Fluoroalkyl siloxane/vinyl copolymer dispersions and pressure-sensitive adhesives having improved solvent resistance prepared therefrom

• US 5,482,991 A
• Filed: 09/16/1994
• Issued: 01/09/1996
• Est. Priority Date: 09/18/1992
• Status: Expired due to Term

• Current Assignee: Snecma Moteurs
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Everaerts, Albert I., Kumar, Ramesh C., Bogaert, Yvan A.
• Primary Examiner(s): Reddick, Judy M.
• Application Number:
  US08/307,936
• Time in Patent Office: 480 Days
• Field of Search: 524/263, 524/457, 524/467, 524/506, 524/547, 524/770, 524/805, 524/806, 524/516, 524/517, 524/519, 524/522, 524/521, 524/523, 524/524, 524/529, 524/530, 524/531, 524/533 , 524/534, 524/535, 524/544, 524/773, 524/532, 524/518
• US Class Current: 524/506
• CPC Class Codes: C09J 151/085 on to polysiloxanes
• CPC Class Codes: C09J 155/005 Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
• CPC Class Codes: C09J 183/10 Block or graft copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09J151/08, C09J153/00

Abstract

Novel pressure-sensitive adhesives are described which show significant resistance to solvents and working fluids such as jet fuel, hydraulic fluid, de-icing fluid and the like. Adhesive compositions comprise nonaqueous dispersions of copolymers of acrylic monomers prepared in the presence of a vinyl-substituted fluoroalkyl siloxane having the general formula I and a macromonomeric stabilizer. The adhesives prepared from the adhesive compositions exhibit excellent adhesion to glass, aluminum, and low surface-energy materials such as fluoroalkyl siloxane elastomers.

The fluoroalkyl siloxane has the formula ##STR1##

Claims

1. An adhesive comprising a cured adhesive composition, wherein the adhesive composition comprises:

a dispersion comprising the polymerization product of a mixture comprising;

(a) about 5 to about 40 parts by weight of a fluoroalkyl siloxane of the formula ##STR3## wherein;

R⁹ is independently selected from the group consisting of --CH₂ CH₂ R_f and -R⁷,

R_f is a fluoroalkyl group independently selected from the group consisting of C_m F_2m-1 and C_n F.sub.(2n+1)-q H_q,

m is an integer ranging from about 1 to about 20;

n is an integer ranging from about 1 to about 20;

q is an integer ranging from about 0 to about 2n;

x is an integer of about 11 or greater;

the fluoroalkylsiloxane comprises 10 or greater --CH₂ CH₂ R_f groups;

the fluoroalkylsiloxane comprises at least 1 R⁷ group;

wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁸ are each independently selected from the group consisting of alkyl groups comprising about 1 to about 12 carbon atoms, aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl, fluoroalkyl, and hydrogen; and

R⁷ is an organic group having at least two carbon atoms wherein at least 1 olefinic moiety is contained within R⁷ ;

wherein the ratio of R⁷ to --CH₂ CH₂ R_f is such that the mole percent of the olefinic moiety content contributed by R⁷ of the fluoroalkyl siloxane is between about 0.1 and about 4;

(b) about 60 to about 95 parts by weight of free radically polymerizable monomer, wherein the free-radically polymerizable monomer comprises;

(i) about 1 to about 20 percent by weight of free radically polymerizable polar monomer; and

(ii) about 80 to about 99 percent by weight of free radically polymerizable non-polar monomer;

wherein the weight percentages of (i) and (ii) are based upon the total weight of (i) plus (ii); and

wherein the total weight of (a) plus (b) equals 100 parts by weight total;

(c) about 0.1 to about 1 part by weight of a free radical initiator based upon 100 parts by weight total of (a) plus (b);

(d) about 2 to about 10 parts by weight of a stabilizer based upon 100 parts by weight of total of (a) plus (b) wherein said stabilizer has a number average molecular weight ranging from about 8000 to about 25,000 and wherein said stabilizer is selected from the group consisting of;

(i) a copolymer comprising (A) about 40 to about 60 parts by weight of monomer selected from the group consisting of vinyl esters of C₁ to C₈ monocarboxylic acids and C₁ to C₁₂ alkyl (meth)acrylates, and (B) about 60 to about 40 parts by weight of monomer selected from the group consisting of N-vinylpyrrolidone, acrylamide, N,N-dimethylacrylamide, N-vinylcaprolactam, and mixtures thereof wherein said copolymer stabilizer comprises 100 parts by weight total of the monomers of (i)(A) plus (i)(B); and

