JP2022514913A - Articles containing water-based top coats - Google Patents

Abstract

Articles include a substrate and a topcoat having a first side surface that is placed in direct contact with the substrate and a second side surface that is exposed to the environment on the outermost side. Topcoats include acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene-vinyl acetate copolymers, modified ethylene-vinyl acetate, vinyl acetate copolymers, ethylene- (meth) acrylic acid ionomers, vinylidene chloride copolymers, Ethylene- (meth) acrylate copolymers, polyesters, natural rubbers, neoprenes, phenol polymers, polyurethanes, polyvinyl acetates, polyvinyl alcohols, styrene butadiene rubbers, caseins, dextrins, starches, polysaccharides, two or more copolymers thereof, and them. The first polymer selected from two or more combinations of, and any two or more of them, and unlike the first polymer, ethylene-acrylic acid copolymers, polyethylene oxide, ethylene-vinyl acetate copolymers, It comprises water and a second polymer selected from ethylene-vinyl acetate-vinyl acetate copolymers, maleated polyolefins, polyethylene homopolymers, polypropylene homopolymers, and any combination of two or more thereof. [Selection diagram] Fig. 1

Description

The present disclosure relates to articles including water-based topcoats. More specifically, the topcoat is placed in direct contact on the substrate.

Adhesives, inks, and coatings are widely used in the industry. In particular, aqueous formulations of such materials are advantageous in terms of cost and toxic properties and are more widely used as renewable, so-called "naturally friendly" alternatives to solvent-based and hot-melt adhesive formulations. Has acceptable potential.

Aqueous adhesives, pressure sensitive adhesives and sealants can be formulated with a wide range of synthetic and natural polymer chemicals. For the sake of brevity, these product groups are simply referred to herein as "adhesives".

Today's water-based adhesives are used in a myriad of end-use markets, favoring their easy-to-use format and environmentally friendly chemistry.
Processing and packaging of paper, substrates, and related products such as disposable non-woven fabrics, sanitary products, pressure sensitive products, corrugated board, and rewetting adhesives.
Leather and textiles, such as sewing and repairing laminates, fabric repair, and base bonding, rugs and carpets,
Consumer products and "Do It Yourself (DIY) products, such as office products, adhesive gels, liquid adhesives,
Buildings, structures, civil engineering, and products, adhesives, for example for on-site and off-site craftsmen,
Wood work and binding, such as cabinet making, furniture making, door and window frame making, structural joining, upholstery, plywood, particle board, and laminates, as well as medical tapes and wound bandages.

Aqueous heat seal adhesives belong to the category of materials that produce films or coatings when dried. A heat seal adhesive is a thermoplastic material that can be coated on a substrate, dried, and then reactivated by heat and pressure. Upon drying, they are thermally activated to form a coating that can be attached to other substrates such as foil seals on commercially available yogurt containers. They are non-sticky materials at ambient temperature and become liquids that melt during thermal activation during the product assembly process. They differ from traditional hot melt adhesives, which are applied in a thawed state and cooled between substrates.

Heat seal adhesives are commonly used in the packaging industry, including film lamination, pouch construction, and blister pack sealing.

Issues continue to be raised in the formulation of water-based packaging inks. In modern printing, for example, an important issue for water-based inks is that they are effective and efficient when used at the high press speeds (> 1000 ft / min) commonly used for solvent inks. Water does not dry as quickly as most organic solvents, but water still has its advantages. Many workers in the field have focused on modifying existing printing equipment to work well with water-based inks. Furthermore, on the raw material side, there is a strong interest in developing emulsions that dry faster, and the industry recognizes the need to move from solvent inks to water-based inks if an effective solution can be found.

The advantages that Applicants can achieve using water-based inks and coatings for printing and laminating applications by implementing adapted solutions as provided by the disclosures described herein are:
Low or no volatile organic compound (VOC) components,
Low odor,
Ink / coating uses sustainable resources,
Non-flammable, and therefore less environmentally regulated,
Longer ink stability compared to solvent-based inks,
Easier to formulate inks for direct or indirect food contact,
Improved working conditions in the factory and increased life of the photopolymer plate (flexographic printing) may be mentioned.

Therefore, there is still a continuing demand for improved water-based adhesives, inks, and coatings that have better adhesion to difficult low energy substrates, as well as better aggregation and shear resistance. A preferred embodiment of the present disclosure addresses these and other demands and provides an effective solution.

In one embodiment, the present disclosure provides an adhesive composition. As used herein, the term adhesive composition provides an adhesive and / or agglomeration property, preferably both, a bond or a bond, including a detachable bond or bond to one or more surfaces or materials. Refers to a composition that can be used for adhesion. Alternatively, the Adhesive Composition may benefit from beneficial properties, including the adhesive properties conferred by the Composition, and / or as an additive to a composition that may require the beneficial properties, or the composition. It can be used as a component of things. By way of example, in certain preferred embodiments, the adhesive composition is used as an additive and / or component for water-based adhesives, water-based inks, water-based paints, water-based coatings, and the like.

In a preferred embodiment, the adhesive composition comprises (a) acrylic polymer, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resin, ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate, vinyl acetate copolymer, ethylene- ( Meta) Ionomer acrylate, vinylidene chloride copolymer, ethylene- (meth) acrylate copolymer, polyester, natural rubber, neoprene, phenol polymer, polyurethane, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch, polysaccharides, The first polymer selected from the group consisting of any two or more of them, and any combination of any two or more thereof, and (b) unlike the first polymer, preferably the first. It has a different molecular weight than the polymer and has ethylene-acrylic acid copolymer, polyethylene oxide, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl acetate copolymer, maleated polyolefin, polyethylene homopolymer, polypropylene homopolymer, or any of them. A second polymer selected from the group consisting of two or more combinations, (c) a surfactant and (d) water, wherein the amount of water is preferably the total weight of the adhesive composition. Based on, it comprises water, which is sufficient to provide a composition having a solid content of greater than about 30%. In a highly preferred embodiment, the polymer components (a) and (b) are about 10 nanometers (nm) to about 2000 nm, preferably about 10 to about 1000 nm, more preferably about 30 to about 600 nm, even more preferably. Is present in the composition in the form of solid particles having a D50 particle size of about 50 to about 500 nm.

