WO1990015853A1

WO1990015853A1 - Internal resin-tackified acrylic polymers containing crosslinkable comonomers

Info

Publication number: WO1990015853A1
Application number: PCT/US1990/003223
Authority: WO
Inventors: Henry Wu-Hsiang Yang
Original assignee: Exxon Chemical Patents Inc.
Priority date: 1989-06-19
Filing date: 1990-06-06
Publication date: 1990-12-27

Abstract

Acrylic copolymer compositions which contain a tackifying hydrocarbon resin and a polyfunctional crosslinking monomer and the use of such composition in pressure-sensitive adhesives are described. The tackifying hydrocarbon resin is dissolved, as is the polyfunctional monomer, in a solution of alkyl(meth)acrylate and (meth)acrylic acid monomers and is present during the polymerization of the monomers to form a tackified acrylic copolymer.

Description

INTERNAL RESIN-TACKIFIED ACRYLIC POLYMERS CONTAINING CROSSLINKABLE COMONOMERS

This Invention relates to acrylic copolymer latex compositions, useful as pressure-sensitive adhesives, which contain an Internal tackifying hydrocarbon resin having improved peel strength and shear properties obtained by including a small amount of a polyfunctional or crosslinkable comonomer in the polymerization reaction mixture. The tackifying hydrocarbon resin is dissolved in acrylic monomers to form a homogeneous solution and is present, along with the

polyfunctional or crosslinkable comonomer, during the polymerization of the monomers to form the acrylic copolymer latex.

Background of the Invention

Tackified acrylic copolymers have long been used as

pressure-sensitive. Such tackified copolymers have been prepared by adding a tackifying petroleum-based hydrocarbon resin or natural resin with an acrylic copolymer. While the resulting adhesive is often satisfactory to certain properties, such as tackiness and peel strength on substrates such as polyester or stainless steel, certain properties are found to be deficient, particularly the holding power on these substrates. Previously, increasing the peel strength of tackified acrylic copolymers to a value greater than 2.0 pounds per Inch often caused diminishing shear adhesion fail temperatures (SAFT) and holding power. It is desirable to maintain high holding power and SAFT, particularly when the pressure-sensitive adhesive is to be used to prepare an adhesive tape.

The prior art describes attempts to prepare satisfactory tackified acrylic copolymers. For example, Japanese Patent

0-59213783 teaches the preparation of a hot-melt pressure-sensitive adhesive by first heating a tackifying resin having a softening point between 60 and 200ºC to above its melting point, and adding to the hot melt a polymerization mixture of an alkyl (meth)acrylate, a functional monomer such as acrylic acid, and a radical initiator over a period of hours, with stirring, to form a pale yellow, transparent, solid hot-melt adhesive.

Japanese Patent J-59227967 discloses a hot-melt polymerization of an alkyl (meth)acrylate main monomer and a copolymerlzable functional monomer Including (meth)acrylic acid, maleic anhydride, maleic acid, and the like, where a surfactant is present with the resin during the polymerization to form a solid mass, hot-melt adhesive. In Japanese Patent 53074041, a polymerized powdery toner product is obtained by dissolving a binder resin such as a vinyl resin, acetal resin, epoxy resin or the like in a polymerizable liquid monomer such as styrene, vinyl toluene, (meth)acrylic acid or its ester, and the like, and polymerizing the monomers in bulk.

In Japanese Patent J-51125472, a petroleum resin emulsion is obtained by polymerizing vinyl monomers in the presence of petroleum resins having softening points of from 40 to 160ºC, an average molecular weight of 300 to 3000, and an acid value and saponification value of less than 1. The monomers include for example, alkyl (meth)acrylates, vinyl acetates andvinyl chlorides, styrene, acrylonltrile, and acrylic acid. The emulsified mixture is then reacted in an emulsion polymerization reaction to form a shelf-stable emulsion adhesive. The resin emulsion produced is described as having fine particle sizes and ample stability, and when cured, the films produced have excellent water resistance and gloss.

Numerous approaches have been used to produce resin emulsions. One approach is to dissolve the resin in a hydrocarbon solvent, combine the resin solution and water to form an emulsion, and strip off the solvent. Invariably some residual hydrocarbon solvent remains in the finished emulsion, which is undesirable in certain applications. This has led to the development of solvent-free dispersions (see U.S. Patent No. 2,809,948) and emulsions (see U.S. Patent No. 3,377,298) of petroleum resins. In both of these formulations, ionic emulsifiers have been utilized; in the former a mixture of cationic and non-ionic surface active agents is used to achieve a resin emulsion; and, in the latter an ionic surfactant is used in combination with an aqueous gel of a swelling earth to produce an emulsion paste of a petroleum resin.