(C) about 0.5 to about 5 weight percent of a chain transfer agent based upon the weight of the monomers of (i)(A) plus (i)(B);

(ii) a macromonomer comprising the reaction product of the copolymer of (d)(i) wherein said chain transfer agent selected provides said copolymer with at least one functional group selected from the group consisting of --NH₂, --COOH, --OH, and combinations thereof, with an endcapping agent selected from the group consisting of isocyanatoethyl methacrylate, alpha, alpha-dimethyl-meta-isopropenyl benzylisocyanate, vinyl azlactone, para(chloromethyl) styrene, glycidyl methacrylate, and mixtures thereof, wherein at least about 95% of the functional groups selected from the group consisting of --NH₂, --COOH, --OH, and combinations thereof, of the copolymer are reacted with the endcapping agent; and

(iii) mixtures thereof; and

(e) about 30 to about 95 percent by weight of an organic solvent based upon the total weight of (a) plus (b) plus (c) plus (d) plus (e).

2. An adhesive comprising a cured adhesive composition, wherein the adhesive composition comprises:

a dispersion comprising the polymerization product of a mixture comprising;

(a) about 10 to about 30 parts by weight of a fluoroalkyl siloxane of the formula ##STR4## wherein;

R⁹ is independently selected from the group consisting of --CH₂ CH₂ R_f and -R⁷,

R_f is a fluoroalkyl group independently selected from the group consisting of C_m F_2m-1 and C_n F.sub.(2n+1)-q H_q,

m is an integer ranging from about 1 to about 20;

n is an integer ranging from about 1 to about 20;

q is an integer ranging from about 0 to about 2n;

x is an integer of about 11 or greater;

the fluoroalkylsiloxane comprises 10 or greater --CH₂ CH₂ R_f groups;

the fluoroalkylsiloxane comprises at least 1 R⁷ group;

wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁸ are each independently selected from the group consisting of alkyl groups comprising about 1 to about 12 carbon atoms, aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl, fluoroalkyl, and hydrogen; and

R⁷ is an organic group having at least two carbon atoms wherein at least 1 olefinic moiety is contained within R⁷ ;

wherein the ratio of R⁷ to --CH₂ CH₂ R_f is such that the mole percent of the olefinic moiety content contributed by R⁷ of the fluoroalkyl siloxane is between about;

0.1 and about 4;

(b) about 70 to about 90 parts by weight of free-radically polymerizable monomer, wherein said free-radically polymerizable monomer comprises;

(i) about 5 to about 15 percent by weight of free-radically polymerizable polar monomer; and

(ii) about 85 to about 95 percent by weight of free-radically polymerizable non-polar monomer;

wherein said weight percentages of (i) and (ii) are based upon the total weight of (i) plus (ii); and

wherein the total weight of (a) plus (b) equals 100 parts by weight total;

(c) about 0.2 to about 0.8 parts by weight of a free radical initiator based upon 100 parts by weight total of (a) plus (b);

(d) about 3 to about 6 parts by weight of a stabilizer based upon 100 parts by weight of total of (a) plus (b) wherein said stabilizer has a number average molecular weight ranging from about 8000 to about 25,000 and wherein said stabilizer is selected from the group consisting of;

(i) a copolymer comprising (A) about 40 to about 60 parts by weight of monomer selected from the group consisting of vinyl esters of C₁ to C₈ monocarboxylic acids and C₁ to C₁₂ alkyl (meth)acrylates, and (B) about 60 to about 40 parts by weight of monomer selected from the group consisting of N-vinylpyrrolidone, acrylamide, N,N-dimethylacrylamide, N-vinylcaprolactam, and mixtures thereof wherein said copolymer stabilizer comprises 100 parts by weight total of the monomer of (i)(A) plus (i)(B); and

(C) about 0.5 to about 5 weight percent of a chain transfer agent based upon the weight of the monomers of (i)(A) plus (i)(B);