In certain embodiments, the first polymer is acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resin, ethylene vinyl acetate, natural rubber, neoprene, phenolic polymer, polyurethane, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber. , Casein, dextrin, starch, and a group consisting of two or more combinations thereof.

In certain embodiments, the adhesive composition is a natural or synthetic tackifier, synthetic polymers such as polybutadiene, polyisobutylene, polyisoprene and styrene block copolymers, silicone-based MQ resins, antioxidants, stabilizers, fillers, It further comprises one or more additives selected from the group consisting of wetting agents and antifoaming agents. In certain embodiments, the tackifier is a resin selected from the group consisting of rosin ester resins, loginic acid resins, synthetic hydrocarbon resins, synthetic terpene resins, and combinations thereof.

In certain embodiments, the solid content in the adhesive composition, preferably the content of components (a) and (b), is greater than about 50%, and in certain other embodiments, the solid content. Is about 30% to about 60%. Unless otherwise stated herein, a reference to% used with respect to an adhesive composition is a weight percentage of the components a) to d) + (if present) e) additives (s) of the adhesive composition. Point to.

In certain embodiments, the first polymer is present in the adhesive composition in an amount of about 50% to about 98.5% of the adhesive composition, and the tackifier, if present, is greater than about 0%. The second polymer comprises up to about 40% and the second polymer comprises from about 2.5% to about 25%.

In certain embodiments of the present disclosure, the second polymer comprises an ethylene-acrylic acid copolymer, preferably then essentially, more preferably composed of it.

In certain embodiments, the number average molecular weight of the first polymer of the adhesive composition is greater than about 500,000 daltons. In some embodiments, the number average molecular weight of the first polymer is less than about 100,000 daltons, preferably more than about 25,000 daltons and less than about 100,000 daltons. In some embodiments, the number average molecular weight of the first polymer of the adhesive composition is at least about 50,000 daltons. In other embodiments, the number average molecular weight of the first polymer is from about 1,000 to about 20,000 daltons. In certain applications, the number average molecular weight of the adhesive composition is at least about 100,000 daltons, or at least about 200,000 daltons, and for these applications the preferred range is from about 250,000 to about 1,500,000. Dalton.

In one embodiment, preferably one in which the adhesive composition comprises at least a portion of a pressure sensitive adhesive (PSA), the number average molecular weight of the first polymer of the adhesive composition is at least about 100,000. The dalton, preferably at least about 200,000 daltons, preferably in the range of about 250,000 to about 1.5 million daltons. In one embodiment, the number average molecular weight of the first polymer is greater than about 500,000 daltons, especially in embodiments where the adhesive composition is included in PSA or consists of PSA.

The adhesive compositions of the present disclosure can be used to improve the adhesive properties of a myriad of materials and compositions, all such uses of which are intended to be within the broad scope of the present disclosure. .. However, in many cases, each of the following types of materials and compositions, particularly and preferably when such materials and compositions are aqueous materials and compositions, contains the adhesive compositions of the present disclosure. Or, in some cases, it may then be or may be beneficial: heat seal adhesives, water-based inks, primer compositions, intercoat compositions, basecoat compositions, topcoat compositions. , Clearcoat compositions, encapsulant compositions, aqueous bond layers, overprint varnishes, rhologic agents, aqueous sealing materials for metal cans, and aqueous spray can coatings. The aforementioned and other materials are believed to achieve certain advantages for adhesive properties in the methods and applications in which the material is applied to or on low energy substrates.

In certain heat-sealed adhesive compositions, the adhesive compositions of the present disclosure have a first polymer component a) having a number average molecular weight of more than about 50,000 daltons, preferably less than about 20,000 daltons. A second polymer b) having an average molecular weight and the like. For certain aqueous ink compositions, the adhesive compositions of the present disclosure include a first polymer component having a number average molecular weight of more than about 50,000 daltons.

Certain embodiments particularly preferably include the above-mentioned adhesives and water-based materials and compositions such as other materials and compositions herein, agglomeration and / or adhesive strength of certain materials and compositions. A method of improving, preferably increasing, preferably substantially increasing, at least one of aggregation and adhesion strength, preferably both, as compared to the same composition without the adhesive composition of the present disclosure. The subject matter is a method comprising adding the adhesive composition of the present disclosure to such an aqueous material or composition in an amount and conditions effective to make it.

In certain preferred embodiments, the present disclosure is a method of improving the adhesion of a paint or ink to increase adhesion to a low energy substrate surface, preferably to a high energy substrate as well. The subject matter is a method comprising adding the adhesive composition of the present disclosure to a water-based paint or ink in such an amount and condition. In certain embodiments, the paint is preferably selected from the group consisting of primers, intercoats, basecoats, topcoats, clearcoats, encapsulants, aqueous bond layers, and overprint varnishes. In certain embodiments, the ink is preferably selected from the group consisting of water-based packaging inks, water-based printing inks, and water-based flexographic inks.

In yet another embodiment, the article comprises a substrate and a topcoat composition, wherein the topcoat composition is placed in direct contact on the substrate on the first side surface and on the outermost side to the environment. It has a second side that is exposed. The top coat composition is
(A) Acrylic polymer, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resin, ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate, vinyl acetate copolymer, ethylene- (meth) acrylic acid ionomer, vinylidene chloride copolymer, ethylene -(Meta) acrylate copolymers, polyesters, natural rubbers, neoprenes, phenol polymers, polyurethanes, vinyl acetates, polyvinyl alcohols, styrene butadiene rubbers, caseins, dextrins, starches, polysaccharides, two or more copolymers thereof, and theirs. A first polymer selected from the group consisting of two or more combinations and any two or more combinations thereof.
(B) Unlike the first polymer, ethylene-acrylic acid copolymer, polyethylene oxide, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl acetate copolymer, maleated polyolefin, polyethylene homopolymer, polypropylene homopolymer, and theirs. A second polymer selected from the group consisting of any two or more combinations, and
(C) Containing with water.

In a further embodiment, the cured article comprises a substrate and a cured topcoat composition having a first side surface placed in direct contact on the substrate and a second side exposed to the environment on the outermost side. including. The cured topcoat contains a cured product of the first polymer. The first polymer is cured in the presence of the second polymer.

