CA2220206C - Water borne pressure sensitive adhesive compositions derived from copolymers of higher vinyl esters - Google Patents
Water borne pressure sensitive adhesive compositions derived from copolymers of higher vinyl esters Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
Abstract
The present invention is directed to improved aqueous based pressure sensitive adhesive emulsion polymers. Conventional emulsion based pressure sensitive adhesives are comprised of a copolymer comprised of polymerized units of acrylic esters and ethylenically unsaturated monomers, the copolymer having a Tg of from -15 to-70°C. The improvement in the aqueous based, emulsion polymerized pressure sensitive adhesives resides in the incorporation of a vinyl C8-13 ester of a neo-acid into the copolymer present in the pressure sensitive adhesives. Such vinyl ester is formed from a mixture of propylene oligomers and such vinyl ester is represented by thechemical formula:
C8-13H17-27C02GH=CH2 N:\RLB\186P5499.apl
C8-13H17-27C02GH=CH2 N:\RLB\186P5499.apl
Description
~ ' j CA 02220206 1997-11-0~ ~
TITLE OF THE INVENTION:
WATER BORNE PRESSURE SENSITIVE ADHESIVE COMPOSITIONS
DERIVED FROM COPOLYMERS OF HIGHER VINYL ESTERS
CROSS-REFERENCE TO RELATED APPLICATIONS
Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR
Not applicable.
BACKGROUND OF THE INVENTION
This invention relates to improved aqueous based pressure sensitive adhesive 10 emulsions, the improvement residing in the incorporation of polymerized units of a vinyl ester of a ne~acid into the copolymer present in these emulsions.
Pressure sensitive adhesives are widely used for fabricating paper labels, laminating polymeric films such as laminating poly(vinyl chloride), polyester, etc., for forming decals and other related products. Most of the pressure sensitive adhesives 15 have been solvent based but in recent years government regulations have forced the industry to develop environmentally friendly aqueous based pressure sensitive adhesives.
Aqueous based pressure sensitive adhesives comprised of polymerized monomer units of vinyl acetate, ethylene, and/or acrylic esters, etc. have been inferior to 20 the solvent based pressure sensitive adhesives in that they do not have sufficient I CA 02220206 1997-11-0~
adhesive power to low surface energy substrates nor do they have good water resistance and so forth.
The following patents describe a variety of emulsion polymers incorporating vinyl esters and/or emulsion based pressure sensitive adhesives:
U.S. 5,461,103 discloses aqueous based pressure sensitive adhesive emulsions having an ability to coat low energy surfaces without retracting or cratering. The emulsion polymers are prepared by a two stage emulsion polymerization process, the first stage resulting in the formation of an alkali insoluble polymeric system incorporating acid functional groups and polymerized hydrophobic monomer units, e.g., C4 12 alkyl 10 acrylates and the second stage incorporating monomer units suited for the manufacture of pressure sensitive adhesives, e.g., acrylic and methacrylic esters, vinyl esters of C2-5 carboxylic acids, e.g., vinyl acetate and vinyl propionate and the like.
U.S. 4,923,919 discloses pressure sensitive adhesive emulsions based on acrylic polymers that contain at least 40% by weight of an alkyl acrylate and a support resin that 15 is alkali soluble. The support resin contains polymerizable carboxylic acid anhydride groups with the polymeric resin having a number average molecular weight of from1000-15,000. Typically the support resins are based on vinyl monomers such as acrylic and methacrylic acid esters, styrene and combinations thereof.
U.S. 4,322,516 discloses aqueous based pressure sensitive adhesives formed 20 from ethylene units, acrylic ester units, vinyl acetate units, acrylamide units and other olefinically unsaturated monomers. Tackifying agents are incorporated into the ethylene based pressure sensitive adhesives.
U.S. 4,939,190 discloses emulsion type pressure sensitive adhesives wherein the emulsions are prepared in a staged procedure, the first stage comprising 25 polymerizing an ethylenically unsaturated monomer such as styrene, acrylonitrile and/or CA 02220206 1997-11-0~ 1 -(meth)acrylates in the presence of a tackifier resin and a second stage comprising polymerizing alkyl acrylates having at least 4 carbon atoms in the presence of the first stage polymer.
U.S. 5,276,084 discloses aqueous based pressure sensitive adhesives based on 5 polymers comprising vinyl acetate, ethylene, alkyl acrylates dialkyl maleate and fumarates, hydroxyalkyl acrylates, acrylamides and unsaturated carboxylic acids such as acrylic acid.
U.S. 3,697,618 discloses acrylic pressure sensitive adhesives incorporating a vinyl ester of a carboxylic acid, e.g., vinyl acetate, a lower alkyl acrylate and a 10 copolymerizable alpha, beta-ethylenically unsaturated dicarboxylic acid or anhydride.
U.S. 3,562,229 discloses solvent polymerized copolymers of ethylene and vinyl esters where the vinyl esters are derived from long chain carboxylic acids, e.g., versatic acid which are mixtures of C9-11 carboxylic acids. Isotridecanoic and isononanoic are representative acids. The solvent based polymers incorporating vinyl esters of versatic 15 acid were alleged to be superior to polymers incorporating vinyl laurate which has the same number of carbon atoms.
U.S. 3,294,727 discloses polymerizing vinyl esters of saturated monocarboxylic acids to form emulsions having suitability for producing freeze-thaw stable paints. The preferred saturated aliphatic monocarboxylic acids for forming vinyl esters are based 20 upon compounds of the formula:
wherein R1 and R2 are alkyl radicals of normal, branched, or cyclic structure and R3 represents a hydrogen or hydrocarbyl radical. The carboxylic acids have from about CA 02220206 1997-11-0~ ~
9-19 carbon atoms. Representative copolymers are comprised of polymerized units of vinyl acetate and/or acrylic acid and the representative vinyl esters.
U.S. 3,669,942 discloses solvent based polymers comprising a vinyl ester of an alpha-branched, saturated aliphatic monocarboxylic acid having from 5-20 carbon atoms 5 and an alpha, beta-ethylenically unsaturated carboxylic acid having 3-5 carbon atoms, a monovinyl aromatic compound and acrylic acid esters including hydroxyalkyl acrylate esters. The compositions are useful as water thinnable paint binders.
U.S. 3,654,213 discloses tacky pressure sensitive adhesives based on interpolymers of vinyl esters and alkyl acrylates, the interpolymers being dissolved at 10 high solids content in organic solvents. Representative interpolymers are based upon vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl valerate with vinyl acetate being preferred. Other monomers which can be incorporated into the polymer include acrylic acid esters such as methyl acrylate, ethyl acrylate and so forth.
U.S. 4,322,516 discloses pressure sensitive adhesive emulsions whose copolymers comprise:
(a) 10-30 wt% ethylene, (b) 29-69 wt% acrylic acid esters of alcohols, (c) 20-55 wt% vinyl acetate, (d) 0.2-8 wt% (meth)acrylamide, and (e) 0-12 wt% other olefinically unsaturated comonomers.
BRIEF SUMMARY OF THE INVENTION
The present invention is directed to improved aqueous based pressure sensitive adhesive emulsion polymers. Conventional aqueous emulsion based pressure sensitive 25 adhesives are comprised of a copolymer comprised of polymerized units of acrylic esters CA 02220206 1997-11-0~ ?
and ethylenically unsaturated monomers, the copolymer having a Tg of from -15 to-70~C. The improvement in the aqueous based, emulsion polymerized pressure sensitive adhesives resides in the incorporation of a vinyl ester of a Ca 13 ne~acid into the copolymers present in the pressure sensitive adhesives. Such copolymers incorporate a vinyl ester formed from a mixture of propylene oligomers and such vinyl ester is represented by the chemical formula:
C8.,3H17 27CO2CH=CH2 There are significant advantages associated with the above aqueous based pressure sensitive adhesive emulsions and the process for producing these emulsions 10 and these advantages include:
~ an ability to provide enhanced properties to pressure sensitive adhesives through the methyl group rich vinyl ester mixture which exhibits a lower solubility parameter compared to the corresponding linear alkyl vinyl esters;
~ an ability to provide enhanced properties to pressure sensitive adhesives through the ability of the vinyl ester monomer to undergo emulsion polymerization with a variety of olefinically unsaturated comonomers;
~ an ability to form an excellent bond and enhanced resistance to plasticizer migration with plasticized poly(vinyl chloride);
~ an ability to generate a class of pressure sensitive adhesives which have an excellent balance of peel and cohesive strength;
~ an ability to provide enhanced thermal and hydrolytic stability to emulsion based pressure sensitive adhesives as compared to aqueous based vinyl acetate counterparts; and, - - -CA 02220206 1997-11-0~
an ability to provide enhanced properties to pressure sensitive adhesives through binding to lower surface energy surfaces of lower polarity, such as polyethylene, by virtue of stronger bonding of the copolymers .
DETAILED DESCRIPTION OF THE lNVENTlON
Emulsion polymerization of ethylenically unsaturated monomers such as lower 10 alkyl acrylates and vinyl esters, typically represented by vinyl acetate or vinyl propionate, to produce aqueous based pressure sensitive adhesive emulsions containing vinyl copolymer is well known. The improvement to emulsion based pressure sensitive adhesives containing vinyl copolymer incorporating polymerized units of ethylenically unsaturated monomer units resides in the incorporation of a vinyl ester of a neo-acid 15 derived from a propylene oligomer feedstock into the vinyl copolymer.
The vinyl ester of a neo-acid of propylene oligomers or mixture thereof is incorporated into the vinyl polymer is comprised of the vinyl ester of a single or mixture of tri- and tetramers of propylene which have been converted to the corresponding single or mixture of C8 ,3 neo-acids. These esters typically are prepared by first 20 converting the tri and tetramers of propylene to the corresponding acids and then converting the corresponding those neo-acids to the vinyl esters. The vinylation of those acids can be achieved either by transvinylation with vinyl acetate or by catalytic addition of the neo-acids to acetylene. Some of the vinyl esters may be represented by a singular neo-acid, but generally the vinyl esters of the neo-acids are present as a 25 mixture.
CA 02220206 l997-ll-0~ j Aqueous based pressure sensitive adhesive emulsions are based on emulsions which comprise a colloidal dispersion of the vinyl copolymer in water. The copolymers present in the pressure sensitive adhesives are typically derived from the following monomers and within the percentage proportions listed below:
(a) 5-40 wt% of a vinyl ester of a C8 13 ne~acid, preferably 15 to 30 - wt%;
(b) 30-80 wt% of a C,-,2 alkyl ester of acrylic or methacrylic acid, preferably 40 to 70 wt%, (c) 0-20% wt% of a vinyl ester of saturated aliphatic acids, preferably 0 to 10%;
(d) 0-30 wt% ethylene, styrene or butadiene, preferably 0 to 20 wt%;
(e) 0-20 wt% di-(C1 ~3)alkyl maleate/fumarate, preferably 0 to 10 wt%;
(f) 0-5 wt% of a hydroxyalkyl (meth)acrylate;
(g) 0-5 wt% (meth)acrylamide; and, (h) 0-10 wt% alpha, beta-ethylenically unsaturated monocarboxylic acid.
A variety of other comonomers, e.g., other ethylenically unsaturated monomers sometimes employed in the formation of the aqueous based pressure sensitive emulsions can be copolymerized with the vinyl ester of a ne~acid to form adhesives.
20 For example, C,.8 alkyl vinyl ethers, vinyl chloride, vinylidene chloride, nitriles, carboxylic amides such as N-vinylformamide and N-vinylacetamide, acrylonitrile and methacrylonitrile to produce a variety of polymers. Examples of useful alkyl vinyl ethers are methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, tert-butyl vinyl ether and n- and isobutyl vinyl ether.
~ CA 02220206 1997-11-05 Component (a) monomers which are the vinyl esters of C813 neo-acids and utilized in producing the improved pressure sensitive adhesives have been defined.
Component (b) monomers utilized in producing the pressure sensitive adhesives containing the vinyl esters of C8 ,3 neo-acids are alkyl esters of acrylic or methacrylic 5 acid. These are esters of acrylic acid or methacrylic acid and a C1 1z alcohol. Examples of suitable alcohols for the preparation of these esters are methanol, ethanol, propanol, isopropanol, n-, iso- and tert-butyl alcohol, neopentyl alcohol, 2-ethyl-hexanol, n-octanol, dodecanol, palmityl alcohol and stearyl alcohol. Specific examples of unsaturated alkyl acrylate monomers include methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl 10 acrylate 2-ethylhexyl acrylate, isooctyl acrylate, isodecyl acrylate and the like.
Component (c) monomers which may be used in forming emulsion polymers for pressure sensitive adhesives can include other vinyl esters than the vinyl esters of neo-acids. Some of the more common vinyl esters used in the polymer synthesis include C3.18 alkanoic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate 15 and the like. These esters, and particularly the lower alkyl esters, may detract from the overall properties of the pressure sensitive emulsion imparted by the vinyl ester of the C8 13 neo-acids.
Component (d) monomers used as a fraction of the polymers utilized in forming emulsion polymers for pressure sensitive adhesives can include hydrocarbon monomers 20 such as ethylene, styrene, butadiene.
Component (e) monomers used in forming many of the pressure sensitive adhesives include an alkyl maleate or fumarate, for the purpose of providing enhanced tack. etc. One may suitably use the diesters of maleic acid or fumaric acid, the diester being formed by the reaction of the acid with a C1 13, such as, n-octyl alcohol, isooctyl -CA 02220206 1997-1l o~; 1 alcohol, butyl alcohol, isobutyl alcohol, methyl alcohol, amyl alcohol and the like.
Preferably a C4 8, alcohol is employed.
Components (f) monomers often are incorporated into the pressure sensitive adhesive polymer. Representative monomers include hydroxyethyl acrylate, 5 hydroxyethyl methacrylate, hydroxypropyl acrylates, hydroxypropyl methacrylate, hydroxypropyl acrylates, hydroxypropyl methacrylates, hydroxybutyl acrylates and hydroxybutyl methacrylates.
Component (g) monomers often are incorporated into the copolymers at some levels. Examples of amides include acrylamide, methacrylamide and N-methylol-1 0 acrylamide.
Component (h) monomers include the alpha, beta-ethylenically unsaturated C3-6 carboxylic acids which can be incorporated into the polymer can be methacrylic acid, crotonic acid, acrylic acid and the like.
The sum of the monomers used to form the pressure sensitive copolymers is 100 15 percent. The emulsion copolymers are designed to have a Tg of less than -15~C, preferably -15 to -70~C and typically -20 to -50~C. The aqueous emulsions contain about 40 to 70 wt% solids.
The emulsion polymerization process typically involves an initial homogenization in which the monomers which include the vinyl esters of ne~acids and the other 20 monomers which are employed to form the vinyl copolymer such as C~.12 alkyl acrylates or methacrylates, vinyl acetate, dialkyl maleate/fumarate, ethylene, acrylamide and other monomers are thoroughly agitated. If ethylene is added to the reactor to form a copolymer, the reactor is pressured to the working pressure to effect solution of the ethylene in the monomers. Then, the reaction medium is gradually heated to CA 02220206 1997-11-0~ ) polymerization temperature. The homogenization period is followed by a polymerization period during which the free radical source is added incrementally.
Various free-radical forming catalysts such as peroxide compounds can be used in carrying out the emulsion polymerization of the monomers. Combination-type catalysts employing both reducing agents and oxidizing agents can also be used. The use of this type of combined catalyst is generally referred to in the art as "redox polymerization" or "redox system." The reducing agent is also often referred to as an activator and the oxidizing agent as an initiator. Suitable reducing agents or activators include bisulfites, sulfoxylates, or other compounds having reducing properties such as ferrous salts, and tertiary aromatic amines, e.g., N,N-dimethylaniline. The oxidizing agents or initiators include hydrogen peroxide, organic peroxides such as benzoyl peroxide, t-butyl hydroperoxide and the like, persulfates, such as ammonium or potassium persulfate, perborates, and the like. A specific combination-type catalyst or redox system which can be used is hydrogen peroxide and sodium formaldehyde 1 5 sulfoxylate.
The initiator is employed in the amount of 0.1 to 2%, preferably 0.25 to 0.75%, based on the weight of monomers introduced into the reactor. The activator is ordinarily added as an aqueous solution and the amount of activator is generally from 0.25 to 1 times the amount of initiator.
A wide variety of nonionic, anionic and cationic surfactants can be used to stabilize the emulsion in emulsion polymerization processes. Suitable nonionic emulsifying agents include polyoxyethylene condensates. Polyoxyethylene condensates may be represented by the general formula:
R ( CH2--CH2-O )nH
CA 02220206 1997-11-0~ , where R is the residue of a fatty alcohol containing 10-18 carbon atoms, an alkylphenol, a fatty acid containing from 10-18 carbon atoms, an amide, an amine, or a mercaptan, and where n is an integer of 1 or above. Some specific examples of polyoxyethylene condensates which can be used include polyoxyethylene aliphatic ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene hydroabietyl ether and the like; polyoxyethylene alkaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether and the like; polyoxyethylene esters of higher fatty acids such as polyoxyethylene laurate, polyoxyethylene oleate and the like as well as condensates of ethylene oxide with resin acids and tall oil acids; polyoxyethylene 10 amide and amine condensates such as N-polyoxyethylene lauramide, and N-lauryl-N-polyoxyethylene amine and the like; and polyoxyethylene thioethers such as polyoxyethylene n-dodecyl thioether. Other suitable nonionic surfactants are alkylarylethoxylate alcohols, alkylethoxylate alcohol, ethoxypropoxylate, alcohols from ethylene oxide and/or propylene oxide reaction products, and the like.
Another class of nonionic surfactants are sold under the Igepal trademark. One example within this class is a polyoxyethylene nonylphenyl ether having a cloud point of between 126 and 133~F and marketed under the trade mark "Igepal C0-630"; another is polyoxyethylene nonylphenyl ether having a cloud point above 212~F and marketed under the trade mark "Igepal C0-887."
Examples of anionic surfactants include metal or ammonium salts of long chain alkyl sulfates and the likes; metal or ammonium salts of alkylarylethoxylated sulfates or sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkylarylsulfonates, alkyl phosphates, etc.
A protective colloid also can be used in the polymerization mixture as a 25 stabilizing agent. Various colloids and amounts conventionally used in emulsion CA 02220206 1997-11-0~ , polymerization can be incorporated into the latices as desired and in combination with the surfactants. Representative colloids which can be used include poly(vinyl alcohol), partially-acetylated poly(vinyl alcohol), e.g., up to 50% acetylated, casein, hydroxyethyl starch, carboxymethylcellulose, gum arabic, and the like.
The concentration range of the total amount of emulsifying agents used in emulsion polymerization is from 0.1 to 10% based on the aqueous phase of the latex regardless of the solids content. The stabilizers employed are, in part, governed by the use to which the copolymer latex is to be put. By utilizing appropriate levels of surfactant and/or protective colloid, one can obtain latex polymer particles having a variety of 10 average particle size ranges and distributions.
In order to maintain the pH of the system at the desired value, there is suitably added a buffering agent of any convenient type. Any alkaline material which is compatible with the stabilizing agent can be used as the buffer. The amount of buffer is that sufficient to adjust the pH of the system within the desired range, e.g., 2.5 to 10 and 15 preferably 3.5 and 8.5. The amount of buffer is generally about 0.1 to 0.5% by weight, based on the monomers.
Reaction temperatures for emulsion polymerizing the vinyl esters of ne~acids along with other monomers are conventional. The reaction temperature can be controlled by the rate of catalyst addition and by the rate of the heat dissipation therefrom. Generally, it is advantageous to maintain a temperature from about 50 to 90~C. While temperatures as low as 0~C can be used, economically, the lower temperature limit is about 40~C.
The reaction time will also vary depending upon other variables such as the temperature, the catalyst, and the desired extent of the polymerization. It is generally desirable to continue the reaction until less than 0.1% of the vinyl ester remains - ' , CA 02220206 1997-11-0~ , unreacted. Under these circumstances, a reaction time of about 4 hours has been found to be generally sufficient for complete polymerization, but reaction times ranging from 2 to 10 hours have been used, and other reaction times can be employed, if desired.
The following examples are provided to illustrate various embodiments of the 5 invention and are not intended to restrict the scope thereof.
Example 1 Preparation of Water Borne Pressure Sensitive Adhesives of Mixed Vinyl Ne~C813 Esters, 2-EHA, Methyl Methacrylate and Acrylic Acid The mixed vinyl ne~C8.13 esters employed in forming the pressure sensitive adhesive emulsions are formed from a propylene oligomer feedstock which is comprised predominately of propylene trimers and tetramers.
To a 2-liter resin reactor are added the following initial reaction mixture comprising 200g of deionized water, 1.28g of sodium citrate and 133g of a pre-emulsion monomer mixture of the following composition:
Deionized water 288.00 g Abex EP-120 (30% active)* 8.23 g Igepal C0-887 (70% active) 8.23 g Aerosol MA-80 (80% active) 7.20 g Vinyl ne~C8.13 ester monomer144.00 g 25.0%*
Methyl methacrylate 74.90 g 13.0%*
TITLE OF THE INVENTION:
WATER BORNE PRESSURE SENSITIVE ADHESIVE COMPOSITIONS
DERIVED FROM COPOLYMERS OF HIGHER VINYL ESTERS
CROSS-REFERENCE TO RELATED APPLICATIONS
Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR
Not applicable.
BACKGROUND OF THE INVENTION
This invention relates to improved aqueous based pressure sensitive adhesive 10 emulsions, the improvement residing in the incorporation of polymerized units of a vinyl ester of a ne~acid into the copolymer present in these emulsions.
Pressure sensitive adhesives are widely used for fabricating paper labels, laminating polymeric films such as laminating poly(vinyl chloride), polyester, etc., for forming decals and other related products. Most of the pressure sensitive adhesives 15 have been solvent based but in recent years government regulations have forced the industry to develop environmentally friendly aqueous based pressure sensitive adhesives.
Aqueous based pressure sensitive adhesives comprised of polymerized monomer units of vinyl acetate, ethylene, and/or acrylic esters, etc. have been inferior to 20 the solvent based pressure sensitive adhesives in that they do not have sufficient I CA 02220206 1997-11-0~
adhesive power to low surface energy substrates nor do they have good water resistance and so forth.
The following patents describe a variety of emulsion polymers incorporating vinyl esters and/or emulsion based pressure sensitive adhesives:
U.S. 5,461,103 discloses aqueous based pressure sensitive adhesive emulsions having an ability to coat low energy surfaces without retracting or cratering. The emulsion polymers are prepared by a two stage emulsion polymerization process, the first stage resulting in the formation of an alkali insoluble polymeric system incorporating acid functional groups and polymerized hydrophobic monomer units, e.g., C4 12 alkyl 10 acrylates and the second stage incorporating monomer units suited for the manufacture of pressure sensitive adhesives, e.g., acrylic and methacrylic esters, vinyl esters of C2-5 carboxylic acids, e.g., vinyl acetate and vinyl propionate and the like.
U.S. 4,923,919 discloses pressure sensitive adhesive emulsions based on acrylic polymers that contain at least 40% by weight of an alkyl acrylate and a support resin that 15 is alkali soluble. The support resin contains polymerizable carboxylic acid anhydride groups with the polymeric resin having a number average molecular weight of from1000-15,000. Typically the support resins are based on vinyl monomers such as acrylic and methacrylic acid esters, styrene and combinations thereof.
U.S. 4,322,516 discloses aqueous based pressure sensitive adhesives formed 20 from ethylene units, acrylic ester units, vinyl acetate units, acrylamide units and other olefinically unsaturated monomers. Tackifying agents are incorporated into the ethylene based pressure sensitive adhesives.
U.S. 4,939,190 discloses emulsion type pressure sensitive adhesives wherein the emulsions are prepared in a staged procedure, the first stage comprising 25 polymerizing an ethylenically unsaturated monomer such as styrene, acrylonitrile and/or CA 02220206 1997-11-0~ 1 -(meth)acrylates in the presence of a tackifier resin and a second stage comprising polymerizing alkyl acrylates having at least 4 carbon atoms in the presence of the first stage polymer.
U.S. 5,276,084 discloses aqueous based pressure sensitive adhesives based on 5 polymers comprising vinyl acetate, ethylene, alkyl acrylates dialkyl maleate and fumarates, hydroxyalkyl acrylates, acrylamides and unsaturated carboxylic acids such as acrylic acid.
U.S. 3,697,618 discloses acrylic pressure sensitive adhesives incorporating a vinyl ester of a carboxylic acid, e.g., vinyl acetate, a lower alkyl acrylate and a 10 copolymerizable alpha, beta-ethylenically unsaturated dicarboxylic acid or anhydride.
U.S. 3,562,229 discloses solvent polymerized copolymers of ethylene and vinyl esters where the vinyl esters are derived from long chain carboxylic acids, e.g., versatic acid which are mixtures of C9-11 carboxylic acids. Isotridecanoic and isononanoic are representative acids. The solvent based polymers incorporating vinyl esters of versatic 15 acid were alleged to be superior to polymers incorporating vinyl laurate which has the same number of carbon atoms.
U.S. 3,294,727 discloses polymerizing vinyl esters of saturated monocarboxylic acids to form emulsions having suitability for producing freeze-thaw stable paints. The preferred saturated aliphatic monocarboxylic acids for forming vinyl esters are based 20 upon compounds of the formula:
wherein R1 and R2 are alkyl radicals of normal, branched, or cyclic structure and R3 represents a hydrogen or hydrocarbyl radical. The carboxylic acids have from about CA 02220206 1997-11-0~ ~
9-19 carbon atoms. Representative copolymers are comprised of polymerized units of vinyl acetate and/or acrylic acid and the representative vinyl esters.
U.S. 3,669,942 discloses solvent based polymers comprising a vinyl ester of an alpha-branched, saturated aliphatic monocarboxylic acid having from 5-20 carbon atoms 5 and an alpha, beta-ethylenically unsaturated carboxylic acid having 3-5 carbon atoms, a monovinyl aromatic compound and acrylic acid esters including hydroxyalkyl acrylate esters. The compositions are useful as water thinnable paint binders.
U.S. 3,654,213 discloses tacky pressure sensitive adhesives based on interpolymers of vinyl esters and alkyl acrylates, the interpolymers being dissolved at 10 high solids content in organic solvents. Representative interpolymers are based upon vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl valerate with vinyl acetate being preferred. Other monomers which can be incorporated into the polymer include acrylic acid esters such as methyl acrylate, ethyl acrylate and so forth.
U.S. 4,322,516 discloses pressure sensitive adhesive emulsions whose copolymers comprise:
(a) 10-30 wt% ethylene, (b) 29-69 wt% acrylic acid esters of alcohols, (c) 20-55 wt% vinyl acetate, (d) 0.2-8 wt% (meth)acrylamide, and (e) 0-12 wt% other olefinically unsaturated comonomers.
BRIEF SUMMARY OF THE INVENTION
The present invention is directed to improved aqueous based pressure sensitive adhesive emulsion polymers. Conventional aqueous emulsion based pressure sensitive 25 adhesives are comprised of a copolymer comprised of polymerized units of acrylic esters CA 02220206 1997-11-0~ ?
and ethylenically unsaturated monomers, the copolymer having a Tg of from -15 to-70~C. The improvement in the aqueous based, emulsion polymerized pressure sensitive adhesives resides in the incorporation of a vinyl ester of a Ca 13 ne~acid into the copolymers present in the pressure sensitive adhesives. Such copolymers incorporate a vinyl ester formed from a mixture of propylene oligomers and such vinyl ester is represented by the chemical formula:
C8.,3H17 27CO2CH=CH2 There are significant advantages associated with the above aqueous based pressure sensitive adhesive emulsions and the process for producing these emulsions 10 and these advantages include:
~ an ability to provide enhanced properties to pressure sensitive adhesives through the methyl group rich vinyl ester mixture which exhibits a lower solubility parameter compared to the corresponding linear alkyl vinyl esters;
~ an ability to provide enhanced properties to pressure sensitive adhesives through the ability of the vinyl ester monomer to undergo emulsion polymerization with a variety of olefinically unsaturated comonomers;
~ an ability to form an excellent bond and enhanced resistance to plasticizer migration with plasticized poly(vinyl chloride);
~ an ability to generate a class of pressure sensitive adhesives which have an excellent balance of peel and cohesive strength;
~ an ability to provide enhanced thermal and hydrolytic stability to emulsion based pressure sensitive adhesives as compared to aqueous based vinyl acetate counterparts; and, - - -CA 02220206 1997-11-0~
an ability to provide enhanced properties to pressure sensitive adhesives through binding to lower surface energy surfaces of lower polarity, such as polyethylene, by virtue of stronger bonding of the copolymers .
DETAILED DESCRIPTION OF THE lNVENTlON
Emulsion polymerization of ethylenically unsaturated monomers such as lower 10 alkyl acrylates and vinyl esters, typically represented by vinyl acetate or vinyl propionate, to produce aqueous based pressure sensitive adhesive emulsions containing vinyl copolymer is well known. The improvement to emulsion based pressure sensitive adhesives containing vinyl copolymer incorporating polymerized units of ethylenically unsaturated monomer units resides in the incorporation of a vinyl ester of a neo-acid 15 derived from a propylene oligomer feedstock into the vinyl copolymer.
The vinyl ester of a neo-acid of propylene oligomers or mixture thereof is incorporated into the vinyl polymer is comprised of the vinyl ester of a single or mixture of tri- and tetramers of propylene which have been converted to the corresponding single or mixture of C8 ,3 neo-acids. These esters typically are prepared by first 20 converting the tri and tetramers of propylene to the corresponding acids and then converting the corresponding those neo-acids to the vinyl esters. The vinylation of those acids can be achieved either by transvinylation with vinyl acetate or by catalytic addition of the neo-acids to acetylene. Some of the vinyl esters may be represented by a singular neo-acid, but generally the vinyl esters of the neo-acids are present as a 25 mixture.
CA 02220206 l997-ll-0~ j Aqueous based pressure sensitive adhesive emulsions are based on emulsions which comprise a colloidal dispersion of the vinyl copolymer in water. The copolymers present in the pressure sensitive adhesives are typically derived from the following monomers and within the percentage proportions listed below:
(a) 5-40 wt% of a vinyl ester of a C8 13 ne~acid, preferably 15 to 30 - wt%;
(b) 30-80 wt% of a C,-,2 alkyl ester of acrylic or methacrylic acid, preferably 40 to 70 wt%, (c) 0-20% wt% of a vinyl ester of saturated aliphatic acids, preferably 0 to 10%;
(d) 0-30 wt% ethylene, styrene or butadiene, preferably 0 to 20 wt%;
(e) 0-20 wt% di-(C1 ~3)alkyl maleate/fumarate, preferably 0 to 10 wt%;
(f) 0-5 wt% of a hydroxyalkyl (meth)acrylate;
(g) 0-5 wt% (meth)acrylamide; and, (h) 0-10 wt% alpha, beta-ethylenically unsaturated monocarboxylic acid.
A variety of other comonomers, e.g., other ethylenically unsaturated monomers sometimes employed in the formation of the aqueous based pressure sensitive emulsions can be copolymerized with the vinyl ester of a ne~acid to form adhesives.
20 For example, C,.8 alkyl vinyl ethers, vinyl chloride, vinylidene chloride, nitriles, carboxylic amides such as N-vinylformamide and N-vinylacetamide, acrylonitrile and methacrylonitrile to produce a variety of polymers. Examples of useful alkyl vinyl ethers are methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, tert-butyl vinyl ether and n- and isobutyl vinyl ether.
~ CA 02220206 1997-11-05 Component (a) monomers which are the vinyl esters of C813 neo-acids and utilized in producing the improved pressure sensitive adhesives have been defined.
Component (b) monomers utilized in producing the pressure sensitive adhesives containing the vinyl esters of C8 ,3 neo-acids are alkyl esters of acrylic or methacrylic 5 acid. These are esters of acrylic acid or methacrylic acid and a C1 1z alcohol. Examples of suitable alcohols for the preparation of these esters are methanol, ethanol, propanol, isopropanol, n-, iso- and tert-butyl alcohol, neopentyl alcohol, 2-ethyl-hexanol, n-octanol, dodecanol, palmityl alcohol and stearyl alcohol. Specific examples of unsaturated alkyl acrylate monomers include methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl 10 acrylate 2-ethylhexyl acrylate, isooctyl acrylate, isodecyl acrylate and the like.
Component (c) monomers which may be used in forming emulsion polymers for pressure sensitive adhesives can include other vinyl esters than the vinyl esters of neo-acids. Some of the more common vinyl esters used in the polymer synthesis include C3.18 alkanoic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate 15 and the like. These esters, and particularly the lower alkyl esters, may detract from the overall properties of the pressure sensitive emulsion imparted by the vinyl ester of the C8 13 neo-acids.
Component (d) monomers used as a fraction of the polymers utilized in forming emulsion polymers for pressure sensitive adhesives can include hydrocarbon monomers 20 such as ethylene, styrene, butadiene.
Component (e) monomers used in forming many of the pressure sensitive adhesives include an alkyl maleate or fumarate, for the purpose of providing enhanced tack. etc. One may suitably use the diesters of maleic acid or fumaric acid, the diester being formed by the reaction of the acid with a C1 13, such as, n-octyl alcohol, isooctyl -CA 02220206 1997-1l o~; 1 alcohol, butyl alcohol, isobutyl alcohol, methyl alcohol, amyl alcohol and the like.
Preferably a C4 8, alcohol is employed.
Components (f) monomers often are incorporated into the pressure sensitive adhesive polymer. Representative monomers include hydroxyethyl acrylate, 5 hydroxyethyl methacrylate, hydroxypropyl acrylates, hydroxypropyl methacrylate, hydroxypropyl acrylates, hydroxypropyl methacrylates, hydroxybutyl acrylates and hydroxybutyl methacrylates.
Component (g) monomers often are incorporated into the copolymers at some levels. Examples of amides include acrylamide, methacrylamide and N-methylol-1 0 acrylamide.
Component (h) monomers include the alpha, beta-ethylenically unsaturated C3-6 carboxylic acids which can be incorporated into the polymer can be methacrylic acid, crotonic acid, acrylic acid and the like.
The sum of the monomers used to form the pressure sensitive copolymers is 100 15 percent. The emulsion copolymers are designed to have a Tg of less than -15~C, preferably -15 to -70~C and typically -20 to -50~C. The aqueous emulsions contain about 40 to 70 wt% solids.
The emulsion polymerization process typically involves an initial homogenization in which the monomers which include the vinyl esters of ne~acids and the other 20 monomers which are employed to form the vinyl copolymer such as C~.12 alkyl acrylates or methacrylates, vinyl acetate, dialkyl maleate/fumarate, ethylene, acrylamide and other monomers are thoroughly agitated. If ethylene is added to the reactor to form a copolymer, the reactor is pressured to the working pressure to effect solution of the ethylene in the monomers. Then, the reaction medium is gradually heated to CA 02220206 1997-11-0~ ) polymerization temperature. The homogenization period is followed by a polymerization period during which the free radical source is added incrementally.
Various free-radical forming catalysts such as peroxide compounds can be used in carrying out the emulsion polymerization of the monomers. Combination-type catalysts employing both reducing agents and oxidizing agents can also be used. The use of this type of combined catalyst is generally referred to in the art as "redox polymerization" or "redox system." The reducing agent is also often referred to as an activator and the oxidizing agent as an initiator. Suitable reducing agents or activators include bisulfites, sulfoxylates, or other compounds having reducing properties such as ferrous salts, and tertiary aromatic amines, e.g., N,N-dimethylaniline. The oxidizing agents or initiators include hydrogen peroxide, organic peroxides such as benzoyl peroxide, t-butyl hydroperoxide and the like, persulfates, such as ammonium or potassium persulfate, perborates, and the like. A specific combination-type catalyst or redox system which can be used is hydrogen peroxide and sodium formaldehyde 1 5 sulfoxylate.
The initiator is employed in the amount of 0.1 to 2%, preferably 0.25 to 0.75%, based on the weight of monomers introduced into the reactor. The activator is ordinarily added as an aqueous solution and the amount of activator is generally from 0.25 to 1 times the amount of initiator.
A wide variety of nonionic, anionic and cationic surfactants can be used to stabilize the emulsion in emulsion polymerization processes. Suitable nonionic emulsifying agents include polyoxyethylene condensates. Polyoxyethylene condensates may be represented by the general formula:
R ( CH2--CH2-O )nH
CA 02220206 1997-11-0~ , where R is the residue of a fatty alcohol containing 10-18 carbon atoms, an alkylphenol, a fatty acid containing from 10-18 carbon atoms, an amide, an amine, or a mercaptan, and where n is an integer of 1 or above. Some specific examples of polyoxyethylene condensates which can be used include polyoxyethylene aliphatic ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene hydroabietyl ether and the like; polyoxyethylene alkaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether and the like; polyoxyethylene esters of higher fatty acids such as polyoxyethylene laurate, polyoxyethylene oleate and the like as well as condensates of ethylene oxide with resin acids and tall oil acids; polyoxyethylene 10 amide and amine condensates such as N-polyoxyethylene lauramide, and N-lauryl-N-polyoxyethylene amine and the like; and polyoxyethylene thioethers such as polyoxyethylene n-dodecyl thioether. Other suitable nonionic surfactants are alkylarylethoxylate alcohols, alkylethoxylate alcohol, ethoxypropoxylate, alcohols from ethylene oxide and/or propylene oxide reaction products, and the like.
Another class of nonionic surfactants are sold under the Igepal trademark. One example within this class is a polyoxyethylene nonylphenyl ether having a cloud point of between 126 and 133~F and marketed under the trade mark "Igepal C0-630"; another is polyoxyethylene nonylphenyl ether having a cloud point above 212~F and marketed under the trade mark "Igepal C0-887."
Examples of anionic surfactants include metal or ammonium salts of long chain alkyl sulfates and the likes; metal or ammonium salts of alkylarylethoxylated sulfates or sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkylarylsulfonates, alkyl phosphates, etc.
A protective colloid also can be used in the polymerization mixture as a 25 stabilizing agent. Various colloids and amounts conventionally used in emulsion CA 02220206 1997-11-0~ , polymerization can be incorporated into the latices as desired and in combination with the surfactants. Representative colloids which can be used include poly(vinyl alcohol), partially-acetylated poly(vinyl alcohol), e.g., up to 50% acetylated, casein, hydroxyethyl starch, carboxymethylcellulose, gum arabic, and the like.
The concentration range of the total amount of emulsifying agents used in emulsion polymerization is from 0.1 to 10% based on the aqueous phase of the latex regardless of the solids content. The stabilizers employed are, in part, governed by the use to which the copolymer latex is to be put. By utilizing appropriate levels of surfactant and/or protective colloid, one can obtain latex polymer particles having a variety of 10 average particle size ranges and distributions.
In order to maintain the pH of the system at the desired value, there is suitably added a buffering agent of any convenient type. Any alkaline material which is compatible with the stabilizing agent can be used as the buffer. The amount of buffer is that sufficient to adjust the pH of the system within the desired range, e.g., 2.5 to 10 and 15 preferably 3.5 and 8.5. The amount of buffer is generally about 0.1 to 0.5% by weight, based on the monomers.
Reaction temperatures for emulsion polymerizing the vinyl esters of ne~acids along with other monomers are conventional. The reaction temperature can be controlled by the rate of catalyst addition and by the rate of the heat dissipation therefrom. Generally, it is advantageous to maintain a temperature from about 50 to 90~C. While temperatures as low as 0~C can be used, economically, the lower temperature limit is about 40~C.
The reaction time will also vary depending upon other variables such as the temperature, the catalyst, and the desired extent of the polymerization. It is generally desirable to continue the reaction until less than 0.1% of the vinyl ester remains - ' , CA 02220206 1997-11-0~ , unreacted. Under these circumstances, a reaction time of about 4 hours has been found to be generally sufficient for complete polymerization, but reaction times ranging from 2 to 10 hours have been used, and other reaction times can be employed, if desired.
The following examples are provided to illustrate various embodiments of the 5 invention and are not intended to restrict the scope thereof.
Example 1 Preparation of Water Borne Pressure Sensitive Adhesives of Mixed Vinyl Ne~C813 Esters, 2-EHA, Methyl Methacrylate and Acrylic Acid The mixed vinyl ne~C8.13 esters employed in forming the pressure sensitive adhesive emulsions are formed from a propylene oligomer feedstock which is comprised predominately of propylene trimers and tetramers.
To a 2-liter resin reactor are added the following initial reaction mixture comprising 200g of deionized water, 1.28g of sodium citrate and 133g of a pre-emulsion monomer mixture of the following composition:
Deionized water 288.00 g Abex EP-120 (30% active)* 8.23 g Igepal C0-887 (70% active) 8.23 g Aerosol MA-80 (80% active) 7.20 g Vinyl ne~C8.13 ester monomer144.00 g 25.0%*
Methyl methacrylate 74.90 g 13.0%*
2-Ethylhexyl acrylate 345.60 g 60.0%*
Acrylic acid 11.52 g 2.0%*
~Abex EP-120 is the ammonium salt of an alkylphenol ethoxylated sulfate, *The percentage of each monomer listed is expressed by weight of the total monomers employed to form the copolymer in the pressure sensitive adhesive emulsion.
The initial reaction mixture is heated to 80~C under nitrogen with 150-200 rpm agitation. A 4.5 g portion of a 5% aqueous solution of sodium persulfate is added over a period of 15 min to initiate the polymerization reaction. After initiation, the additions of - - -CA 02220206 1997-11-0~ , both the pre-emulsion mixture delay-feed (6.2 g/min) and the persulfate initiator delay-feed (0.3 g/min), respectively, are begun. 755 g of the pre-emulsion mixture and 36 g of initiator solution are consumed over 150 min. An additional 5 g portion of the 5%
sodium persulfate solution is added to complete the polymerization reaction to a residual monomer value less than 1000 ppm. The copolymerization temperature is maintainedat 81-83~C. The resultant copolymer latex has 55% solids, a viscosity of 2,350 cps at 20 rpm ~RVT #3 spindle), and a pH of 2.6, a Tg = -42~C. and the particle size number values, Dn = 145 nm and particle size weight values, Dw - 163 nm.
Example 2 Preparation of Water Borne Pressure Sensitive Adhesives of Mixed Vinyl Ne~C813 Esters, Butyl Acrylate, Methyl Methacrylate and Acrylic AcidThe procedure of Example 1 was followed except for the substitution of butyl acrylate for the 2-ethylhexyl acrylate in the polymerization formulation. The resultant latex has 55% solids, a viscosity of 725 cps at 20 rpm (#3 spindle), a pH of 3.1 and a Tg of -28~C.
Example 3 Preparation of Water Borne Pressure Sensitive Adhesives of Vinyl Versatate, 2-EHA, Methyl Methacr,vlate and Acrylic Acid The procedure of Example 1 was followed except for the substitution of vinyl versatate (VeoVa 10), for the mixed vinyl ne~Ca.,3 ester monomer in the polymerization formulation. The resultant VeoVa 10 ester based copolymer latex had 54.4% solids, a - viscosity of 1250 cps at 20 rpm (RVT #3 spindle), a pH of 2.8 and a Tg of -34~C.
CA 02220206 1997-11-0~ ~
Example 4 Preparation of Water Borne Pressure Sensitive Adhesives of Vinyl Versatate, Butyl Acrylate, Methyl Methacrylate and Acrylic Acid 5The procedure of Example 3 was followed except for the substitution of butyl acrylate for 2-ethylhexyl acrylate in the polymerization recipe. The resultant latex has 55% solids, a viscosity of 2350 cps at 20 rpm ( RVT #3 spindle), a pH of 2.6 and a Tg of -24~C .
1 0Example 5 Preparation of Water Borne Pressure Sensitive Adhesives of Vinyl 2-Ethylhexanoate, 2-EHA, Methyl Methacrylate and Acrylic Acid The procedure of Example 1 was followed except for the substitution of vinyl 2-15ethylhexanoate for the mixed ne~C8,3 ester monomer in the polymerization recipe. the purpose was to determine the influence of the more linear ester on the resulting product vis-à-vis the mixed ne~C813 ester monomer. The resultant copolymer latex has 51%solids, a viscosity of 475 cps at 20 rpm (RVT #3 spindle), a pH of 2.8 and a Tg of -39~C.
20Example 6 Preparation of Water Borne Pressure Sensitive Adhesives of Mixed Vinyl Neo~C~l3 Esters, 2-EHA, Ethylene, 2-hydroxypropyl Acrylate and Acrylic Acid To a high pressure one-gallon reactor is added a premix of the following 25ingredients:
Deionized water 720.1 g Versulf S-1333~ (40% active) 21.3 9 Versulf NOS-25 (35% active) 41.4 g Sodium vinyl sulfonate (25% active)9.5 9 Acrylic acid 14.2 g Ammonium ferrous sulfate (1 % active) 1.7 9 *Versulf S-1333 is from the sodium sulfosuccinate family.
~Versulf NOS-25 is from a sodium salt of a nonylphenol ethoxylate sulfate.
CA 02220206 1997-11-0~ ~
The pH of the premix is adjusted to 3.5 with 2.6 g of 14% aqueous ammonium hydroxide. A monomer mixture of:
580.3 9 of vinyl ne~C8.13 ester monomer and 177.7 9 of 2-ethyihexyl acrylate is subsequently added to the reactor, followed by nitrogen and ethylene purge. The reactor is then blocked off and stirred at 200 rpm. When the reactor temperature reaches 50~C, ethylene is charged in and equilibrated to 840 psig for 5 min and shut off.
The agitator speed is increased to 800 rpm. A separate feed of initiator and activator 10 solutions are added at 0.4 ml/min. to initiate the polymerization reaction. The composition of the delay feeds are listed as follows:
Initiator solution: Amount (q) Ammonium persulfate 15.0 NH40H (28%) 9-0 Deionized water 190.0 Activator solution Sodium formaldehyde sulfoxylate7.5 Deionized water 200.0 Monomer mixture 2-Ethylhexyl acrylate 656.1 Acrylic acid 22.5 2-Hydroxypropyl acrylate 77.0 SurfactanVemulsifier feed Versulf NOS-25 %35% active) 360 Deionized water 110 After the initiation, the monomer and surfactant delay feeds are started at a rate of 3.2 ml/min and 0.8 ml/min respectively. After 2.5 hr, the monomer delay feed is reduced to 2.4 ml/min and the surfactant feed is reduced to 0.6 ml/min. After four hr, a total of 755 g of monomer and 175 ml of surfactant are added. The initiator and activator delay solutions are continued until the residual monomer value is at or less than 1000 ppm. At the end of initiator and activator delay, the reaction mixture is cooled - - -CA 02220206 1997-11-0~ ~
to 30~C and is then transferred to the degasser to release excess ethylene pressure.
The resultant latex has 50% solids, a pH of 4.2, a viscosity of 94 cps at 20 rpm, a Tg of -49~C and particle size values of Dn = 176 nm and Dw = 287 nm.
Example 7 Preparation of Water Borne Pressure Sensitive Adhesives of Mixed Vinyl Ne~C8 13 Esters, Butyl Acrylate, Ethylene, 2-hydroxypropyl Acrylate and Acrylic Acid The procedure of Example 6 was followed except for the substitution of butyl acrylate for 2-ethylhexyl acrylate in the polymerization recipe. The resultant copolymer latex has 46% solids, a viscosity of 114 cps at 20 rpm (RVT #3 spindle), a pH of 4.4 and a Tg of -43~C.
Example 8 Preparation of Water Borne Pressure Sensitive Adhesives of Mixed Vinyl Ne~C8,3 Esters, 2-EHA, Ethylene, Vinyl Acetate, Methyl Methacrylate and Acrylic Acid To a 2-liter resin reactor, equipped with an agitator, condenser and external thermal controls are added the following initial reaction mixture comprising 320 g of deionized water, 1.6 g of sodium citrate and 166.4 g of a pre-emulsion mixture of the following composition:
Wt%
Deionized water 360.0 g Abex EP-120 (30% active), 10.29 g Igepal C0-887 (70% active) 10.29 g Aerosol MA-80 (80% active) 9.0 g vinyl acetate 36.0 g 5%
vinyl ne~C8 ,3 monomer 144.0 g 20%
methyl methacrylate 93.6 g 13%
2-ethylhexyl acrylate 432.0 g 60%
acrylicacid 14.4 g 2%
The initial reaction mixture is heated to 80~C under nitrogen atmosphere with agitation of 150-200 rpm. The polymerization reaction is initiated by addition of 3.4 g of CA 02220206 1997-11-0~
a 5% sodium persulfate solution over a period of 14 minutes. After initiation, both the pre-emulsion delay feed (6.2 g/min) and the initiator feed (0.3 g/min), respectively are begun. At the end of 150 minutes, a total of 926 g of pre-emulsion mixture and 45 g of the 5% sodium persulfate are consumed. Additional 3 g of the sodium persulfate solution 5 is added to reduce the residual monomer below the value of 1,000 ppm determined by GC, The polymerization temperature is maintained at 80-830C. The resultant copolymer latex has a solids of 49%, a viscosity of 160 cps at 20 rpm (RVT #2 spindle), and a pH of 3.5, a Tg = -37~C. and particle size values of Dn = 157 nm and Dw = 169 nm.
10Example 9 Performance Evaluation of Pressure Sensitive Adhesive on Polyester The emulsions of Examples 1-8, when coated onto 50 ~Lm polyester film (Mylar) 15at a dry weight of 22-24 g/m2, after drying for 5 min at 110~C, gives the pressure sensitive adhesive properties (peel, tack and shear) measured by the following Pressure Sensitive Tape Council (PSTC) methods: The results are reported in Table 1.
Pressure Sensitive TaPe Council (PSTC) Methods 20~ 180~ angle peel adhesion is measured, after 20 minute dwell time, for a 25.4 mm wide strip on stainless steel at 23~C and 50% relative humidity condition at a peel rate of 30.48 cm/min (12 intmin, PSTC-1).
~ Loop tack is measured by an instantaneous contact of a 25.4 mm 25wide loop perpendicular to a stainless steel test panel plane of 6.45 cm2 (1 in2) area CA 02220206 1997-11-0~ ~
~ Shear is measured in terms of time required to pull a standard area of tape from a stainless steel test panel under a standard load (PSTC-7).
Table 1.
PSA Properties of Examples 1-8 Adhesion Shear (hr) Example180~ Peel (g)Loop tack (g) (1.61 cm2 x 500 g loads) - 271 953 , 25 2 135 590 400+
3 452 10 i 19 - 044 6~ 280+
- 35 63~ 7.8 6 - 80 817 2.5 The results show that the higher Tg material of Example 2 versus the lower Tg 10 material of Example 1 resulted in similar peel strength values but higher cohesive strength (shear) than the lower Tg material. Loop tack was lower which is expected from adhesives having higher shear. The vinyl versatate system of Example 3 had the best peel strength while having good shean Again, the higher Tg of Example 4 had higher shear than the Example 3 product. Peel was noticeably effected but remained good 15 relative to commercial systems. Example 5 shows the deleterious effect on cohesive strength when a higher, linear vinyl ester is substituted for the vinyl neo-C8 l3 esters.
Pressure sensitive adhesives incorporating ethylene had significantly lower shear as would be expected because of the softness imparted by the ethylene. However, with regard to comparable ethylene based pressure sensitive adhesives, those values are 20 good. Example 8 shows that replacing up to 5% of the vinyl ne~C8.,3 esters with a lower aliphatic vinyl ester, viz. vinyl acetate can adversely affect peel and loop tack. Although shear is somewhat better in the vinyl acetate containing adhesive.
- - - - - - - - -CA 02220206 1997-11-0~
Example 10 Performance Evaluation of Pressure Sensitive Adhesive on Plasticized PVC~
The pressure sensitive adhesive constructions are prepared by coating the liquiddispersions on a siliconized release liner, dried and laminated onto the plasticized flexible PVC film with a coatweight of 27-29 g/m . The pressure sensitive performance properties for both the initial samples and the thermally aged (70~C for 7 days on 10 siliconized liner) samples are presented in Table 2:
Table 2 180~ Peel (g)180~ Peel (g) Loop EmulsionInitial Thermal Aged Tack Shear (hr) (g) 20 min 24hr (6.45 cm2 Dwell Dwell On Liner x 2 kg loads) Examp e 1 2497 3133 2225 1226 46 Examp e 2 2043 2633 999 953 292 Examp e 3 2224 2769 1680 15~4 81 FL-1625* 1571 2256 459 1166 9 * Flexbond 1625 emulsion is a commercial, water based, acrylic pressure sensitive adhesive.
The results show excellent peel and cohesive strength on plasticized PVC. An important feature is the 180~ peel, thermal aged. The emulsions having vinyl polymers incorporating the C8.13 vinyl esters of ne~acids of the formula C813H1,27C02CH=CH2 resulted in substantially better adhesion and resistance to plasticizer migration in the PVC as compared to the commercial adhesive.
Example 11 Comparable PSA Performance vs Commercial Products On Plasticized Flexible Poly(vinyl chloride) Film CA 02220206 1997-11-0~ 1 Similar to Example 10, pressure sensitive adhesive constructions were prepared by coating the liquid dispersion on a siliconized release liner, dried and laminated onto the plasticized flexible poly(vinyl chloride) film (FW 400 vinyl film) with a coat weight of 27 g/m2. The pressure sensitive properties and the thermally aged (70~C for 7 days on 5 siliconized liner) for the Examples 1 and 4 adhesives, two water based commercial acrylic emulsions and one commercial solvent acrylic based pressure sensitive adhesive were determined and the results are presented in Table 3.
Table 3 Product Peel Adhesion Peel Adhesion Initial (g) Therm l Aged (g) Example ~ 2315 - 498 Example ~ 1998 - 317 Commerc al 1498 272 Acrylic Emulsion 1 Commercial 1725 817 Acrylic Emulsion 2 Commercial 1998 999 solvent Acrylic based The results show superior peel and thermal aged properties for the emulsion based pressure sensitive adhesives in PVC films incorporating the vinyl neo-C8 ,3 esters of the formula C8 13H,7 27CO2CH=CH2 as compared to commercial water based presure sensitive adhesive emulsions and the commercial solvent based pressure sensitive 1 5 adhesive.
N:\RL~\1 86P5499.apl
Acrylic acid 11.52 g 2.0%*
~Abex EP-120 is the ammonium salt of an alkylphenol ethoxylated sulfate, *The percentage of each monomer listed is expressed by weight of the total monomers employed to form the copolymer in the pressure sensitive adhesive emulsion.
The initial reaction mixture is heated to 80~C under nitrogen with 150-200 rpm agitation. A 4.5 g portion of a 5% aqueous solution of sodium persulfate is added over a period of 15 min to initiate the polymerization reaction. After initiation, the additions of - - -CA 02220206 1997-11-0~ , both the pre-emulsion mixture delay-feed (6.2 g/min) and the persulfate initiator delay-feed (0.3 g/min), respectively, are begun. 755 g of the pre-emulsion mixture and 36 g of initiator solution are consumed over 150 min. An additional 5 g portion of the 5%
sodium persulfate solution is added to complete the polymerization reaction to a residual monomer value less than 1000 ppm. The copolymerization temperature is maintainedat 81-83~C. The resultant copolymer latex has 55% solids, a viscosity of 2,350 cps at 20 rpm ~RVT #3 spindle), and a pH of 2.6, a Tg = -42~C. and the particle size number values, Dn = 145 nm and particle size weight values, Dw - 163 nm.
Example 2 Preparation of Water Borne Pressure Sensitive Adhesives of Mixed Vinyl Ne~C813 Esters, Butyl Acrylate, Methyl Methacrylate and Acrylic AcidThe procedure of Example 1 was followed except for the substitution of butyl acrylate for the 2-ethylhexyl acrylate in the polymerization formulation. The resultant latex has 55% solids, a viscosity of 725 cps at 20 rpm (#3 spindle), a pH of 3.1 and a Tg of -28~C.
Example 3 Preparation of Water Borne Pressure Sensitive Adhesives of Vinyl Versatate, 2-EHA, Methyl Methacr,vlate and Acrylic Acid The procedure of Example 1 was followed except for the substitution of vinyl versatate (VeoVa 10), for the mixed vinyl ne~Ca.,3 ester monomer in the polymerization formulation. The resultant VeoVa 10 ester based copolymer latex had 54.4% solids, a - viscosity of 1250 cps at 20 rpm (RVT #3 spindle), a pH of 2.8 and a Tg of -34~C.
CA 02220206 1997-11-0~ ~
Example 4 Preparation of Water Borne Pressure Sensitive Adhesives of Vinyl Versatate, Butyl Acrylate, Methyl Methacrylate and Acrylic Acid 5The procedure of Example 3 was followed except for the substitution of butyl acrylate for 2-ethylhexyl acrylate in the polymerization recipe. The resultant latex has 55% solids, a viscosity of 2350 cps at 20 rpm ( RVT #3 spindle), a pH of 2.6 and a Tg of -24~C .
1 0Example 5 Preparation of Water Borne Pressure Sensitive Adhesives of Vinyl 2-Ethylhexanoate, 2-EHA, Methyl Methacrylate and Acrylic Acid The procedure of Example 1 was followed except for the substitution of vinyl 2-15ethylhexanoate for the mixed ne~C8,3 ester monomer in the polymerization recipe. the purpose was to determine the influence of the more linear ester on the resulting product vis-à-vis the mixed ne~C813 ester monomer. The resultant copolymer latex has 51%solids, a viscosity of 475 cps at 20 rpm (RVT #3 spindle), a pH of 2.8 and a Tg of -39~C.
20Example 6 Preparation of Water Borne Pressure Sensitive Adhesives of Mixed Vinyl Neo~C~l3 Esters, 2-EHA, Ethylene, 2-hydroxypropyl Acrylate and Acrylic Acid To a high pressure one-gallon reactor is added a premix of the following 25ingredients:
Deionized water 720.1 g Versulf S-1333~ (40% active) 21.3 9 Versulf NOS-25 (35% active) 41.4 g Sodium vinyl sulfonate (25% active)9.5 9 Acrylic acid 14.2 g Ammonium ferrous sulfate (1 % active) 1.7 9 *Versulf S-1333 is from the sodium sulfosuccinate family.
~Versulf NOS-25 is from a sodium salt of a nonylphenol ethoxylate sulfate.
CA 02220206 1997-11-0~ ~
The pH of the premix is adjusted to 3.5 with 2.6 g of 14% aqueous ammonium hydroxide. A monomer mixture of:
580.3 9 of vinyl ne~C8.13 ester monomer and 177.7 9 of 2-ethyihexyl acrylate is subsequently added to the reactor, followed by nitrogen and ethylene purge. The reactor is then blocked off and stirred at 200 rpm. When the reactor temperature reaches 50~C, ethylene is charged in and equilibrated to 840 psig for 5 min and shut off.
The agitator speed is increased to 800 rpm. A separate feed of initiator and activator 10 solutions are added at 0.4 ml/min. to initiate the polymerization reaction. The composition of the delay feeds are listed as follows:
Initiator solution: Amount (q) Ammonium persulfate 15.0 NH40H (28%) 9-0 Deionized water 190.0 Activator solution Sodium formaldehyde sulfoxylate7.5 Deionized water 200.0 Monomer mixture 2-Ethylhexyl acrylate 656.1 Acrylic acid 22.5 2-Hydroxypropyl acrylate 77.0 SurfactanVemulsifier feed Versulf NOS-25 %35% active) 360 Deionized water 110 After the initiation, the monomer and surfactant delay feeds are started at a rate of 3.2 ml/min and 0.8 ml/min respectively. After 2.5 hr, the monomer delay feed is reduced to 2.4 ml/min and the surfactant feed is reduced to 0.6 ml/min. After four hr, a total of 755 g of monomer and 175 ml of surfactant are added. The initiator and activator delay solutions are continued until the residual monomer value is at or less than 1000 ppm. At the end of initiator and activator delay, the reaction mixture is cooled - - -CA 02220206 1997-11-0~ ~
to 30~C and is then transferred to the degasser to release excess ethylene pressure.
The resultant latex has 50% solids, a pH of 4.2, a viscosity of 94 cps at 20 rpm, a Tg of -49~C and particle size values of Dn = 176 nm and Dw = 287 nm.
Example 7 Preparation of Water Borne Pressure Sensitive Adhesives of Mixed Vinyl Ne~C8 13 Esters, Butyl Acrylate, Ethylene, 2-hydroxypropyl Acrylate and Acrylic Acid The procedure of Example 6 was followed except for the substitution of butyl acrylate for 2-ethylhexyl acrylate in the polymerization recipe. The resultant copolymer latex has 46% solids, a viscosity of 114 cps at 20 rpm (RVT #3 spindle), a pH of 4.4 and a Tg of -43~C.
Example 8 Preparation of Water Borne Pressure Sensitive Adhesives of Mixed Vinyl Ne~C8,3 Esters, 2-EHA, Ethylene, Vinyl Acetate, Methyl Methacrylate and Acrylic Acid To a 2-liter resin reactor, equipped with an agitator, condenser and external thermal controls are added the following initial reaction mixture comprising 320 g of deionized water, 1.6 g of sodium citrate and 166.4 g of a pre-emulsion mixture of the following composition:
Wt%
Deionized water 360.0 g Abex EP-120 (30% active), 10.29 g Igepal C0-887 (70% active) 10.29 g Aerosol MA-80 (80% active) 9.0 g vinyl acetate 36.0 g 5%
vinyl ne~C8 ,3 monomer 144.0 g 20%
methyl methacrylate 93.6 g 13%
2-ethylhexyl acrylate 432.0 g 60%
acrylicacid 14.4 g 2%
The initial reaction mixture is heated to 80~C under nitrogen atmosphere with agitation of 150-200 rpm. The polymerization reaction is initiated by addition of 3.4 g of CA 02220206 1997-11-0~
a 5% sodium persulfate solution over a period of 14 minutes. After initiation, both the pre-emulsion delay feed (6.2 g/min) and the initiator feed (0.3 g/min), respectively are begun. At the end of 150 minutes, a total of 926 g of pre-emulsion mixture and 45 g of the 5% sodium persulfate are consumed. Additional 3 g of the sodium persulfate solution 5 is added to reduce the residual monomer below the value of 1,000 ppm determined by GC, The polymerization temperature is maintained at 80-830C. The resultant copolymer latex has a solids of 49%, a viscosity of 160 cps at 20 rpm (RVT #2 spindle), and a pH of 3.5, a Tg = -37~C. and particle size values of Dn = 157 nm and Dw = 169 nm.
10Example 9 Performance Evaluation of Pressure Sensitive Adhesive on Polyester The emulsions of Examples 1-8, when coated onto 50 ~Lm polyester film (Mylar) 15at a dry weight of 22-24 g/m2, after drying for 5 min at 110~C, gives the pressure sensitive adhesive properties (peel, tack and shear) measured by the following Pressure Sensitive Tape Council (PSTC) methods: The results are reported in Table 1.
Pressure Sensitive TaPe Council (PSTC) Methods 20~ 180~ angle peel adhesion is measured, after 20 minute dwell time, for a 25.4 mm wide strip on stainless steel at 23~C and 50% relative humidity condition at a peel rate of 30.48 cm/min (12 intmin, PSTC-1).
~ Loop tack is measured by an instantaneous contact of a 25.4 mm 25wide loop perpendicular to a stainless steel test panel plane of 6.45 cm2 (1 in2) area CA 02220206 1997-11-0~ ~
~ Shear is measured in terms of time required to pull a standard area of tape from a stainless steel test panel under a standard load (PSTC-7).
Table 1.
PSA Properties of Examples 1-8 Adhesion Shear (hr) Example180~ Peel (g)Loop tack (g) (1.61 cm2 x 500 g loads) - 271 953 , 25 2 135 590 400+
3 452 10 i 19 - 044 6~ 280+
- 35 63~ 7.8 6 - 80 817 2.5 The results show that the higher Tg material of Example 2 versus the lower Tg 10 material of Example 1 resulted in similar peel strength values but higher cohesive strength (shear) than the lower Tg material. Loop tack was lower which is expected from adhesives having higher shear. The vinyl versatate system of Example 3 had the best peel strength while having good shean Again, the higher Tg of Example 4 had higher shear than the Example 3 product. Peel was noticeably effected but remained good 15 relative to commercial systems. Example 5 shows the deleterious effect on cohesive strength when a higher, linear vinyl ester is substituted for the vinyl neo-C8 l3 esters.
Pressure sensitive adhesives incorporating ethylene had significantly lower shear as would be expected because of the softness imparted by the ethylene. However, with regard to comparable ethylene based pressure sensitive adhesives, those values are 20 good. Example 8 shows that replacing up to 5% of the vinyl ne~C8.,3 esters with a lower aliphatic vinyl ester, viz. vinyl acetate can adversely affect peel and loop tack. Although shear is somewhat better in the vinyl acetate containing adhesive.
- - - - - - - - -CA 02220206 1997-11-0~
Example 10 Performance Evaluation of Pressure Sensitive Adhesive on Plasticized PVC~
The pressure sensitive adhesive constructions are prepared by coating the liquiddispersions on a siliconized release liner, dried and laminated onto the plasticized flexible PVC film with a coatweight of 27-29 g/m . The pressure sensitive performance properties for both the initial samples and the thermally aged (70~C for 7 days on 10 siliconized liner) samples are presented in Table 2:
Table 2 180~ Peel (g)180~ Peel (g) Loop EmulsionInitial Thermal Aged Tack Shear (hr) (g) 20 min 24hr (6.45 cm2 Dwell Dwell On Liner x 2 kg loads) Examp e 1 2497 3133 2225 1226 46 Examp e 2 2043 2633 999 953 292 Examp e 3 2224 2769 1680 15~4 81 FL-1625* 1571 2256 459 1166 9 * Flexbond 1625 emulsion is a commercial, water based, acrylic pressure sensitive adhesive.
The results show excellent peel and cohesive strength on plasticized PVC. An important feature is the 180~ peel, thermal aged. The emulsions having vinyl polymers incorporating the C8.13 vinyl esters of ne~acids of the formula C813H1,27C02CH=CH2 resulted in substantially better adhesion and resistance to plasticizer migration in the PVC as compared to the commercial adhesive.
Example 11 Comparable PSA Performance vs Commercial Products On Plasticized Flexible Poly(vinyl chloride) Film CA 02220206 1997-11-0~ 1 Similar to Example 10, pressure sensitive adhesive constructions were prepared by coating the liquid dispersion on a siliconized release liner, dried and laminated onto the plasticized flexible poly(vinyl chloride) film (FW 400 vinyl film) with a coat weight of 27 g/m2. The pressure sensitive properties and the thermally aged (70~C for 7 days on 5 siliconized liner) for the Examples 1 and 4 adhesives, two water based commercial acrylic emulsions and one commercial solvent acrylic based pressure sensitive adhesive were determined and the results are presented in Table 3.
Table 3 Product Peel Adhesion Peel Adhesion Initial (g) Therm l Aged (g) Example ~ 2315 - 498 Example ~ 1998 - 317 Commerc al 1498 272 Acrylic Emulsion 1 Commercial 1725 817 Acrylic Emulsion 2 Commercial 1998 999 solvent Acrylic based The results show superior peel and thermal aged properties for the emulsion based pressure sensitive adhesives in PVC films incorporating the vinyl neo-C8 ,3 esters of the formula C8 13H,7 27CO2CH=CH2 as compared to commercial water based presure sensitive adhesive emulsions and the commercial solvent based pressure sensitive 1 5 adhesive.
N:\RL~\1 86P5499.apl
Claims (12)
1. In an aqueous emulsion based pressure sensitive adhesive, capable of bonding to a substrate on instantaneous contact, comprised of a copolymer having polymerized units of C1-12, esters of acrylic or methacrylic acid, the improvement residing in the properties of the pressure sensitive adhesive which comprises a copolymer having a glass transition temperature of from -25 to -50°C and consisting of polymerized units of the following monomers:
(a) 5-40 wt % of a vinyl C8-13 ester of a neo-acid obtained from a feedstock of propylene oligomer;
(b) 30-80 wt % of a mixture of methyl methacrylate and at least one other monomer selected from the group consisting of
(a) 5-40 wt % of a vinyl C8-13 ester of a neo-acid obtained from a feedstock of propylene oligomer;
(b) 30-80 wt % of a mixture of methyl methacrylate and at least one other monomer selected from the group consisting of
2-ethylhexyl acrylate and butyl acrylate; and (c) an alpha, beta-ethylenically unsaturated monocarboxylic acid in an amount from 2% up to 10 wt %.
2. The emulsion of claim l, wherein the mixture is present in an amount of from 40 to 70 wt %.
2. The emulsion of claim l, wherein the mixture is present in an amount of from 40 to 70 wt %.
3. The emulsion of claim 2 wherein the C8-13 vinyl ester of a neo-acid is vinyl versatate.
4. The emulsion of claim 3, wherein the copolymer consists of polymerized units of methyl methacrylate, 2-ethylhexyl acrylate, vinyl versatate and acrylic acid.
5. The emulsion of claim 2, wherein the level of vinyl C8-13 ester of a neo-acid obtained from a feedstock of propylene oligomers is from 15 to 30 wt %.
6. The emulsion of claim 5, wherein the copolymer consists of polymerized units of methyl methacrylate, 2-ethylhexyl acrylate, acrylic acid and vinyl versatate.
7. In a process for producing an aqueous emulsion based pressure sensitive adhesive comprised of a copolymer having polymerized units of C1-12 esters of acrylic or methacrylic acid and an ethylenically unsaturated monomer, which comprises forming a surfactant stabilized system and then polymerizing said C1-12 esters of acrylic or methacrylic acid and said monomer under conditions to form said copolymer, the improvement comprising incorporating as said monomers (a) 5-40 wt% of a vinyl C8-13 ester of a neo-acid obtained from a feedstock of propylene oligomer;
(b) 30-80 wt % of a mixture of methyl methacrylate and at least one other monomer selected from the group consisting of 2-ethylhexyl acrylate and butyl acrylate; and (c) an alpha, beta-ethylenically unsaturated monocarboxylic acid in an amount from 2% up to 10 wt % and wherein said copolymer has a glass transition temperature of from -25 to -50°C.
(b) 30-80 wt % of a mixture of methyl methacrylate and at least one other monomer selected from the group consisting of 2-ethylhexyl acrylate and butyl acrylate; and (c) an alpha, beta-ethylenically unsaturated monocarboxylic acid in an amount from 2% up to 10 wt % and wherein said copolymer has a glass transition temperature of from -25 to -50°C.
8. The process of claim 7, wherein the mixture is present in an amount of from 40 to 70 wt %.
9. The process of claim 8, wherein the C8-13 vinyl ester of a neo-acid is vinyl versatate.
10. The process of claim 9, wherein the copolymer consists of polymerized units of methyl methacrylate, 2-ethylhexyl acrylate, vinyl versatate and acrylic acid.
11. The process of claim 8, wherein the level of vinyl C8-13 ester of a neo-acid obtained from a feedstock of propylene oligomers is from 15 to 30 wt %.
12. The process of claim 11, wherein the copolymer consists of polymerized units of methyl methacrylate, 2-ethylhexyl, acrylic acid and vinyl versatate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/748,216 US6084024A (en) | 1996-11-12 | 1996-11-12 | Water borne pressure sensitive adhesive compositions derived from copolymers of higher vinyl esters |
| US08/748,216 | 1996-11-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2220206A1 CA2220206A1 (en) | 1998-05-12 |
| CA2220206C true CA2220206C (en) | 2002-01-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2220206 Expired - Fee Related CA2220206C (en) | 1996-11-12 | 1997-11-05 | Water borne pressure sensitive adhesive compositions derived from copolymers of higher vinyl esters |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US6084024A (en) |
| EP (2) | EP1634897A3 (en) |
| KR (1) | KR100259555B1 (en) |
| CA (1) | CA2220206C (en) |
| DE (1) | DE69737546T2 (en) |
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| DE4040959C1 (en) * | 1990-12-20 | 1992-03-12 | Wacker-Chemie Gmbh, 8000 Muenchen, De | |
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| DE4141168A1 (en) * | 1991-12-13 | 1993-06-17 | Wacker Chemie Gmbh | AQUEOUS CONTACT ADHESIVE DISPERSIONS, METHOD FOR THEIR PRODUCTION AND USE THEREOF |
| JP3550159B2 (en) * | 1992-04-10 | 2004-08-04 | 住友化学工業株式会社 | adhesive |
| TW338043B (en) * | 1992-12-11 | 1998-08-11 | Minnesota Mining & Mfg | Tacky microspheres having pendant hydrophilic polymeric or oligomeric moieties |
| WO1994014891A1 (en) * | 1992-12-18 | 1994-07-07 | Exxon Chemical Patents Inc. | Neo-acid ester acrylic adhesives |
| US5514435A (en) * | 1993-03-10 | 1996-05-07 | New Oji Paper Co., Ltd. | Adhesive sheet |
| US5461103A (en) * | 1993-05-11 | 1995-10-24 | Air Products And Chemicals, Inc. | Process for producing a stable aqueous pressure sensitive adhesive polymer emulsion |
| US5480720A (en) * | 1994-03-01 | 1996-01-02 | Rohm And Haas Company | Adhesive composition |
| US5512612A (en) * | 1994-04-04 | 1996-04-30 | Minnesota Mining And Manufacturing Company | Pressure sensitive adhesive employing a water-dispersible polymer and articles made there from |
| AU672159B2 (en) * | 1994-06-14 | 1996-09-19 | National Starch And Chemical Investment Holding Corporation | High performance PVOH stabilised EVA adhesives |
-
1996
- 1996-11-12 US US08/748,216 patent/US6084024A/en not_active Expired - Lifetime
-
1997
- 1997-11-05 CA CA 2220206 patent/CA2220206C/en not_active Expired - Fee Related
- 1997-11-10 KR KR1019970058944A patent/KR100259555B1/en active IP Right Grant
- 1997-11-11 DE DE1997637546 patent/DE69737546T2/en not_active Expired - Lifetime
- 1997-11-11 EP EP20050020957 patent/EP1634897A3/en not_active Withdrawn
- 1997-11-11 EP EP19970119725 patent/EP0841351B1/en not_active Expired - Lifetime
-
1999
- 1999-02-03 US US09/243,776 patent/US6426151B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69737546T2 (en) | 2007-12-13 |
| KR100259555B1 (en) | 2000-06-15 |
| DE69737546D1 (en) | 2007-05-16 |
| EP1634897A2 (en) | 2006-03-15 |
| CA2220206A1 (en) | 1998-05-12 |
| EP0841351A3 (en) | 1998-08-26 |
| EP0841351A2 (en) | 1998-05-13 |
| EP0841351B1 (en) | 2007-04-04 |
| KR19980042244A (en) | 1998-08-17 |
| EP1634897A3 (en) | 2006-03-22 |
| MX9708673A (en) | 1998-05-31 |
| US6426151B1 (en) | 2002-07-30 |
| US6084024A (en) | 2000-07-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
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| MKLA | Lapsed |
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