As mentioned above, there has generally been a decrease in shear properties associated with an increase of peel strength and

tackiness. There is a need to improve peel strength of

pressure-sensitive adhesives while still maintaining a high SAFT.

My copending application Serial No. 360507, filed June 2, 1989, for "Internal Resin-Tackified Acrylics Polymers" (P-1413) deals with the problem somewhat but further improvement has been found to be desirable, particularly in improving the holding power at higher temperatures (SAFT).

Accordingly, it is an object of this invention to prepare a resin-tackified acrylic copolymer which has an improved peel strength and SAFT for application as pressure-sensitive adhesives.

It is a further object to provide a resin-tackified acrylic copolymer, wherein the tackifying resin is dissolved in the acrylic monomer solution with a crosslinkable monomer prior to the

polymerization reaction to Improve the peel strength and adhesion properties.

It is a still further objective of this Invention to cause additional Improvement In the SAFT by incorporating Into the monomer polymerization mixture a crosslinkable comonomer.

It is a still further object of this Invention to provide pressure-sensitive adhesives useful to prepare tapes and useful laminating adhesives.

Summary of the Invention

A tackified acrylic copolymer is prepared by dissolving a hydrogenated hydrocarbon resin in a liquid monomer mixture from which the copolymer is to be prepared by free radical initiated emulsion polymerization. The resin, having an aromatic content of at least 10 wt.%, is present in amounts of about 10 to about 100 parts by weight. preferably 20 to 60 parts, per 100 parts of the monomer solution. The resin Is dissolved in the monomers at ambient temperatures or higher, and the free-radical polymerization reaction is conducted, with stirring, at a temperature from about 25ºC to about 90ºC.

Included in the reaction mixture is a small, but effective amount, usually from about 0.1 wt.% to about 3 wt.%, of a crosslinkable monomer.

A dispersion of polymer in the form of a latex is produced which may be easily applied to a substrate such as flexible polyester or polyolefin films where it Is dried to form a pressure sensitive adhesive having a balance of good peel strength and shear strength, with the additional advantage of a high shear adhesion fail

temperature (SAFT) provided by the presence of an effective amount of the crosslinking comonomer.

Detailed Description of the Invention

Resins useful in the instant invention are generally well known and are defined as hydrogenated natural resins and thermoplastic resins obtained by polymerization, in the presence of a catalyst of the Friedel-Crafts type, of steam-cracked petroleum distillates, boiling in the range between about 30ºC and 280ºC, or any fraction of these distillates boiling within the said range, or of polymerized mixtures of olefins and diolefins.

The hydrocarbon resins useful according to this invention are preferably petroleum resins prepared by homo and copolymerization of olefins, diolefins, andvinyl aromatic components, predominantly the C-5 to C-9 species, from distillates of cracked petroleum stocks. The feed stocks for the resin must, however, have at least about 10X by weight vinyl aromatic constituents, such as, for example, styrenes, alpha-methyl styrene, indene and vinyl toluene and other well known vinyl aromatic compounds. A Friedel-Crafts catalyst is typically employed and this resin-forming polymerization is performed at temperatures which range generally from 0º to 70ºC. and preferably from 30ºC to 55ºC. The resulting resin is then hydrogenated in accordance with the methods described in U.S. Patent Nos. 4,650,829; 4,328,090 and 4,629,766 for example, the disclosures of which are incorporated herein by reference in their entirety for all purposes. The resulting hydrogenated resin retains a ring and ball softening point in the range of -20ºC to about 150ºC, preferably from about 10ºC to about 100ºC. In the practice of this invention the

pressure-sensitive adhesive formed from resins having a softening point from 15ºC to about 40ºC typically find their best use as laminating adhesives or as adhesives for labels. Those having softening points from about 70ºC to 100ºC for tapes.

Broadly, hydrocarbon resins are polymerized from petroleum cracked distillates boiling in the range of about 30ºC to 280ºC or any fraction boiling within this range having a vinyl aromatic content as set forth above. As is well known, the resins are prepared by treating the distillate with from 0.25 to 2.5% by weight of a Friedel-Crafts-type catalyst such as aluminum chloride, aluminum bromide, boron trifluoride, and the like or solutions, slurries, or complexes thereof. The reactions are conducted at temperatures in the range of 0º to 70ºC, and preferably 30ºC to 55ºC. Residual catalyst is quenched by suitable methods such as addition of methyl alcohol and subsequent filtration, water, and/or caustic washing. The final solution is then stripped of unreacted hydrocarbons and low molecular weight oils by vacuum or steam distillation. Properties of the hydrocarbon resins can be varied by changing conditions and feedstock as is well known.