In yet another embodiment, the present disclosure is a method of forming an article comprising a substrate and a topcoat composition, wherein the topcoat composition is placed in direct contact with the substrate. And provide a method having a second aspect exposed to the environment on the outermost side. The method consists of the steps of providing the substrate and water, as well as acrylic polymer, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resin, ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate, vinyl acetate copolymer, ethylene- ( Meta) Ionomer acrylate, vinylidene chloride copolymer, ethylene- (meth) acrylate copolymer, polyester, natural rubber, neoprene, phenol polymer, polyurethane, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch, polysaccharides, A step of providing a water-based coating comprising a first polymer selected from the group consisting of two or more copolymers thereof, and two or more combinations thereof, and any two or more combinations thereof, and water. , Surface active agents, and unlike the first polymer, ethylene-acrylic acid copolymer, polyethylene oxide, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl acetate copolymer, maleated polyolefin, polyethylene homopolymer, polypropylene homopolymer, And a step of providing an emulsion of a second polymer selected from the group consisting of any two or more combinations thereof, a step of combining the emulsion and the aqueous coating composition, and the emulsion and the aqueous coating composition. The combination comprises applying the combination to a substrate to form a topcoat composition having a first aspect disposed in direct contact on the substrate and a second aspect exposed to the environment on the outermost side. ..

A chart of adhesive properties on different substrates of pressure sensitive adhesives according to the procedure and materials described in Example 1 is shown.

The properties show the shear adhesion properties of the same pressure sensitive adhesive shown in FIG. 1, except that the histogram scale is magnified.

FIG. 3 shows a chart of adhesive properties, including the effects of deterioration of pressure sensitive adhesives according to the procedures and materials described in Example 1 on different substrates.

A chart of adhesive properties on different substrates of pressure sensitive adhesives according to the procedure and materials described in Example 1 is shown.

FIG. 3 shows a chart of adhesive properties, including the effects of deterioration of pressure sensitive adhesives according to the procedures and materials described in Example 1 on different substrates.

A chart of adhesive properties on different substrates of pressure sensitive adhesives according to the procedure and materials described in Example 1 is shown.

An example of poor adhesion according to the procedure described in Example 14 is shown. An example of poor adhesion according to the procedure described in Example 14 is shown.

It is a photograph of the paint adhesion result of the control sample in the example compared with the semi-glossy white top coat arranged on the corona-treated substrate and the non-corona-treated substrate.

It is a photograph of the paint adhesion result of the semi-glossy white topcoat arranged on the corona-treated substrate to the semi-glossy white topcoat containing P1 arranged on the same substrate.

It is a photograph of the paint adhesion result of the semi-glossy white topcoat arranged on the corona-treated substrate to the semi-glossy white topcoat containing P2 arranged on the same substrate.

It is a photograph of the paint adhesion result of the semi-glossy white topcoat arranged on the corona-treated substrate to the semi-glossy white topcoat containing P3 arranged on the same substrate.

It is a photograph of the paint adhesion result of the semi-glossy white topcoat arranged on the corona-treated substrate to the semi-glossy white topcoat containing P4 arranged on the same substrate.

It is a photograph of the paint adhesion result of the semi-glossy white topcoat arranged on the non-corona treated substrate to the semi-glossy white topcoat containing P5 arranged on the same substrate.

It is a photograph of the paint adhesion result of the semi-glossy white topcoat arranged on the corona-treated substrate to the semi-glossy white topcoat containing P6 arranged on the same substrate.

It is a photograph of the paint adhesion result to the semi-glossy white top coat containing P6 arranged on the same substrate on the corona-treated substrate.

It is a photograph of the paint adhesion result of the semi-glossy white topcoat arranged on the non-corona treated substrate to the semi-glossy white topcoat containing P7 arranged on the same substrate.

It is a photograph of the paint adhesion result of the semi-glossy white topcoat arranged on the corona-treated substrate to the semi-glossy white topcoat containing P7 arranged on the same substrate.

It is a photograph of the paint adhesion result of the semi-glossy white topcoat arranged on the corona-treated substrate to the semi-glossy white topcoat containing P8 arranged on the same substrate.

It is a photograph of the paint adhesion result of the control sample in the example compared with the outer flat white top coat placed on the corona-treated substrate and the non-corona-treated substrate.

It is a photograph of the paint adhesion result of the outer flat white topcoat arranged on the corona-treated substrate to the outer flat white topcoat containing P1 arranged on the same substrate.

It is a photograph of the paint adhesion result of the outer flat white topcoat arranged on the corona-treated substrate to the outer flat white topcoat containing P3 arranged on the same substrate.

It is a photograph of the paint adhesion result of the outer flat white topcoat arranged on the corona-treated substrate to the outer flat white topcoat containing P4 arranged on the same substrate.

It is a photograph of the paint adhesion result of the outer flat white topcoat arranged on the corona-treated substrate to the outer flat white topcoat containing P8 arranged on the same substrate.

Applicants say that the adhesive compositions of the present disclosure, preferably containing high solid content and low surfactant concentration, are used in a variety of aqueous materials and compositions, including adhesives, coatings, and inks. It has been found that it is possible to provide both improved aggregation and adhesive strength. Accordingly, according to one aspect, the invention adhesive composition can be added as a component or adhesion enhancer to another formulation, composition, or material to provide the desired properties. Accordingly, the present disclosure is based on the weight of all components in an aqueous material or composition, including adhesives, coatings, or ink formulations, from about 1% to about 25% by weight, preferably about 2% by weight. % To about 20% by weight, more preferably from about 5% by weight to about 15% by weight, preferably comprising the adhesive compositions of the present disclosure (ie, the components (a)-(e) described above). Includes a variety of materials and compositions, preferably water-based materials and compositions, including certain water-based adhesives, coatings, inks, and the like.

In certain preferred embodiments, the adhesive composition is in the form of an emulsion, preferably components (a) and (b) are emulsified and / or dispersed in an aqueous component. Applicants have found that one advantage of the adhesive compositions in the form of emulsions of the present disclosure (hereinafter sometimes referred to as "adhesive emulsions") is the high levels in the emulsions, preferably previously commonly used. It is the ability to achieve a solid in a higher amount than the solid being, more preferably substantially higher, and this ability has been found to provide one or more, preferably all of the following advantages: 1) Reduced cost of transportation (compositions with less water generally cost less to ship), 2) Faster drying resulting from less water to be emulsified, 3) Higher film thickness 4) Higher substrate protection, 5) better barrier properties, and 6) a smaller total number of coatings required to achieve the desired coverage.