(ii) a macromonomer comprising a reaction product of the copolymer of (d)(i) wherein said chain transfer agent selected provides said copolymer with at least one functional group selected from the group consisting of --NH₂, --COOH, --OH, and combinations thereof, with an endcapping agent selected from the group consisting of isocyanatoethyl methacrylate, alpha, alpha-dimethyl-meta-isopropenyl benzylisocyanate, vinyl azlactone, para(chloromethyl) styrene, glycidyl methacrylate, and mixtures thereof, wherein at least about 95% of the functional group(s) selected from the group consisting of --NH₂, --COOH, --OH, and combinations thereof, of the copolymer are reacted the with end-tapping agent; and

(iii) mixtures thereof; and

(e) about 40 to about 50 percent by weight of an organic solvent based upon the total weight of (a) plus (b) plus (c) plus (d) plus (e).

3. An adhesive comprising a cured adhesive composition, wherein the adhesive composition comprises:

a dispersion comprising the polymerization product of a mixture comprising;

(a) about 15 to about 25 parts by weight of a fluoroalkyl siloxane of the formula ##STR5## wherein;

R⁹ is independently selected from the group consisting of --CH₂ CH₂ R_f and -R⁷,

R_f is a fluoroalkyl group independently selected from the group consisting of C_m F_2m-1 and C_n F.sub.(2n+1)-q H_q,

m is an integer ranging from about 1 to about 20;

n is an integer ranging from about 1 to about 20;

q is an integer ranging from about 0 to about 2n;

x is an integer of about 11 or greater;

the fluoroalkylsiloxane comprises 10 or greater --CH₂ CH₂ R_f groups;

the fluoroalkylsiloxane comprises at least 1 R⁷ group;

wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁸ are each independently selected from the group consisting of alkyl groups comprising about 1 to about 12 carbon atoms, aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl, fluoroalkyl, and hydrogen; and

R⁷ is an organic group having at least two carbon atoms wherein at least 1 olefinic moiety is contained within R⁷ ;

wherein the ratio of R⁷ to --CH₂ CH₂ R_f is such that the mole percent of the olefinic moiety content contributed by R⁷ of the fluoroalkyl siloxane is between about 0.1 and about 2; and

wherein said fluoroalkyl siloxane has a weight average molecular weight of about 250,000 to about 600,000, and a fluorine content of at least about 30 weight percent;

(b) about 75 to about 85 parts by weight of free-radically polymerizable monomer, wherein said free-radically polymerizable monomer comprises;

(i) about 8 to about 12 percent by weight of free-radically polymerizable polar monomer; and

(ii) about 85 to about 92 percent by weight of free-radically polymerizable non-polar monomer;

wherein said weight percentages of (i) and (ii) are based upon the total weight of (i) plus (ii); and

wherein the total weight of (a) plus (b) equals 100 parts by weight total;

(c) about 0.3 to about 0.5 parts by weight of a free radical initiator based upon 100 parts by weight total of (a) plus (b);

(d) about 4 to about 5 parts by weight of a stabilizer based upon 100 parts by weight of total of (a) plus (b) wherein said stabilizer has a number average molecular weight ranging from about 8000 to about 25,000 and wherein said stabilizer is selected from the group consisting of;

(i) a copolymer comprising (A) about 40 to about 60 parts by weight of monomer selected from the group consisting of vinyl esters of C₁ to C₈ monocarboxylic acids and C₁ to C₁₂ alkyl (meth)acrylates, and (B) about 60 to about 40 parts by weight of monomer selected from the group consisting of N-vinylpyrrolidone, acrylamide, N,N-dimethylacrylamide, N-vinylcaprolactam, and mixtures thereof wherein said copolymer comprises 100 parts by weight total of the monomers of (i)(A) plus (i)(B); and

(C) about 0.5 to about 5 weight percent of a chain transfer agent based upon the weight of the monomers of (i)(A) plus (i)(B);

(ii) a macromonomer comprising the reaction product of the copolymer of (d)(i) wherein said chain transfer agent selected provides said copolymer with at least one functional group selected from the group consisting of --NH₂, --COOH, --OH, and combinations thereof, with an endcapping agent selected from the group consisting of isocyanatoethyl methacrylate, alpha, alpha-dimethyl-meta-isopropenyl benzylisocyanate, vinyl azlactone, para(chloromethyl) styrene, glycidyl methacrylate, and mixtures thereof, such that at least about 95% of the functional group(s) selected from the group consisting of --NH₂, --COOH, --OH, and combinations thereof, of the copolymer are reacted with the endcapping agent; and

(iii) mixtures thereof; and

(e) about 35 to about 40 percent by weight of an organic solvent based upon the total weight of (a) plus (b) plus (c) plus (d) plus (e).

4. An adhesive comprising a cured adhesive composition wherein the adhesive composition comprises:

a dispersion comprising the polymerization product of a mixture comprising;

(a) about 5 to about 40 parts by weight of a fluoroalkyl siloxane of the formula ##STR6## wherein;

R⁹ is independently selected from the group consisting of --CH₂ CH₂ R_f and -R⁷,

R_f is a fluoroalkyl group independently selected from the group consisting of C_m F_2m-1 and C_n F.sub.(2n+1)-q H_q,

m is an integer ranging from about 1 to about 20;

n is an integer ranging from about 1 to about 20;

q is an integer ranging from about 0 to about 2n;

x is an integer of about 11 or greater;

the fluoroalkylsiloxane comprises 10 or greater --CH₂ CH₂ R_f groups;

the fluoroalkylsiloxane comprises at least 1 R⁷ group;

wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁸ are each independently selected from the group consisting of alkyl groups comprising about 1 to about 12 carbon atoms, aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl, fluoroalkyl, and hydrogen; and

R⁷ is an organic group having at least two carbon atoms wherein at least 1 olefinic moiety is contained within R⁷ ;

wherein the ratio of R⁷ to --CH₂ CH₂ R_f is such that the mole percent of the olefinic moiety content contributed by R⁷ of the fluoroalkyl siloxane is between about 0.1 and about 4;

(b) about 60 to about 95 parts by weight of free radically polymerizable monomer, wherein the free-radically polymerizable monomer comprises;

(i) about 1 to about 20 percent by weight of free radically polymerizable polar monomer; and

(ii) about 80 to about 99 percent by weight of free radically polymerizable non-polar monomer;

wherein the weight percentages of (i) and (ii) are based upon the total weight of (i) plus (ii); and

wherein the total weight of (a) plus (b) equals 100 parts by weight total;

(c) about 0.1 to about 1 part by weight of a free radical initiator based upon 100 parts by weight total of (a) plus (b);

(d) about 2 to about 10 parts by weight of a stabilizer based upon 100 parts by weight of total of (a) plus (b) wherein said stabilizer has a number average molecular weight ranging from about 8000 to about 25,000 and wherein said stabilizer is selected from the group consisting of;

(i) a copolymer comprising (A) about 40 to about 60 parts by weight of monomer selected from the group consisting of vinyl esters of C₁ to C₈ monocarboxylic acids and C₁ to C₁₂ alkyl (meth)acrylates, and (B) about 60 to about 40 parts by weight of monomer selected from the group consisting of N-vinylpyrrolidone, acrylamide, N,N-dimethylacrylamide, N-vinylcaprolactam, and mixtures thereof wherein said copolymer stabilizer comprises 100 parts by weight total of the monomers of (i)(A) plus (i)(B); and

(C) about 0.5 to about 5 weight percent of a chain transfer agent based upon the weight of the monomers of (i)(A) plus (i)(B);

(ii) a macromonomer comprising the reaction product of the copolymer of (d)(i) wherein said chain transfer agent selected provides said copolymer with at least one functional group selected from the group consisting of --NH₂, --COOH, --OH, and combinations thereof, with an endcapping agent selected from the group consisting of isocyanatoethyl methacrylate, alpha, alpha-dimethyl-meta-isopropenyl benzylisocyanate, vinyl azlactone, para(chloromethyl) styrene, glycidyl methacrylate, and mixtures thereof, wherein at least about 95% of the functional groups selected from the group consisting of --NH₂, --COOH, --OH, and combinations thereof, of the copolymer are reacted with the endcapping agent; and

(iii) mixtures thereof;

(e) about 30 to about 95 percent by weight of an organic solvent based upon the total weight of (a) plus (b) plus (c) plus (d) plus (e); and

(f) about 0.1 to about 0.5 percent by weight of a crosslinker based upon the weight of (a) plus (b) plus (c) plus (d).

6. The adhesive of claim 4 wherein said crosslinker is selected from the group consisting of soluble metal salts, metal complexes, silanes, triazines, aromatic ketone monomers, multifunctional aziridine amides and mixtures thereof.

5. An adhesive composition comprising:

a dispersion comprising the polymerization product of a mixture comprising;

(a) about 10 to about 30 parts by weight of a fluoroalkyl siloxane of the formula ##STR7## wherein;

R⁹ is independently selected from the group consisting of --CH₂ CH₂ R_f and -R⁷,

R_f is a fluoroalkyl group independently selected from the group consisting of C_m F_2m-1 and C_n F.sub.(2n+1)-q H_q,

m is an integer ranging from about 1 to about 20;

n is an integer ranging from about 1 to about 20;

q is an integer ranging from about 0 to about 2n;

x is an integer of about 11 or greater;

the fluoroalkylsiloxane comprises 10 or greater --CH₂ CH₂ R_f groups;

the fluoroalkylsiloxane comprises at least 1 R⁷ group;

wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁸ are each independently selected from the group consisting of alkyl groups comprising about 1 to about 12 carbon atoms, aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl, fluoroalkyl, and hydrogen; and

R⁷ is an organic group having at least two carbon atoms wherein at least 1 olefinic moiety is contained within R⁷ ;

wherein the ratio of R⁷ to --CH₂ CH₂ R_f is such that the mole percent of the olefinic moiety content contributed by R⁷ of the fluoroalkyl siloxane is between about 0.1 and about 4;

(b) about 70 to about 90 parts by weight of free-radically polymerizable monomer, wherein said free-radically polymerizable monomer comprises;

(i) about 5 to about 15 percent by weight of free-radically polymerizable polar monomer; and

(ii) about 85 to about 95 percent by weight of free-radically polymerizable non-polar monomer;

wherein said weight percentages of (i) and (ii) are based upon the total weight of (i) plus (ii); and

wherein the total weight of (a) plus (b) equals 100 parts by weight total;

(c) about 0.2 to about 0.8 parts by weight of a free radical initiator based upon 100 parts by weight total of (a) plus (b);

(d) about 3 to about 6 parts by weight of a stabilizer based upon 100 parts by weight of total of (a) plus (b) wherein said stabilizer has a number average molecular weight ranging from about 8000 to about 25,000 and wherein said stabilizer is selected from the group consisting of;

(i) a copolymer comprising (A) about 40 to about 60 parts by weight of monomer selected from the group consisting of vinyl esters of C₁ to C₈ monocarboxylic acids and C₁ to C₁₂ alkyl (meth)acrylates, and (B) about 60 to about 40 parts by weight of monomer selected from the group consisting of N-vinylpyrrolidone, acrylamide, N,N-dimethylacrylamide, N-vinylcaprolactam, and mixtures thereof wherein said copolymer stabilizer comprises 100 parts by weight total of the monomer of (i)(A) plus (i)(B); and

(C) about 0.5 to about 5 weight percent of a chain transfer agent based upon the weight of the monomers of (i)(A) plus (i)(B);

(ii) a macromonomer comprising a reaction product of the copolymer of (d)(i) wherein said chain transfer agent selected provides said copolymer with at least one functional group selected from the group consisting of --NH₂, --COOH, --OH, and combinations thereof, with an endcapping agent selected from the group consisting of isocyanatoethyl methacrylate, alpha, alpha-dimethyl-meta-isopropenyl benzylisocyanate, vinyl azlactone, para(chloromethyl) styrene, glycidyl methacrylate, and mixtures thereof, wherein at least about 95% of the functional group(s) selected from the group consisting of --NH₂, --COOH, --OH, and combinations thereof, of the copolymer are reacted the with end-capping agent; and

(iii) mixtures thereof; and

(e) about 40 to about 50 percent by weight of an organic solvent based upon the total weight of (a) plus (b) plus (c) plus (d) plus (e); and

(f) about 0.1 to about 0.5 percent by weight of a crosslinker based upon the weight of (a) plus (b) plus (c) plus (d).

7. The adhesive of claim 5 wherein said crosslinker is selected from the group consisting of soluble metal salts, metal complexes, silanes, triazines, aromatic ketone monomers, multifunctional aziridine amides, and mixtures thereof.