pad. In carrying out the experiments, the relative amounts of the components were typically about 125.15 gm (1 equivalent) of MDI, 297 gms (0.297 equivalents) of a polyol (~ 3600 from Mobay 5 Corporation) and about 1 Z relative tO the weight of the MDI and polyol, of the indicated phosphite.
Adhesive testing: the viscosities of the systems were measured at about 23C using a Brookfield viscometer (RVT or LVTD). Coating weights used in film 10 laminations were between 1.0 and 1.5 lbs/ream. Peel strength was determined using a Scott Tester at a cross-head speed of 12 inches/min after aging (24 hours or 1 week) at room temperature. The adhesives failure mode was determined as one of: adhesive failure, 15 cohesive failure and/or substrate failure. The testing of the prepolymers was performed on various laminations as follows: polypropylene (PP) to Mylar~-and polypropylene to polyethylene (PE).
Peel Stren~th (4) pli Phosphite Viscosity NCO
added mPa.s Z 1 day 1 week --- 6,725 6.90 0 2(3)(C) 0 4(3)(A) 0.3 0.5 Polygard HR(l) 6,730 6.79 0.2(C) 0.9 0.7(C) 0.7 Poly~d HR/ 7,725 6.68 0.9 0.8 T-12 0.8 0.8 30 Triethylphos- 17,300 6.96 0.6 0.8 phite 0.6(A) 0.7 Tris(2-ethyl- 9,100 6.90 0.8 0.8 hexyl)phosphite 0.8 0.8 Triisopropyl- 150,150 6.80 0.6 0.8 35 phosphite 0.6 0.9 Tris(dipropy- 114,700 5.04 0.8 0.8 leneglycol) 0.6(A) 0.5(A) phosphite Mo-2828 * - Trademark , t----_5 1 334233 Peel Stren~th (4) pli Phosphite Viscosity NC0 added mPa.s Z 1 dav 1 week 5 Tris(nonvl- 8,600 6.98 0.8 0.8 phenyl)phos- 0.6 0.8 phite Tristearyl- 8,160 6.77 0.8 0.8 Phosphite 0.6 0.8 10 Tris(2-tolyl)- 9,000 7.20 0.5(A) 0.7 phosphite 0.6(A) 0.7 (5) 10,000 7.65 0.2(A) 0.3(A) 0.5(A) 0.4(A) (6) 8,484 7.52 0.2(A) 0.2(A) 0.8 0.6 (1) Tri(mixed mono and dinonylphenyl) phosphite with 1 triisopropanol.~ine (2) Tin Catalyst (3) The indicated peel strength values are listed first for a Mylar7PP laminate and second for a PE/PP
laminate (4) Except where noted a failure in the propylene substrate was observed. (A) indicates failure in the adhesion to polypropylene. (C) indicates cohesive failure (5) Multiflex*N - isocyanate terminated MDI prepolymer (6) Multiflex~NM-35 - isocyanate terminated MDI
prepolymer The peel strength of the phosphite modified 30 adhesives of the invention compare favorably with commercial, solvent.free, products .(Peter Cooper adhesives Multiflex N and MultifleY~NM-35) as is noted in the table.
The adhesive of the invention is suitable for 35 use 8S a film laminating adhesive or as a structural adhesive. Among the film laminating systems where the adhesive of the invention is suitable mention is made of combinations of propylene, aluminum, polyethylene and Mo-2828 -. `, * - Trademark polyester films (for instance Mylar). The structural components for which the adhesive of the invention is suitable include combinations of stainless steel, aluminum, SMC, RIM and reinforced RIM.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the 10 spirit and scope of the invention except as it may be limited by the claims.
Mo-2828
Claims (7)
1. A polyurethane based film laminating adhesive comprising a prepolymer prepared by reacting MDI
with a polyol in the presence of an organic phosphite, said phosphite being present in an amount of about 0.1 to about 10% relative to the weight of said prepolymer, said prepolymer having an isocyanate content of from about 1 to about 25% by weight.
with a polyol in the presence of an organic phosphite, said phosphite being present in an amount of about 0.1 to about 10% relative to the weight of said prepolymer, said prepolymer having an isocyanate content of from about 1 to about 25% by weight.
2. The polyurethane based film laminating adhesive of Claim 1 wherein said polyol is selected from the group consisting of polyether polyol, polyester polyol and polycarbonate polyol.
3. The polyurethane based film laminating adhesive of Claim 1 wherein said phosphite conforms to wherein T independently is a hydrogen atom, alkyl, aryl or an alkaryl group with the provision that not more than two T groups are hydrogen atoms.
4. The polyurethane based film laminating adhesive of Claim 1 wherein said phosphite conforms to wherein Ar is an aromatic radical and Z is an alkyl radical having at least 4 carbon atoms.
5. The polyurethane based film laminating adhesive of Claim 1 wherein said phosphite is at least one member selected from the group consisting of mono(nonylphenyl)phosphite, di(nonylphenyl)phosphite, triethylphosphite, tris(2-ethylhexyl)phosphite, triisopropyl phosphite, tris(dipropylene glycol) phosphite, tris(nonylphenyl)phosphite, tristearyl-phosphite and tris(2-tolyl)phosphite.
6. The polyurethane based film laminating adhesive of Claim 5 wherein said amount is about 0.3 to about 3%.
7. The polyurethane based film laminating adhesive of Claim 5 comprising a solvent in an amount of at most 40% by weight of the system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90271786A | 1986-09-02 | 1986-09-02 | |
| US902,717 | 1986-09-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334233C true CA1334233C (en) | 1995-01-31 |
Family
ID=25416292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 530618 Expired - Fee Related CA1334233C (en) | 1986-09-02 | 1987-02-25 | Polyurethane adhesives containing organophosphites |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1334233C (en) |
-
1987
- 1987-02-25 CA CA 530618 patent/CA1334233C/en not_active Expired - Fee Related
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |