Process for solvent casting a film

• US 4,664,859 A
• Filed: 01/10/1986
• Issued: 05/12/1987
• Est. Priority Date: 12/02/1983
• Status: Expired due to Fees

• Current Assignee: Congress Financial Corporation (Wells Fargo & Company)
• Original Assignee: VCF Films Incorporated DIV of PMC
• Inventors: Knoop, Henry E.
• Primary Examiner(s): Thurlow, Jeffery
• Application Number:
  US06/817,842
• Time in Patent Office: 487 Days
• Field of Search: 264/102, 264/166, 264/171, 264/300, 264/331.18, 264/331.21, 264/338, 264/345, 264/204, 264/169
• US Class Current: 264/102
• CPC Class Codes: C08J 2333/06 of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers

Abstract

A process for solvent casting acrylic films having superior properties by casting a solution comprising an organic solvent and a polymer system of one or more acrylic polymers onto a carrier, removing the solvent thereby forming the film on the carrier, and stripping the film from the carrier, is disclosed.

The polymer system comprises at least one polymer having the following properties: Total Elongation (%) of about 120-250; Tear Resistance of about 4.5-12.5 g/mil (which is about 177-492 mg/micron); Tensile Strength of about 4500-5000 lbs/in² (about 317-387 kg/cm²); Molecular Weight (amu) of about 250,000-500,000; Acid Content (%) of about 0.05-5.0; and Tucon hardness (Knoop No.) of about 6-12.

The acrylic film has Total Elongation, Tensile Strength, Tear Resistance, Acid Content and Tucon hardness in the aforesaid ranges, and is substantially free of reactive groups, such as hydroxy groups. The residual solvent in the film is (weight %) about 0-3. The film has dimensional stability (% shrinkage at about 130° C. for films of 0.5-5.0 mils, which is about 13-127 microns) of about 0.3. The thickness of the films is generally about 0.5-5.0 mils (which is about 13-127 microns). The films have excellent flexibility and extensibility, are completely free of pinholes, gels and imperfections, and have excellent weatherability.

Claims

1. A process for producing an acrylic film comprising the steps of:

(1) adding an organic solvent to a mixer;

(2) adding a polymer system to said organic solvent in said mixer;

(3) mixing said solvent and said polymer system to form a mixture that is a true solution of all components;

(4) degassing said mixture to remove all bubbles;

(5) casting said degassed mixture on a casting surface;

(6) removing said organic solvent from said cast, degassed mixture on said casting surface thereby forming said acrylic film on said casting surface;

wherein said acrylic film consists essentially of about 97-100% of said polymer system and about 0-3% of said organic solvent;

said polymer system consisting essentially of a polymer or mixture of polymers, each of said polymers consisting essentially of monomers of formula (I);

##STR2## wherein R₁ is selected from the group consisting of hydrogen and methyl, and R₂ is selected from the group consisting of straight or branched alkyl groups of from 1 to 20 carbon atoms,

each of said polymers having the following properties;

(a) a total elongation of about 120-250%;

(b) a tear resistance of about 4.5-12.5 g/mil (177-492 mg/micron);

(c) a tensile strength of about 4500-5000 lbs/in² (about 317-387 kg/cm²);

(d) a molecular weight of about 250,000-500,000 amu;

(e) an acid content of about 0.0-5.0%;

(f) a Tucon hardness in Knoop numbers of about 6-12;

(g) being substantially free of reactive groups;

said film having each of the aforesaid properties (a) through (c) and (e) through (g), having a thickness of about 0.5-5.0 mils (13-127 microns), having dimensional stability of less than 3.0% shrinkage, being completely free of pinholes and gels.

2. The process of claim 1, wherein:

said step (3) comprises the following substeps (3.1) through (3.3);

(3.1) closing said mixer and sealing it off from the atmosphere;

(3.2) mixing said solvent and said polymer system by the action of a high shear mixing blade;

(3.3) heating the contents of said mixer while mixing to a mixing temperature in excess of the boiling point of said organic solvent;

said step (4) comprises the following substeps (4.1) through (4.3);

(4.1) removing said mixture resulting from step (3) from said mixer and filtering the same to remove contaminants and any coarse undissolved ingredients;

(4.2) adding said filtered mixture of substep (4.1) to a holding tank and allowing it to cool to a temperature below the boiling point of said organic solvent;

(4.3) allowing said cooled mixture of substep (4.2) to stand for a period of time sufficient to allow all bubbles to rise to the surface of said cooled mixture;

said mixture of said organic solvent and said polymer system not being exposed to the atmosphere from said closing of said mixer in said substep (3.1) until said casting in said step (5).

3. The process of claim 2, wherein:

the amount of said organic solvent added to said mixer in step (1) is such that said solvent is about 50-75% of all components added to said mixer,

said step (3) further comprises the following substeps (3.4) after said substep (3.3);

(3.4) continuing said mixing at said mixing temperature until the viscosity of the said contents of said mixer is about 2,000-3,000 centipose;

said step (4) further comprises the following substep (4.4) after said substep (4.3);

(4.4) removing said degassed mixture of substep (4.3) from the base of said holding tank whereby bubbles are never formed in said degassed mixture, filtering said degassed mixture to remove all contaminants and solids, and transferring said filtered degassed mixture to a casting tank whereby said filtered degassed mixture never contacts the surface of the liquid in said casting tank thereby preventing the formation of any bubbles in said filtered degassed mixture;

said step (5) comprises the following substeps (5.1) through (5.2);

(5.1) removing said filtered degassed solution of substep (4.4) from the bottom of said casting tank without every emptying said casting tank thereby preventing the formation of bubbles in said filtered degassed solution;

(5.2) spreading said filtered degassed solution onto said casting surface at a temperature sufficiently below the boiling point of said solution to prevent the formation of bubbles in the solution as it contacts the atmosphere thereby forming a cast solution on said casting surface, said casting surface being continuous and moving relative to the stationary point of said spreading;

said step (6) comprises the following substeps (6.1) through (6.4);

(6.1) moving said cast solution by means of said moving casting surface into at least one heating zone;

(6.2) as said casting surface moves through said heating zone, heating said cast solution to vaporize a substantial portion of said organic solvent, thereby forming said acrylic film on said casting surface, said heating being gradual enough so that bubbles of solvent vapor are not formed in the film;

(6.3) moving said acrylic film by means of said moving casting surface into at least one cooling zone;

(6.4) as said acrylic film moves through said cooling zone, cooling said acrylic film;

said process further comprising the following step (7) after substep (6.4);

(7) stripping said acrylic film from said casting surface.

4. The process of claim 3, wherein:

said organic solvent is selected from the group consisting of Acetone, Aniline, Dimethyl Sulfoxide (DMSO), Benzene, Dimethyl Formamide (DMF), Methyl Ethyl Ketone (MEK), Ethyl Acetate, Ethylene Dichloride, Toluene, and Tetrahydrofuran (THF);

said filtering of substep (4.1) and said filtering of substep (4.4) are both by means of a plate frame filter and both to 15 microns;

said period of time of substep (4.3) is about 2-4 hours;

said casting surface is selected from the group consisting of drums and belts of stainless steel, copper and silicon rubber, and drums and belts of any material coated with an insoluble polymeric material or release paper;

said casting surface moving relative to said stationary spreading point at a speed of about 12-30 m/min.

5. The process of claim 4, wherein said organic solvent is THF, said mixing temperature of substep (3.3) is about 190°

-210°

F. (about 88°

-99°

C.), and said viscosity of substep (3.4) is about 2,200-2,800 centipoise.

6. The process of claim 1, wherein:

said R₂ is selected from the group consisting essentially of straight or branched alkyl groups of from 1 to 8 carbon atoms;

said acid content (e) is about 0.0-2.0%;

said film thickness is about 0.75-3.0 mils (about 19-76 microns);

said residual organic solvent is present in an amount of about 0-2%;

and said polymer system is present in an amount of about 98-100%.

7. The process of claim 6, wherein:

said total elongation (a) is about 150-210%;

said tear resistance (b) is about 6-10 g/ml (about 236-394 mg/micron);

said tensile strength (c) is about 4800-5200 lbs/in² (about 338-366 kg/cm²);

said molecular weight (d) is about 300,000-400,000 amu;

said Tucon hardness (f) is about 8-10 Knoop Nos.;

said dimensional stability is about 0-2%;

said residual organic solvent is present in an amount of about 0.1-1.0%; and

said polymer system is present in an amount of about 99.0-99.9%.

8. The process of claim 7, wherein:

said total elongation (a) is about 170-190%;

said tear resistance resistance (b) is about 8-9 g/mill (about 315-354 mg/micron);

said tensile strength (c) is about 4900-5100 lbs/in² (about 345-359 kg/cm²);

said acid content (e) is about 0.1-0.9%;

said Tucon hardness (f) is about 8-10 Knoop Nos.;

said film thickness is about 1.0-2.5 mils (about 25-63 microns); and

said dimensional stability is about 0.1-10%.

9. The process of claim 1, wherein:

said polymer system consists essentially of a first graft copolymer, said first graft copolymer consisting essentially of monomers of formula (I), said first graft copolymer comprising a plurality of sections, at least one of said sections comprising monomers of at least one alkyl acrylate and at least said alkyl methacrylate, and each of said sections having a different monomer composition.

10. The process of claim 1, wherein:

said polymer system consists essentially of a second graft copolymer consisting essentially of monomers of said formula (I);

said second graft copolymer comprising three sections (A), (B), and (C);

said second (A) consisting essentially of about 80-100% of an alkyl (of 1-8 carbons) acrylate monomer or monomers and about 0-20% of an alkyl (of 1-12 carbons) methacrylate monomer or monomers, and being present in an amount of about 5-35% of said second graft copolymer;

said section (B) consisting essentially of about 10-60% of an alkyl (of 1-8 carbons) acrylate monomer or monomers, about 40-90% of an alkyl (of 1-4 carbons) methacrylate monomer or monomers, and about 0-20% of an alkyl (of 1-12 carbons) methacrylate monomer or monomers; and

being present in an amount of about 1-70% of said second graft copolymer;

said section (C) consisting essentially of about 60-100% of an alkyl (of 1-4 carbons) methacrylate monomer or monomers and about 0-40% of an alkyl (of 1-12 carbons) methacrylate monomer or monomers, and being present in an amount of the remainder of said second graft copolymer.

11. The process of claim 1, wherein:

said polymer system consists essentially of a third graft copolymer consisting essentially of monomers of formula (I);

said third graft copolymer consisting essentially of four sections (A), (B), (C), and (D);

said section (A) consisting essentially of about 51-100 parts of an alkyl (of 1-4 carbons) methacrylate monomer or monomers, about 0-49 parts of an alkyl (of 1-8 carbons) acrylate monomer or monomers, about 0-10 parts of a polyfunctional monomer, and about 0.1-5 parts of a graftlinking agent, and being present in an amount of 5-35% of said third graft copolymer;

said section (B) consisting essentially of about 80-120 parts of an alkyl (of 1-8 carbons) acrylate monomer or monomers, about 0-10 parts of a polyfunctional monomer, and about 0.1-5 parts of a graftlinking agent, and being present in an amount of about 5-45% of said third graft copolymer;

said section (C) consisting essentially of about 10-90 parts of an alkyl (1-4 carbons) methacrylate monomer or monomers, about 90-100 parts of an alkyl (1-8 carbons) acrylate monomer or monomers, about 0.1-5 parts of a graftlinking agent, and about 0-10 parts of a polyfunctional monomer, and being present in an amount of about 5-35% of said third graft copolymer; and

said section (D) consists essentially of about 50-100 parts of an alkyl (of 1-4 carbons) methacrylate monomer or monomers, and about 0-49 parts of an alkyl (1-8 carbons) acrylate monomer or monomers, and being present in an amount of about 10-80% of said third graft copolymer.

12. The process of claim 1, wherein:

said polymer system consists essentially of a first mixed copolymer consisting essentially of monomers of said formula (I);

said R₂ is straight or branched alkyl of about 1-8 carbon atoms;

said first mixed copolymer consisting essentially of about 10-60% of an alkyl acrylate monomer or monomers, and about 40-90% of an alkyl mwethacrylate monomer or monomers.

13. The process of claim 2, wherein:

said R₂ is straight or branched alkyl of about 1-4 carbon atoms;

said copolymer system consists essentially of a first mixed copolymer which consists essentially of about 30-50% of an alkyl acrylate monomer or monomers and about 50-70% of an alkyl methacrylate monomer or monomers;

said first mixed copolymer having a total elongation of about 150-210%, a tear resistance of about 6-10 g/mil (about 236-394 mg/micron), a tensile strength of about 4800-5200 lbs/in² (about 338-366 kg/cm²), a molecular weight of about 300,000-400,000 amu, an acid content of about 0.1-2.0, and a Tucon hardness of about 7-11 Knoop Nos.;

said film consists essentially of about 98-99.9% of said polymer system and about 0.1-2.0% of said residual organic solvent;

and said film has a dimensional stability of about 0-2%, and a thickness of about 0.75-3.0 mils (about 19-76 microns).

14. The process of claim 5, wherein:

said polymer system consists essentially of a first mixed copolymer which consists essentially of about 35-45% of a single alkyl acrylate monomer of formula (I), and about 55-65% of a single alkyl methacrylate monomer of formula (I);

said R₂ is alkyl of about 1-2 carbon atoms;

said total elongation (a) is about 170-190%;

said tear resistance (b) is about 8-9 g/mil (about 315-354 mg/micron);

said tensile strength (c) is about 4900-5100 lbs/in² (about 345-359 kg/cm²);

said molecular weight (d) is about 325,000-375,000 amu;

said acid content (e) is about 0.1-0.9%;

said Tucon hardness (f) is about 8-10 Knoop Nos.;

said film having each of the aforesaid properties (a) through (c) and (e) through (g), having a thickness of about 1.0-2.5 mils (about 25-63 microns), having a dimensional stability of about 0.1-1.0%; and

said film consisting essentially of about 0.1-1.0% of said residual organic solvent and about 99.0-99.9% of said polymer system.

15. The process of claim 1, wherein:

said polymer system further consists essentially of about 1-50% of a second polymer;

said second polymer consisting essentially of monomer units of formula (I), and having the following properties;

a total elongation of about 3-7%;

a tensile strength of about 8,000-10,000 lbs/in² (about 563-704 kg/cm²);

a tear resistance of about 4-6 g/mil (about 157-236 mg/micron);

a molecular weight of about 90,000-120,000 amu;

an acid content of about 0.0-5.0%; and

a Tucon hardness of about 12-22 Knoop Nos.;

and said second polymer is completely miscible in all compatible polymers of said polymer system when dissolved in said organic solvent.

16. The process of claim 10, wherein:

said polymer system further consists essentially of about 1-50% of a second polymer;

said second polymer consisting essentially of monomer units of formula (I), and having the following properties;

a total elongation of about 3-7%;

a tensile strength of about 8,000-10,000 lbs/in² (about 563-704 kg/cm²);

a tear resistance of about 4-6 g/mil (about 157-236 mg/micron);

a molecular weight of about 90,000-120,000 amu;

an acid content of about 0.0-5.0%; and

a Tucon hardness of about 12-22 Knoop Nos.;

and said second polymer is completely miscible in all compatible polymers of said polymer system when dissolved in said organic solvent.

17. The process of claim 11, wherein:

said polymer system further consists essentially of about 1-50% of a second polymer;

said second polymer consisting essentially of monomer units of formula (I), and having the following properties;

a total elongation of about 3-7%;

a tensile strength of about 8,000-10,000 lbs/in² (about 563-704 kg/cm²);

a tear resistance of about 4-6 g/mil (about 157-236 mg/micron);

a molecular weight of about 90,000-120,000 amu;

an acid content of about 0.05-5.0%, and a Tucon hardness of about 12-22 Knoop Nos.;

said second polymer is completely miscible in all compatible polymers of said polymer system when dissolved in said organic solvent.

18. The process of claim 12, wherein:

said polymer system further consists essentially of about 1-30% of a second polymer;

said second polymer consisting essentially of monomer units of formula (I) and having the following properties;

a total elongation of about 3-7%;

a tensile strength of about 8,000-10,000 lbs/in² (about 563-704 kg/cm²);

a tear resistance of about 4-6 g mil (about 157-236 mg/micron);

a molecular weight of about 100,000-110,000 amu;

an acid content of about 0.0-2.0%; and

a Tucon hardness of about 15-19 Knoop Nos.;

said second polymer is completely miscible in all compatible polymers of said polymer system when dissolved in said organic solvent;

said second polymer consists essentially of about 3-10% of said alkyl acrylate monomer or monomers of formula (I) and about 90-97% of said alkyl methacrylate monomer or monomers of formula (I).

19. The process of claim 13, wherein:

said polymer system further consists essentially of about 5-20% of a second polymer;

said second polymer consisting essentially of monomer units of formula (I), and having the following properties;

a total elongation of about 3-7%;

a tensile strength of about 8,000-10,000 lbs/in² (about 563-704 kg/cm²);

a tear resistance of about 4-6 g/mil (about 157-236 mg/micron);

a molecular weight of about 100,000-110,000 amu;

an acid content of about 0.1-0.9%; and

a Tucon hardness of about 15-19 Knoop Nos.;

and said second polymer is completely miscible in all compatible polymers of said polymer system when dissolved in said organic solvent;

and said second polymer consists essentially of about 3-10% of said alkyl acrylate monomer or monomers of formula (I) and about 90-97% of said alkyl methacrylate monomer or monomers of formula (I).

20. The process of claim 14, wherein:

said polymer system further consists essentially of about 8-12% of a second polymer;

said second polymer consisting essentially of monomer units of formula (I), and having the following properties;

a total elongation of about 3-7%;

a tensile strength of about 8,000-10,000 lbs/in² (about 563-704 kg/cm²);

a tear resistance of about 4-6 g/mil (about 157-236 mg/micron);

a molecular weight of about 104,000-106,000 amu;

an acid content of about 0.1-0.9%; and

a Tucon hardness of about 15-19 Knoop Nos.;

said second polymer is completely miscible in all compatible polymers of said polymer system when dissolved in said organic solvent;

and said second polymer consists essentially of about 3-10% of said alkyl acrylate monomer of formual (I) and about 90-97% of said alkyl methacrylate monomer of formula (I).