The preferred adhesive composition of the present disclosure comprises a solid with a particle size profile found to be advantageous. The preferred particle size range according to the present disclosure, together with and in view of the other aspects of the present disclosure, preferably at the same time provides improved scratch, abrasion, and matte resistance. It preferably has the advantage of not causing deterioration of the gloss of the coating. Accordingly, the adhesive compositions of the present invention comprising an adhesive emulsion are solids, preferably from about 10 nm to about 2000 nm, preferably from about 25 to about 1000 nm, more preferably from about 50 to about 600 nm, even more preferably. Provided are a first component (a) and a second component (b) in the form of solid fine particles having a D50 particle size of about 100 to about 500 nm. In some embodiments, the D50 particle size is greater than about 100 nm and less than about 1000 nm. In other embodiments, the D50 particle size is greater than about 200 nm and less than about 700 nm. In still other embodiments, the D50 particle size is greater than about 300 nm and less than about 600 nm. In certain preferred embodiments of an adhesive composition comprising an emulsion composition, a solid thereof, preferably a first component (a) and a second component (b) in the form of solid fine particles, D10 of about 10 nm or more and about. It has a D90 of 2000 nm or less, more preferably a D10 of about 25 or more and a D90 of about 1000 nm or less, even more preferably a D10 of about 50 or more and a D90 of about 600 nm or less, still more preferably about 100 or more. It has a particle size distribution with D10 and D90 of about 500 nm or less. In some embodiments, the particle size distribution has a D10 of about 100 nm or more and a D90 of about 1000 nm or less. In other embodiments, the particle size distribution has a D10 of about 200 nm or more and a D90 of about 700 nm or less. In still other embodiments, the particle size has a distribution having a D10 of about 300 nm or more and a D90 of about 600 nm or less.

Applicants surprisingly find that certain of the preferred embodiments of the present adhesive composition advantageously use low concentrations of surfactant to improve effective adhesion and / or aggregation. Found that it is possible to achieve. More specifically, the unexpected ability by using low surfactant concentrations according to the present disclosure, especially for adhesive compositions in the form of emulsions, is excellent water resistance (water from the environment after the coating has dried). It has the advantage of assisting in the formation of dry coatings and films that have a lower tendency to absorb) and / or have improved film forming ability. Therefore, an adhesive composition according to a preferred embodiment of the present disclosure is preferably from more than about 0% to about 10%, more preferably from about 0.001% to about 5%, even more preferably from about 0.01% to. It contains an amount of surfactant of about 1%, even more preferably about 0.05% to about 0.5%. In certain preferred embodiments, the amount of surfactant contained in the adhesive composition is less than about 5%, more preferably less than about 3%, even more preferably less than about 1%. In certain preferred embodiments, the adhesive composition is less than about 0.5%, preferably less than about 0.1%, more preferably less than about 0.05%, even more preferably less than about 0.01%. Contains a surfactant in the amount of.
Water-based adhesive

Preferred aqueous synthetic polymers intended for use in accordance with the present disclosure include acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene vinyl acetate, natural rubber, neoprene, phenolic resins, polyurethanes, polyvinyl acetate. Examples include vinyl, polyvinyl alcohol, and styrene-butadiene rubber. Preferred aqueous natural polymers intended for use in accordance with the present disclosure include carbohydrate and protein biomacromolecules such as casein, cellulose derivatives, dextrins, and starch.

When used with an aqueous adhesive, the adhesive formulation preferably comprises (a) a first polymer disclosed above, (b) a second polymer disclosed above, (c) a surfactant and the like. It comprises (d) water and (e) optionally other additives. The polymer and potentially other functional ingredients (including stabilizers) are preferably present as solid particles dispersed in water, preferably having the particle size distribution described herein. Some proportions of the solid components (a) and (b) may be present as solutes in the water / aqueous solvent, which is generally unfavorable. As mentioned above, when used with an aqueous adhesive, the first polymer of the adhesive composition is preferably acrylic polymer, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resin, ethylene vinyl acetate, natural rubber, It is selected from the group consisting of neoprene, phenols, polyurethane, polyvinyl acetate, polyvinyl alcohol, styrene-butadiene rubber, casein, and polysaccharides such as dextrin and starch. In such embodiments, the second polymer is preferably homopolymer polyethylene (polyethylene, PE) wax, homopolymer polypropylene (polypropylene, PP) wax, ethylene-propylene copolymer wax, oxidized PE homopolymer wax; EAA copolymer. It is selected from the group consisting of wax, EVA copolymer wax, oxidized EVA copolymer wax, PE wax grafted with maleic anhydride, and PP wax grafted with maleic anhydride.

Other functional ingredients may optionally be included in the adhesive compositions of the present disclosure. In one particular preferred embodiment, the other functional ingredient is a natural tackifier resin, a synthetic tackifier resin, polybutadiene, functionalized polybutadiene, polyisobutylene, functionalized polyisobutylene, polyisoprene, functionalized polyisoprene, butadiene. Styrene block copolymer, styrene block copolymer with isoprene, styrene block copolymer with ethylene-butadiene rubber block, uncapped silicone MQ resin and capped silicone MQ resin, thickener, wetting agent, defoaming agent, antioxidant It is selected from the group consisting of agents, pigments, fillers, and combinations of any two or more of them.

Applicants believe that this adhesive composition provides a combination of benefits that are difficult to achieve, including:

Viscosity: The viscosity of the adhesive is low enough to allow easy handling and processing, but not too low to avoid excessive penetration into the porous substrate, so that the substrate wets slowly. Not too expensive.

Dry content: The solid content of the adhesive is raised as much / as high as actually required to allow drying within an acceptable period in any given bond formation process. You may.

The ability of the composition to provide this combination of performance characteristics is that previously known synthetic adhesives have limited load-bearing capacity, creep tendency under load, cold flow tendency, and limited performance frame for temperature / humidity. , And the unexpected advantage due, at least in part, to the fact that it presented problems including brittle fracture to mechanical impact. It is believed that the present adhesive composition is capable of overcoming these defects.