The hydrocarbon resin is prepared by the hydrogenation of polymerized olefinically unsaturated monomers derived from petroleum cracking, preferably cyclic diolefins, (such as, for example, dicyclopentadiene) styrene alpha-methylstyrene and the like. Such resins, their preparation and hydrogenation are well known in the art and are commercially available under the trade designation, for example, ESCOREZ, Arcon, and the like.

Naturally occurring resins suitable for use in the present invention may be resin esters or terpenes such as alpha-pinene, beta-pinene, carene, limonene or other readily available terpinous materials, alpha-pinene and limonene being preferred. The material may be pure or the commercially available concentrates such as gum terpentine or alpha-pinene concentrates, which tend to be mixtures of various terpinous materials. A suitable natural resin contains from about 70 to 95 wt.% alpha-pinene, the remainder being other

terpenes. Limonene streams are available and are known to those skilled in the art. These are typical streams useful in the present invention. The hydrogenation of these naturally occurring resins is well known and can be carried out using the procedures of the above-identified U.S. Patents.

In the practice of this invention the most successful tackified acrylic copolymers are produced when the resin is soluble in the selected monomer mixture at ambient temperature. Such resin should have a molecular weight of from about 500 to about 5000, preferably from about 1000 to about 2500. When the aromatic contents of the resin, usually a styrene or a vinyl toluene or vinyl xylene

derivatives, decreases below about 30 wt.%, the mixture of acrylic monomers must be adjusted to reduce overall polarity of the monomer mixture in a manner well known to those skilled in such

polymerizations. For example, a substitution of butyl acrylate for 2-ethylhexyl acrylate would reduce polarity. By lowering the polarity of the monomer mixture lower aromaticity in the resin can be tolerated and the resin will still dissolve in the monomers to form a solution.

It has further been discovered that aliphatic resins, such as those formed from amylenes, piperylene, cydopentadiene and its derivatives are not necessarily soluble in the monomers selected, and thus are normally not used. In accordance with this invention, as previously mentioned, in order to form a suitable polymerization reaction mixture, it is necessary that the resins comprise from at least about 10% to 100% by weight vinyl aromatic content, preferably from about 20% to about 65% aromatic content; with 30% to 50% being the most preferred range.

The mononers used in the practice of this invention are vinyl monomers which are polymerizable by free radical reaction, preferably those materials described as acrylics; i.e., alkyl (meth)acrylates and (meth)acrylic acid. Mixtures of alkyl acrylates are usually included, which affect the solubility of the petroleum resins prior to polymerization, as well as final properties of the composition. These acrylate monomer mixtures generally comprise lower

alkyl(meth)acrylates having 1 to 3 carbon atoms in the alkyl group of the ester and upper alkyl (meth)acrylates having 4 or more, usually up to about 14, preferably 4 to 8 carbon atoms. The other monomer component is the (meth) acrylic acid. Some preferred examples of monomers are as follows: acrylic acid, methacrylic acid, crotonic add, maleic acid, itaconic acid, methyl (meth) acrylate,

ethyl (meth)acrylate, propyl acrylate, 2-ethylhexyl acrylate, or n-butyl acrylate. Other monomeric material which can be employed can include acrylonitrile, vinyl acetate, vinyledene chloride, styrene, methyl styrene, and the like. The monomer mixture would contain from IX to about 15%, preferably about 2% to about 6% of the (meth) acrylic acid; 0 to about 50%, preferably about 10% to 35%, lower alkyl (meth)acrylate; and from about 25% to 99%, preferably from 60X to about 88% upper alkyl (meth)acrylate. All percents are by weight of the monomer mixture. It should be noted that some "acrylic" monomer mixtures available include minor amounts of acrylonltrile, styrene, or vinyl acetate, and the like.

In the practice of the instant invention it has been discovered that the peel strength, shear strength, and SAFT of Internally tackified acrylic copolymers can be dramatically improved and balanced by the incorporation in such reaction solution as described above of a small amount usually up to about 3 wt.%, preferably from

0.1 to 2 wt.% of the reaction components; i.e., the monomer with the dissolved petroleum hydrocarbon resi n, a polyfunctional crossl i nkabl e monomer. For instance, the crosslinkable comonomer helps to maintain the holding properties, particularly the shear and SAFT unlike other changes made to improve the peel strength. The effectiveness of the added amount can be easily determined by the following the examples set forth herein. Only a few simple experiments are necessary to determine the small effective amount necessary.

This crosslinkable comonomer can be (i) a linear diene, (ii) an olefin with a terminal functional group which acts as a starting material, or (iii) produced from a polyfunctional compound with a functionality of from 2 to about 4, depending upon the starting material used to prepare the monomer including olefinic, preferably terminal unsaturation. For example, a polyethylene or polypropylene glycol, the preferred species, would have a functionality of 2 and can be reacted with acrylic add to provide an acrylatediester with the required double bonds to act as a crosslinking monomer. The glycol would have an average molecular weight of from 200 to about 1000, preferably from 400 to 800. Other Initiators such as

triethanolamine or trimethylolpropane could be reacted directly, or reacted with an epoxide such as ethylene oxide or propylene oxide to adjust the molecular weight and then reacted, with a (meth)acrylic add to form a trimethacrylate, which is the preferred terminating polymerizable species providing the terminal double bond. The functional radical could be hydroxyl, amine, carboxyl, or cyano. The preferred initiator is the ester of a polyhydroxy initiator. It was unknown and, of course, somewhat surprising that the incorporation of a small amount of such crosslinkable monomer into the internally tackified copolymer would produce dramatic Improvement in the holding properties of pressure-sensitive adhesive. Some useful crosslinkable comonomers are the dimethacrylate of a 600 molecular weight

polyethylene glycol and trlmethylolpropane trimethacrylate. Of course, many other crosslinkable comonomers can be used and are readily determined by those in the art.

The above-mentioned crosslinkable monomers are dissolved in the polymerizable monomer solution in the presence of the hydrocarbon resin as mentioned above. Generally, the reaction of acrylic monomers to form acrylic copolymers is well-known to those of ordinary skill in the art to include the water to adjust the solids content, a surfactant to aid in the formation of monomer-in-water emulsion and to act as a suspending agent for the solids in the final copolymer, which are dispersed in the aqueous medium both during and after the polymerization. The surfactants useful In the practice of this invention are well-known and are present in quantities

sufficient to place the reactants in the emulsion prior to reaction and maintain the product in suspension after reaction. Of particular applicability are blends of anionic and nionic surfactants having a HLB of from about 15 to 42, especially around 40. Especially preferred are the widely used disodium sulfosuccinate as an anionic surfactant and ethylene oxide adducts of nonyl phenol as nonionic surfactants. While the ranges of surfactants are well-known, the amount will preferably range from about 1 to about 5 parts, normally 2 to 4 parts, per 100 parts of the monomers. Also in the reaction mixture is an initiator, such as for example, sodium persulfate or an ammonium persulfate present in catalytic amounts well-known to those skilled in the art, such as for example, about 0.1 part per 100 parts of reaction mixture. In some instances it may be advantageous to buffer the pH of the solution by including a well-known buffering agent such as, for example, sodium bicarbonate.

Notwithstanding the foregoing, the selected petroleum resin is mixed with the selected monomers to form a monomer solution

containing from about 10 to about 100 parts resin per 100 parts (PHR) of the liquid mixture of monomer reactants and more preferably from about 20 to about 60 parts per 100 parts of monomer reactants. Most preferably, from 25 to 55 parts resin per 100 parts monomer reactants are present. As stated herein before, the petroleum resin is selected so that it will be soluble in the monomer mixture at ambient temperatures, but notwithstanding such, the temperature could be raised to the point where it is easily solubilized; i.e., from about 25ºC to about 40ºC.

Included also in the solution is polyfunctional crosslinkable monomers as mentioned above. The crosslinkable monomer may be incorporated in the entire polymerizable mixture or fed into it after the reaction has begun, thus being present in the later stages of the reaction. When the crosslinkable comonomer is not mixed with the entire mixture. It is preferably added with about the last 25% of the polymerizable reaction mixtures.

The molecular weight of such copolymers is normally controlled by commonly known nonolefin chain transfer agent in the polymerization mixture. In the practice of the present invention, the copolymer is to be formed with no chain transfer agent being used which restricts the molecular weight of the copolymer. Similarly we have discovered that the presence of an antioxidant in the resin is to be avoided because it causes the same problem, low molecular weight of the polymer. It is preferred that the solution of monomers and resin be dispersed Into a water medium to form an emulsion at ambient temperatures in the presence of a satisfactory surfactant. The reaction mixture thus formed, including the initiators, must be placed in a reaction vessel, evacuated of oxygen by nitrogen purge, and the polymerization reaction conducted with stirring in the sealed container preferably under a nitrogen blanket.

The addition of the monomer solution containing the hydrocarbon resin and polyfunctional crosslinker is normally carried out intermittently and over a period of time. For example, about 15 wt.% of the monomer solution would be charged would be initially metered Into the reaction mixture Initially and polymerized for a short period of time, to begin the reaction system. Preferably, no crosslinking monomer is present at this point. Normally when this is accomplished, the solids content of the reaction would be about 18 wt.%, which is preferably a benchmark content. Once the selected solids level is attained, the balance of the monomer solution would be evenly metered into the reaction vessel over a period of time, normally several hours, usually 3 to 6 hours depending upon the size of the reaction and quantity to be added. Once the addition of the monomer solution including the crosslinker is complete, the

polymerization is allowed to continue, usually for another hour while maintaining the reaction temperature, normally, with the range of from 45ºC to about 90ºC, preferably between about 50ºC and 80ºC. The polymerization continues until the total solids content of the material in the reactor reaches its theoretical level based upon the amount of reactants charge to the reaction mixture, usually. In practice, about 45 to about 55 wt.%, but the overall solids content may be as high as 70% with there being no real lower limit. While there Is no real theoretical lower limit, a practical lower limit of about 30% solids content is recognized by those skilled in the art. In a commercial sense, the highest limits attainable are preferred.

Once the reaction is complete the solids in the form of a dispersed polymer latex is allowed to cool to room temperature, and the dispersed polymer latex is separated from coagulum formed during polymerization, usually by filtration. In the practice of the

Invention 200-mesh "sock" filter has been found satisfactory. Such latex can be coated on a substrate film for use as a tape, for example. The coated substrate would be dried, usually by circulating hot air at from about 100ºC to about 110ºC for about a few, usually from about 2 to about 5, minutes. Those skilled in the art would readily recognize other processing parameters for such coated substrate. The latex coating usually results in a dried adhesive film of from about 0.5 to about 1.5 mils, preferably about 1.0 mil of thickness, even though thicker or thinner films may be desired in certain applications of the instant invention. Thus dried and cured, the product is in condition for use as a pressure-sensitive adhesive tape.

In certain embodiments of the practice of this invention, the adhesives formed find applications as non-pressure-sensitive adhesives such as, for example, labels, laminating adhesives, binders for woven and nonwoven fabrics, and binders for pressed wood production. For example, the certain species useful as laminating adhesives; i.e., those with high peel strength but low shear properties, would be used to join two or more sheets of material together such as a layer of plastic sheeting to a layer of wood or a multiple layer of wood to form a plywood product.

The foregoing Invention having now been described, the following examples are provided to further teach the preferred embodiment and best modes for practicing the described Invention and to aid others in the practice of the scope of such invention herein provided.

Example 1 ╌ Comparative

This example illustrates the synthesis of acrylic copolymer emulsions. The actual Ingredients charged into the reactor are summarized in Table 1 below. Various amounts of the chain transfer agent, t-dodecanethiol are used in the preparation of Samples 1-4, in order to obtain the copolymers with various molecular weight. TABLE 1

A. Initial Charge:

24.0 parts distilled water

0.1 parts Igepal CO-850, an ethylene oxide adduct

of nonyl phenol (sold by GAF)

0.2 parts sodium bicarbonate

0.05 parts sodium persulfate B. Monomer Solution:

24.2 parts distilled water

3.16 parts Emcol K-8300, an anionic surfactant

manufactured by Witco Chemical

0.05 parts sodium persulfate

37.5 parts 2-ethylhexyl acrylate

10.5 parts ethyl acrylate

2.0 parts acrylic add

0-0.1 part t-dodecanethiol

A 2-liter, four-neck reaction flask equipped with a stirrer, a condenser, a thermosensor, and a monomer addition tube was flushed with nitrogen for 15 minutes. The initial charge (A) was placed in the flask with stirring and continued nitrogen purging for additional 20 minutes. At the end of the 20 minutes, the temperature was rai sed to 65ºC. In a separate vessel, a monomer solution according to the composition (B) was prepared. When the reaction flask temperature was equilibrated at 65ºC, 15 wt.% of the monomer solution (B) was added to the flask and allowed to polymerize for 30 minutes. The total solids at the end of the 30 minutes was about 18%. When the total solids reached this range, the remaining monomer solution (B) was evenly metered into the flask over a period of 3 hours. After the monomer addition, the reaction was allowed to continue at 65ºC for 2 additional hours and then cooled to room temperature. Stirring was continued throughout the procedure.

The final total solids was 50% by weight, particle size 150-250 nm, and Brookfield viscosity 500-1,000 cp. The coagulum content of about 2% of the total reactants charged was removed by filtration. Pressure-Sensitive Adhesive (PSA) Performance Test

The dispensed polymer latex prepared as described above was knife-coated on a Mylar^® film and dried in an air circulating oven for 3 minutes at 110ºC. The dried adhesive coating was approximately 1.5 mils thick. The adhesive was bonded to a stainless steel surface for PSA performance tests. Peel (180º) adhesion was obtained using Test No. PSTC-1 of the Pressure Sensitive Tape Council. Shear test was performed using PSTC-7. SAFT (Shear

Adhesion Fall Temperature) test was similar to shear test except that the test temperature is increased at the rate of 10ºF. per 15 minutes. The temperature at which shear failed is reported as SAFT. Both SAFT and shear were tested at 1 square inch and 1,000-gram hang weight.

PSA performance is sensitive to the molecular weight of the polymer. A chain transfer agent such as t-dodecanethiol is commonly used to control the molecular weight and demonstrate this

Samples 1-4 which were synthesized according to the above procedures, but with various amounts of chain transfer agent. TABLE 2

Dodecanethiol 180º Peel SAFT Shear

Samples (parts) (lbs/in) (ºF) (hrs)

1 0.0 1.1 290+ 100+ 2 0.025 1.1 290+ 100+ 3 0.05 1.6 290+ 18+

4 0.075 1.7 112 3

Samples with t-dodecanethiol level higher than 0.075 parts show cohesion failure in the peel test and have very poor shear, less than 1 hour. These samples are not useful for PSAs.

Example 2

The synthesis procedure described in Example 1 was followed using the initial charge and monomer emulsion compositions of Table 1, except that the monomer composition for the Samples 5-8 were changed to include different amounts of petroleum resins (ESCOREZ

ECR-149╌Exxon Chemical Company, Houston, TX, is a hydrogenation hydrocarbon resin containing 50% aromaticity with a softening point of about 95ºC) dissolved in the monomer solution as illustrated in Table 3 below (all ingredient units are in parts by weight). No chain transfer agent was used. ECR-149 has an average molecular weight of about 1000, 50 wt.% aromaticity and similar structure and softening point to the starting resin of resin emulsion ECR-109A. It is obtained by the hydrogenation of such starting resin (ECR-109A⁾.

TABLE 3

2-Ethylhexyl

Samples ECR-149 Acryl ic Ac id Ethyl Acrylate Acrylate

5 10.0 1.6 8.4 30.0 6 11.6 2.3 7.7 28.4 7 11.6 1.5 8.1 28.8 8 15.0 1.4 7.4 26.2 The PSA performance results of above samples were obtained following same procedures and at same conditions are summarized on Table 4 below. TABLE 4 180º Peel SAFT Shear Samples (lbs/in) (ºF) (hrs) 5 1.6 290+ 100+ 6 2.4 290+ 100+ 7 2.5 290+ 26 8 3.1 188 22 Comparing the results in Table 4 with Table 2, it is clear that a significantly higher peel strength PSA product was obtained while maintaining high shear properties. The improved balance of peel and shear properties cannot be obtained through conventional acrylic composition using externally Introduced tackifier.

Example 3

The same procedure as described in Example 1 above was followed per the tests below. All of the initial charge (A) and the Monomer Solution (B) are the same as Example 1, except that the composition of the monomer solution which also contain the dissolved

crosslinkable comonomer according to Table 5 below (all ingredient units are in parts by weight):

TABLE 5

Acrylic Ethyl 2-Ethylhexyl S-

Samples ECR-149 Acid Acrylate Acrylate 252*

9 0 2.0 10.5 37.5 0.00

10 0 2.0 10.5 37.4 0.24

11 0 2.0 10.5 37.4 0.62

12 15 1.4 7.4 26.2 0.00

13 15 1.4 7.4 26.2 0.11

*S-252 is Polyethylene glycol (600 mol.wt.)

dimethacrylate manufactured by Sartomer Company For Samples 10 and 11, the crosslinkable comonomer was mixed with the whole monomer emulsion. For Sample 13, the crosslinkable comonomer was only mixed with the last 25X monomer emulsion added to the reaction vessel.

Table 6 below summarized the PSA performances of these samples:

TABLE 6

180* Peel SAFT Shear Samples (lbs/in) (ºF) (hrs) 9 1.1 290+ 100+ 10 1.0 290+ 100+ 11 0.53 290+ 100+ 12 3.1 188 22 13 3.1 223. 87 Samples 1 to 3 demonstrate the effect of a crosslinkable

comonomer on peel strength with no resin present. The peel strength normally suffers if the degree of the crosslinking is too high. By incorporating hydrocarbon resin in the acrylic copolymer particles, as in Sample 12, significant increase of peel strength is obtained. Sample 13 contains minor amounts of a crosslinkable comonomer, S-252, together with the same amount of resin in the composition as that of Sample 12. The shear properties are much Improved while the peel adhesion is maintained at the same level.

Example 4

Following the procedure and formulations of Examples 1 and 2, IX of several crosslinkable comonomers was added to the polymerizable solutions incorporating the resin ESCOREZ ECR-149-ID (EXXON), having a softening point of 90.5ºC. The crosslinkable comonomer was changed as set forth in Table 7 below to illustrate the properties of the pressure-sensitive adhesives prepared and tested as described above.

TABLE 7 INTERNAL RESIN TACKIFYING ACRYLICS

CONTAINING 1% (MOD CROSSLINKABLE COMONOMER (RESIN USED: ECR-149-1D. SOFTENING POINT - 90.5ºC

Resin

Sample Level Crosslinkable Peel SAFT Shear

Number (PHR) Comonomer (lbs/in) an (hrs)

14 40 Control, No Comonomer 2.6 253 100+

15 40 Glycidyl Acrylate 2.2 300+ 100+

16 40 2-Hydroxy ethyl acryl ate 2.2 300+ 39

17 40 N-Methylol Acrylamide 2.4 300+ 14

18 40 TMPTMA* * 2.4 300+ 54

19 40 PEG-600-DMA * * * , 0.2X 2.3 280 100+

20 40 PEG-600-DMA * * * , 0.4X 2.4 287 100+

21 50 PEG-600-DMA * * * , 0.2X 2.7 219 100+

22 50 PEG-600-DMA * * * , 0.4X 2.6 241 100+

23 50 Control, No Comonomer 2.8 244 100+ * * Trimethylolpropane Trimethacryl ate (Sartomer-350) .

* * * Polyethyl ene Glycol (600) Dimethacryl ate (Sartomer-252) , Exampl e 5

Following the procedure set forth above in Examples 1 and 2, additional internally tackified acrylic copolymers containing crosslinkable comonomers were compared using resins having different softening points, to wit: ESCOREZ ECR-149 having a softening point of 95ºC. and ECR-149-BPC having a softening point of 87ºC. The results of these tests are given on Table 8 following.

It is seen by the foregoing that the internally tackified copolymers themselves have Improved holding properties by the inclusion of the effective amount of the crosslinkable polyfunctional comonomer.

As Is apparent from the foregoing description, the materials prepared and the procedures followed describe specific embodiments of the invention. It is apparent from the foregoing description that, while predictive forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of this invention. Accordingly, it is not intended that the invention be limited except by the appended claims.

TABLE 8

INTERNAL RESIN TACKIFYING ACRYLICS CONTAINING CROSSLINKABLE COMONOMER

1. ECR-149, SOFTENING POINT = 95ºC; 2. ECR-149-BPC, SOFTENING POINT = 87^ºC

PSA PERFORMANCE

Level (%)

Sample Crosslinkable of X-1 Peel SAFT Shear Nυmber Resin (PHR) Comonomer Comonomer (lbs/in) (ºF) (Hours)

24 ECR-149 40 PEG-600-DMA 0.2 2.6 300+ 19

25 ECR-149 50 PEG- 600 -DMA 0.2 2.2 300+ 20

26 ECR-149-BPC 40 PEG-600-DMA 0.2 3.1 223 87

27 ECR-149-BPC 50 PEG-600-DMA 0.2 3.1 131 57

28 ECR-149 40 ╌ 0 3.1 188 22

29 ECR-149-BPC 40 ╌ 0 2.7 136 71

30 ECR-149-BPC 50 ╌ 0 3.3 128 40

Claims

CLAIMS :

1. In a tackified acrylic copolymer composition comprising:

a hydrogenated hydrocarbon resin, having a molecular weight of from about 500 to about 5000 and an aromatic content of at least 10X by weight; and

an acrylic copolymer formed by free radical initiated

polymerization of a polymerizable monomer mixture comprising alkyl(meth)acrylate and (meth)acrylic add monomers having dissolved therein from about 10 to about 100 parts of the resin per 100 parts polymerizable monomer;

the improvement which comprises, including In the polymerizable monomer mixture an effective amount of a crosslinking comonomer.

2. The tackified copolymer latex composition of Claim 1 wherein the crosslinking comonomer is present in amount of from 0.1 wt.% to about 2 wt.% based upon the total monomer solution present.

3. The tackified copolymer latex composition of Claim 1 wherein the crosslinking comonomer is a methacrylate ester of a polyhydroxy Glycol .

4. The tackified copolymer latex composition of Claim 3 wherein the polyhydroxy Glycol is glycerine, trimetholpropane ethylene glycol, propylene glycol, or epoxide adducts thereof.

5. The tackified copolymer latex composition of Claim 1 wherein the resin is a hydrogenated petroleum hydrocarbon resin having an aromatic content of from about 20 wt.% to about 65 wt.%.

6. The tackified acrylic copolymer latex of Claim 5 wherein the monomer polymerized comprises form 1 to about 15 wt.% of an (meth) acrylic add, 0 to about 50 wt.% of a lower alkyl

(meth)acrylate ester and from about 25 wt.% to 99 wt.% of an upper alkyl (meth)acrylate ester.

7. The tackified copolymer latex composition of Claim 2 wherein the resin is a hydrogenated petroleum hydrocarbon resin having an average molecular weight of from about 100 to about 2500 and an aromatic content of from about 20 wt.% to about 65 wt.% and the monomers include 2 wt.% to 6 wt.% acrylic add, 10 wt.% to 35 wt.% ethyl acrylate and 60 wt.% to 88 wt.% 2-ethylhexyl acrylate, wherein, the resin is present in the polymerization solution in amounts of from 20 to about 55 parts resin per 100 parts monomers polymerized.

8. The tackified acrylic copolymer latex of Claim 1 wherein the

acrylic copolymer also includes one or more of acrylonitrile, vinyl acetate, vinylidene chloride, styrene and methyl styrene.

9. A method for preparing a tackified acrylic copolymer latex

composition having increased peel strength while resisting loss of holding properties which comprises the steps of:

dissolving from about 10 to about 100 parts of a

hydrogenated hydrocarbon resin per 100 parts in a liquid mixture of free-radical polymerizable monomers to form a polymerizable vinyl monomer reactant

solution, the hydrocarbon resin having an average molecular weight of from about 500 to about 5000 and an aromatic content of at least about 10% by weight;

emulsifying the reactant solution in an aqueous medium, polymerizing the emulsified monomers, in absence of oxygen, in the presence of the resin, a free-radical

polymerization initiator and a small, but effective, amount of a polymerizable crosslinking comonomer to form an acrylic copolymer latex; and

recovering the tackified acrylic copolymer latex internally tackified by the resin.

10. The method of Claim 9 wherein the crosslinklng comonomer is

present in the amount of from 0.1 wt.% to about 2 wt.% based upon the total monomer solution present.

11. The method of Claim 10 wherein the crosslinking comonomer is mixed and added with the polymerizable monomers after the polymerization has begun.

12. The method of Claim 11 wherein the crosslinking comonomers is mixed and added to the polymerization with the last 25X of the polymerizable monomers.

13. The method of Claim 9 wherein the monomer polymerized comprise from one to about 15 wt.% of an (meth) acrylic add, 0 to about 50 wt.% of a lower alkyl (meth) acrylate ester and from about 25 wt.% to 99 wt.% of an upper alkyl (meth) acrylate ester.

14. The method of Claim 13 wherein the monomer comprises form 2X to about 6X of an (meth) acrylic add, from about 10 wt.% to about 35 wt.% of an lower alkyl (meth) acrylate add, from about 60 wt.% to about 88 wt.% of an upper alkyl (meth) acrylate.

15. The method of Claim 14 wherein the resin is a hydrogenated

petroleum hydrocarbon resin having an average molecular weight of from about 500 to about 5000 and an aromatic content of from about 20 wt.% to about 65 wt.% and the monomers include 2 wt.% to 6 wt.% acrylic add, 10 wt.% to 35 wt.% ethyl acrylate and 60 wt.% to 88 wt.% 2-ethylhexyl acrylate, wherein, the resin is present in the polymerization solution in amounts of from 25 to about 55 parts per 100 parts monomers polymerized.

16. A pressure-sensitive adhesive film comprising a film having

coated thereon a coating of an internally resin-tack1fied acrylic copolymer material of Claim 15.

17. The pressure-sensitive film of Claim 16 wherein the copolymer coating is from 0.5 to about 1.5 mils thick.

18. A laminating adhesive composition comprising the coating material of claim 16 and a substrate.