One aspect of the present disclosure is homopolymer polyethylene wax, homopolymer polypropylene wax, ethylene-propylene copolymer wax, polyethylene oxide homopolymer wax, ethylene acrylic acid copolymer wax, ethylene vinyl acetate wax, vinyl oxide copolymer wax, maleic anhydride. Polyethylene wax grafted, polypropylene wax grafted with maleic anhydride, natural and synthetic tackifier resins, polybutadiene and functionalized polybutadiene, polyisobutylene and functionalized polyisobutylene, polyisobutylene and functionalized polyisobutylene, styrene block polymers, and New aqueous dispersions and / or emulsions of one or more polymers and resins selected from silicon-based MQ resins are targeted.

By including the adhesive composition of the present disclosure in an aqueous material or composition and acting as an adhesion improver, it is possible to formulate higher performance products obtained based on either synthetic or natural polymer chemicals. .. Therefore, these environmentally friendly products can be used in more demanding applications that have traditionally been offered using less sustainable techniques, especially sustainable natural raw materials in adhesive formulations. Allows you to expand the use of. Such adhesives are characterized by increased elastic and loss modulus, as well as the ability to maintain their physical characteristics over a wider temperature range, compared to unmodified adhesive polymers.

The number average molecular weight of the first polymer in many preferred adhesive composition embodiments of the present disclosure is about 100,000 daltons or greater. However, in many preferred heat-sealed adhesives according to the present disclosure, the first polymer of the adhesive composition has a number average molecular weight of less than about 250,000 daltons, more preferably less than about 100,000 daltons. In some preferred heat seal embodiments, the number average molecular weight of the first polymer present in the adhesive composition of the present disclosure is from about 50,000 to about 100,000 daltons.

It is contemplated that the heat seal adhesives according to the present disclosure may be applied by a variety of coating techniques, including coating via gravure, slot dies, or extrusion processes. Preferably, low melting point polymers such as EVA, acrylic polymers, vinyl acetate copolymers, polyurethanes, polyesters are preferably used in heat seal adhesives and the present adhesive compositions are preferably added to these materials by mixing. Thus, a heat-sealed adhesive with improved adhesion and / or aggregation properties is formed. High-performance heat-sealing adhesives for commercial use have a hot green strength of at least about 1 psi for difficult-to-bond materials such as PP, PE, PET, and aluminum foil, from 180 to. It is necessary to provide the remaining non-adhesive properties of up to 130 ° F with a low thermal activation temperature of 300 ° F.

In one particular preferred method aspect of the present disclosure, the high performance heat seal adhesive is a low molecular weight ethylene-acrylic copolymer, polyethylene oxide, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl acetate copolymer, maleated polyolefin, PE, PP. Prepared by incorporating a homopolymer of wax, and an emulsion of these combinations into the formulation, it has improved anti-blocking, low activation temperature binding, and improved adhesion to difficult-to-adhere substrates, and high heat. Provides the benefits of green strength.

In a preferred embodiment, the adhesive composition for use as, with, or in addition to the heat seal adhesive composition is
(A) Acrylic polymer, ethylene-vinyl acetate copolymer, modified EVA, vinyl acetate copolymer, polyurethane, ethylene- (meth) acrylic acid ionomer, vinylidene chloride copolymer, ethylene- (meth) acrylate copolymer, polyester, and two or more of them. The first polymer selected from the group consisting of combinations of
(B) Selected from the group consisting of ethylene-acrylic acid copolymers, polyethylene oxide, ethylene vinyl acetate copolymers, ethylene-vinyl acetate copolymers, maleated polyolefins, homopolymers of PE and PP, and combinations thereof. With the second polymer,
(C) Optionally, with other additives such as tackifiers, antiblocking agents, antioxidants, stabilizers, fillers, wetting agents, etc.
(D) Water, wherein the components (a) and (b) are present in the water in the form of an emulsion.
Enhanced water-based primer adhesion:

By adding the adhesion composition of the present disclosure, preferably in the form of an emulsion of the present disclosure, in many embodiments, the aqueous primer is provided with improved adhesion quality and enhanced adhesion characteristics based on its aqueous compatibility. Can be done. Many conventional uses of aqueous primers have the drawback that when such a primer is applied onto a low energy substrate, the primer does not properly wet the substrate and does not adhere to the substrate. The addition of a preferred adhesive composition, and even more preferably the adhesive emulsion of the present disclosure, can correct problems such as these and others.

Enhanced intercoat adhesion; two different coatings of ink or paint:

When applying a primer to a substrate, continuous coating adhesion can be difficult if the primer, especially oil or alkyd-based ones, is applied. The adhesive composition of the invention, preferably the adhesive emulsion of the present disclosure, is added to the aqueous topcoat to enhance adhesion to the primer with lower surface energy and result in better binding.
Aqueous bond layer:

Adhesive compositions with adhesive qualities, preferably the adhesive emulsions of the present disclosure, can themselves function as an aqueous bond layer between two similar or dissimilar substrates. It can also be added to another adhesive composition to provide an aqueous bond layer composition.
OPV (Overprint Varnish):

Typically, high-gloss transparent coatings require good water, scratch, matte, and abrasion resistance. In the past, OVPs required water-based waxes, typically high-density water-oxidizing waxes in the form of emulsions, in order to provide these properties, typically to acrylic OPVs. Adhesive compositions, preferably the adhesive emulsions of the present disclosure, are small enough to retain transparency and be glossy neutral, but have a preferred particle size that provides higher levels of scratch, glazing, and wear resistance than microemulsions. Have. Further, the micronized wax tends to impair gloss or transparency, but is not impaired by the addition of the present adhesive composition / emulsion.
Aqueous rheology agent.

The compositions of the present disclosure, wherein the first polymer or copolymer has a number average molecular weight of less than about 20,000 daltons, preferably less than about 12,000 daltons, are used as aqueous and / or water reducible rheology control agents. And / or when used as an additive in other compositions used or applied as an aqueous and / or water-reducable rheology control agent, it exhibits efficacy. In some preferred embodiments of this type, the first polymer of the adhesive composition has a number average molecular weight of less than about 1,000 daltons. Adhesive compositions of the present disclosure, preferably such compositions comprising a polyethylene-based polymer as a rheology control agent or an additive to a rheology control agent, are 1) less susceptible to attack by microorganisms and 2) susceptible to PH. No, 3) non-shear sensitive, 4) no need for peeling or activating solvent, providing ease of incorporation (from liquid to liquid), and 5) providing the best rheological profile properties for coating. Advantages, including being thixotropic and exhibiting efficacy in aqueous and / or water-reducible rheological control, are several-fold compared to those currently on the market. In some embodiments, the first polymer is EAA or a metal ionomer thereof.
The aqueous sealing compound of the metal can be the end or lid of the body of the metal can, the O-ring seal, or the end sealing compound.

Adhesive compositions, preferably the adhesive emulsions of the present disclosure, are as aqueous sealing compounds and other aqueous formulations of the sealing material (sometimes referred to as "sealing compounds") at the end (lid) of the can body. It provides an advantage as an ingredient in or an additive thereof. According to the preferred method embodiments of the present disclosure, the sealing material is improved by using the present adhesive composition, preferably an adhesive emulsion, which is then lined in an annular groove on the inner perimeter of the can lid to form an O-ring. It is ventilated and dried in a "casquette" similar to the ring configuration. Preferably, the can lid is then double spliced to the flange of the can body to seal the can. Preferred aqueous edge seaming formulations are predominantly composed of aqueous latex styrene-butadiene rubber (SBR), fillers, tackifiers, dispersants, and rheology modifiers. In one embodiment of the aqueous sealing formulation, the adhesive composition comprises, as the first polymer a), an acrylic modified polyethylene copolymer (such as EAA) having a low number average molecular weight (less than 10,000 daltons), the composition comprising. It is preferably in the form of an aqueous high solid (30-60%, eg, 55% solid) emulsion. In such embodiments, the adhesive composition is capable of providing compatibility and tack-imparting benefits. Without being bound by theory, this advantage is believed to be at least partially due to the dual aspects of the formulation: polar (eg, acrylic) and non-polar (eg, polyethylene characteristics). Invention Aqueous sealing formulations also provide improved adhesion of the formulations to metal lids. Again, without being bound by theory, this advantage is believed to be at least partially due to the presence of carboxyl functional groups attached to the metal. Moreover, the invented aqueous sealing formulation provides a faster drying time of the formulation due to the high solid concentration and requires less time for water removal (low water content). All of these factors are combined to increase performance and line speed in can end sealing manufacturing operations.
Aqueous spray can coating for 2-piece cans.

The emulsions of the present disclosure also have advantages as an aqueous spray coating and as a component of such materials or additives to such materials, which are coatings used inside beer, beverages, or food two-piece cans. Can be provided. The carboxyl group functional group can further crosslink the amine or hydroxyl functional group available from the cross-linking agent from the binder component to provide a reactive moiety that results in in-situ polymerization under thermosetting conditions. In one embodiment, the EAA chemicals in the composition of the invention comprise a low molecular weight (LMW) EAA polymer. As used herein, the term "low molecular weight" means a number average molecular weight of less than 10,000 daltons, unless otherwise stated herein. The EAA polymer is readily incorporated into the crosslinked polymer network because the polymerization is subject to minimal steric hindrance. Any remaining unreacted free carboxyl groups provide additional adhesion to the metal can. The EAA's Inactive Polyethylene backbone provides polymer flexibility, reducing internal polymer stress, which allows for improved flexibility. These properties also allow for downstream flow during flange formation of two-piece body cans. Sprayability is assisted by the rheological profile of the composition of the invention, allowing shear thinning during spraying. The composition of the invention also allows thixotropic recovery of the applied wet film before drying and curing under heating. The high solid (30-60%) feature of the preferred emulsion assists in spraying the formulation, if desired, to achieve a higher film weight per can.
Aqueous flexo ink formulated to be printed on low energy substrates.

Since flexo inks are applied by anilox rollers with small pores as thin films, the agglutination properties of such materials are considered to be particularly important, so by combining this adhesive composition with such inks. Benefits can be achieved. In such embodiments, the invention adhesive compositions, adhesive emulsions are preferably used, and the components in the aqueous flexographic formulation are specifically unique for printing on plastics, films, and foil substrates. Provide an effect. Aqueous flexo inks are widely used on cellulosic wavy substrates, and most flexo inks are easily absorbed by these substrates. However, the non-absorbent substrate has a lower surface tension than the substrate to be printed, is easily wetted with the low energy substrate, and is remixed so as to adhere to the substrate during curing (hot air). Requires water-based flexo ink. The composition of the invention addresses these demands and allows the formulation of high solid, low surface energy, water-based inks with the desired rheology for printing low energy substrates.

Without wishing to be bound by any particular theory, it is believed that the improved adhesion of the composition of the invention is related to the presence of carboxyl functional groups, resulting in much higher molecular weight polymerization upon curing. This enhances adhesion to other substrates, especially difficult substrates with low energy surfaces. In addition, free carboxyl functional groups provide potential cross-linking sites that are important for water-based adhesives, inks, and coatings.

In certain preferred embodiments, the adhesive composition contains an acrylate polymer and a tackifier. Acrylate polymers are commonly used to improve the aggregation and shear resistance of pressure sensitive adhesives. On the other hand, tackifiers are commonly used to improve adhesion. The term "adhesive" generally refers to low molecular weight resins having a number average molecular weight in the range of about 270 to about 1400 Daltons. Most commercially available tackifiers have a number average molecular weight in the range of about 800 to about 1200 daltons. Molecules with a number average molecular weight of more than about 2000 daltons are commonly referred to as polymers. Commercially available tackifiers are generally based on rosin esters, but may also be based on certain types of synthetic resins such as rosin acid, dimerized rosin acid, and terpene resins and C9 / C5 hydrocarbon resins. .. The tackifier improves peel-off adhesion to "difficult-to-bond substrates" such as polyethylene, and also improves rapid sticking (sticking) properties to low-energy and high-energy surfaces. However, there are many drawbacks to using the tackifier resin. The tackifier resin needs to be dispersed with a much higher concentration of surfactant than the polymer type. Excess surfactant absorbs moisture, which can adversely affect the convertibility of pressure sensitive adhesives. Further, the resin is a super-cooling liquid and exhibits a flow tendency. This results in sticking to the edges and stickiness of the knife. In addition, the low molecular weight resins allow them to move to the paper substrate, resulting in loss of adhesion. This effect is exacerbated by heat and humidity.

At present, it is possible to produce an adhesive containing less rosin-based tackifier than many commercially available adhesives, and thus the above-mentioned problems can be solved by using the adhesive composition of the present disclosure, particularly an adhesive emulsion. It has been found that it is unlikely to occur. In addition, the adhesives incorporating the adhesive compositions of the present disclosure have better aggregation and shear resistance overall and at the same time do not use the compositions on certain difficult substrates, especially after degradation. It has the same or better adhesion as the adhesives made but mainly containing acrylate polymers and rosin esters.

The present disclosure also provides an aqueous composition adapted for adhesion to low energy substrates. This composition comprises acrylic polymer, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resin, ethylene vinyl acetate, natural rubber, neoprene, phenol polymer, polyurethane, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, and dextrin. , Stheat, two or more copolymers thereof, and a first polymer selected from the group consisting of two or more combinations herein. In one embodiment, the compositions of the present disclosure also comprise a tackifier resin selected from the group consisting of rosin ester resins, loginic acid resins, synthetic hydrocarbon resins, synthetic terpene resins, and combinations thereof. include. In one embodiment, the composition of the present disclosure is also selected from the group consisting of ethylene-acrylic acid copolymers, polyethylene oxide, ethylene-vinyl acetate-vinyl acetate copolymers, maleated polyolefins, and combinations thereof. Contains the polymer of.

式中、Ｒ１が、水素原子又はメチル基を表し、Ｒ２が、アルキル基を表す。Ｒ２のアルキル基の例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ペンチル基、イソアミル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、イソオクチル基、２－エチルヘキシル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、ドデシル（ラウリル）基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、及びオクタデシル（ステアリル）基などの１～１８個の炭素原子を有する線状又は分岐状アルキル基が挙げられる。 Acrylic polymers (polymers composed of acrylic acid or acrylic acid derivatives) and copolymers (polymers composed of acrylic acid or acrylic acid derivatives) have conventionally been used in the art of pressure sensitive adhesives and are disclosed herein. The types of acrylate polymers and copolymers that can be used in are not particularly limited. However, alkyl acrylates and alkyl methacrylates may be combined and described as "alkyl (meth) acrylates" and are preferably used as the main monomer component in the acrylate polymers and copolymers of the present disclosure. These alkyl (meth) acrylates are represented by the following general formula:

In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group. Examples of the alkyl group of R2 are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isoamyl group, neopentyl group, hexyl group and heptyl group. Group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl (lauryl) group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and Examples thereof include a linear or branched alkyl group having 1 to 18 carbon atoms such as an octadecyl (stearyl) group.

Examples of alkyl (meth) acrylates include methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, Isoamyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, Examples thereof include isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate.

In addition to the alkyl (meth) acrylate as the main constituent monomer component, another submonomer component copolymerizable with the alkyl (meth) acrylate may also be used. The amount of alkyl (meth) acrylate relative to the total amount of monomers constituting the acrylate polymer or copolymer is preferably 50% or more by weight. Two or more types of alkyl (meth) acrylates may be used in the same acrylate polymer and copolymer.

Copolymerizable monomer components may be used to introduce crosslinked sites into the acrylate polymer or to improve the agglutination capacity of the acrylate polymer. One type or several different types of monomers may be used for the copolymerization.

In order to introduce the crosslinked moiety into the acrylate polymer, a monomer containing a specific functional group may be used as a copolymerizable monomer component. The use of functional group-containing monomer components can improve the adhesive strength of the polymer. The functional group-containing monomer component is not particularly limited. This is a monomer component copolymerizable with an alkyl (meth) acrylate having a functional group as a cross-linking site. Non-limiting examples of such monomers include carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and isocrotonic acid, or maleic anhydride and itaconic anhydride. Those acid anhydrides, hydroxyl group-containing monomers, such as hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, and 2-hydroxybutyl (meth) acrylates. Also again, vinyl alcohol, and allyl alcohol, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N. -Amid-based monomers such as methoxymethyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide, aminoethyl (meth) acrylates, N, N-dimethylaminoethyl (meth) acrylates, and t-butylaminoethyl (meth). ) Amino group-containing monomers such as acrylates, epoxy group-containing monomers such as glycidyl (meth) acrylates and methyl glycidyl (meth) acrylates, cyano-containing monomers such as acrylonitrile and methacrylonitrile, N-vinyl-2-pyrrolidone, N-methyl. Vinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazin, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholin, N-vinyl Examples thereof include caprolactam and monomers having a nitrogen atom-containing ring such as N- (meth) acryloylmorpholine.

Other copolymerizable monomers may be used to improve the agglutination capacity of the acrylate polymer. Non-limiting examples of other copolymerizable monomer components include vinyl ester-based monomers such as vinyl acetate and vinyl propionate, styrene, styrene-based monomers such as substituted styrene (such as α-methylstyrene and vinyltoluene), and the like. Non-aromatic ring-containing (meth) acrylate esters such as cycloalkyl (meth) acrylates (cyclohexyl (meth) acrylates, cyclopentyldi (meth) acrylates, bornyl (meth) acrylates, and isobornyl (meth) acrylates], aryl (meth) ) Acrylate [eg, phenyl (meth) acrylate], aryloxyalkyl (meth) acrylate (eg, phenoxyethyl (meth) acrylate), and arylalkyl (meth) acrylate (eg, benzyl (meth) acrylate). Olefin monomers such as ring-containing (meth) acrylate esters, ethylene, propylene, isoprene, butadiene, isobutylene, vinyl chloride, and vinylidene chloride, isocyanate group-containing monomers such as 2- (meth) acryloyloxyethyl isocyanate, methoxyethyl (meth). Alkoxy group-containing monomers such as acrylates and ethoxyethyl (meth) acrylates, vinyl ether-based monomers such as methyl vinyl ethers and ethyl vinyl ethers, and 1,6-hexanediol di (meth) acrylates, ethylene glycol di (meth) acrylates, diethylene glycol di ( Meta) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, Glycerindi (Meta) Acrylate, Epoxy Acrylate, Polyester Polyfunctional monomers such as acrylates, urethane acrylates, divinylbenzenes, butyldi (meth) acrylates, hexyldi (meth) acrylates, and combinations of any two or more of these monomers can be mentioned.

In some embodiments of the present disclosure, the acrylate polymer or copolymer comprises 2-ethylhexyl acrylate and / or butyl acrylate as the main monomer component and methyl methacrylate, vinyl acetate, and / or styrene as the submonomer component.

Processes for polymerizing acrylate polymers and acrylate copolymers are generally known in the art. Non-limiting examples of such processes include emulsion (co) polymerization, solution (co) polymerization, suspension (co) polymerization, all component filling process (at once polymerization process), and monomers. It is a dropping process (continuously dropping process, partial dropping process (portion-wise dropping process)).

The polymerization initiator used is selected from those generally known in the art, depending on the type of polymerization process involved. Non-limiting examples of polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylpropion-amidin) disulfate, and 2,2'-azobis (2-2'-azobis). Amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutyramidin) , 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile) ), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4,4-trimethylpentane), dimethyl-2,2'-azobis (2-methyl-propionate), And 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate and other azo polymerization initiators, persulfate-based polymerization initiators such as potassium persulfate and ammonium persulfate, and excess. Benzoyl oxide, t-butylhydroperoxide, di-t-butylperoxide, t-butylperoxybenzoate, dicumylperoxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1 -Azobis (t-butylperoxy) cyclododecane, peroxide-based polymerization initiators such as hydrogen peroxide, substituted ethane-based polymerization initiators such as phenyl-substituted ethane, aromatic carbonyl compounds, and oxidation-reduction-based initiators. Will be. The polymerization initiator may be used alone or in combination of two or more.

The amount of the polymerization initiator is typically generally used in the art, for example, about 0.01 to 1 part by weight, preferably about 0.01 to 1 part by weight, based on 100 parts by weight of the total monomer component to be polymerized. It can be selected from the range of 0.02 to 0.5 parts by weight.

The polymerization temperature is selected according to the type of monomer, the type of initiator, etc., as is generally known in the art, and may be, for example, in the range of 20 ° C to 100 ° C.

The acrylate polymer and acrylate copolymer composition may be dispersed or emulsified in a medium such as water. Any suitable emulsifier may be used for that purpose. Non-limiting examples of anionic emulsifiers include anionic emulsifiers of the type of alkyl sulfates such as sodium lauryl sulfate, ammonium lauryl sulfate, and potassium lauryl sulfate, and polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate. Anionic emulsifiers of salt type, anionic emulsifiers of polyoxyethylene alkyl phenyl ether sulfate types such as polyoxyethylene lauryl phenyl ether ammonium sulfate and sodium polyoxyethylene lauryl phenyl ether sulfate, sulfonic acids such as sodium dodecylbenzene sulfonate. Examples include anionic emulsifiers of the salt type, anionic emulsifiers of the sulfosuccinate type such as disodium lauryl sulfosuccinate and disodium lauryl polyoxy-ethylene sulfosuccinate. Further, non-limiting examples of non-ionic emulsifiers include non-ionic emulsifiers of the type of polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ethers, and polyoxyethylene alkyl phenyl ethers such as polyoxyethylene lauryl phenyl ethers. Types of nonionic emulsifiers, polyoxyethylene fatty acid esters, nonionic emulsifiers such as polyoxyethylene-polyoxypropylene block polymers, combinations of any two or more of these monomers can be mentioned.

The amount of emulsifier used is not particularly limited as long as it is possible to prepare an acrylate polymer or an acrylate copolymer in the form of an emulsion. For example, the amount may be selected from the range of about 0.3 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, based on 100 parts by weight of the acrylate polymer or acrylate copolymer or their monomer components. can.

The acrylate copolymer for use in this adhesive composition can be obtained from BASF Corporation (Charlotte, NC, USA) under the trade name ACRONAL® V215. ACRONAL® V215 has the following specifications: solid content 68-70%, pH value 3.5-6.0, viscosity at 23 ° C. (Blockfield RVT, Spindle # 3). , 50 rpm) is 400-2000 cps, the density is about 8.4 lb / gal, the viscosity at 23 ° C. (shear rate 100 seconds -1) is 200-1000 cps, and the median particle size is about 0. It is 0.6 μm, the type of dispersion is anionic, and the glass transition temperature (DSC) is about 43 ° C.

Another acrylate copolymer useful according to this composition is sold by Organic Kimya (Turkey) under the name ORGAL AX1260.

The tackifier has been conventionally used in the art of pressure-sensitive adhesives, and the types of tackifiers that can be used in the present disclosure are not particularly limited. Non-limiting examples of potentially suitable tackifiers include rosin-based tackifiers, terpene-based tackifiers, hydrocarbon-based tackifiers, epoxy-based tackifiers, polyamide-based tackifiers, elastomers. Examples thereof include a system-based adhesive-imparting resin, a phenol-based adhesive-imparting resin, and a ketone-based adhesive-imparting resin. The tackifier resin can be used alone or in combination of two or more of them.

Rosin is primarily, but not limited to, a solid form of resin obtained from coniferous plants (rosin obtained from this source is sometimes referred to as gum rosin). Other sources of rosin include rosin obtained from a distillate of crude tall oil (called tall oil rosin). Rosin can also be obtained from degraded pine stumps (typically called wood rosin). Rosin mainly consists of different loginic acids, especially abietic acid, neo-avietic acid, pulsed toric acid, levopimalic acid, dehydroabietic acid, pimaric acid, sandaracopimaric acid, and isopimaric acid.

Examples of the rosin-based tackifier resin include unmodified rosins (raw rosins) such as gum rosin, wood rosin, and tall oil rosin, as well as rosins modified by hydrogenation, disproportionation, polymerization, or other processes. .. Non-limiting examples of rosin derivatives include rosin esters obtained by esterifying unmodified rosins, and modified rosins including, for example, hydride rosins, disproportionated rosins, polymerized rosins and the like. Unsaturated fatty acid-modified rosin or rosin ester obtained by modifying the obtained rosin ester, unmodified rosin or modified rosin (hydrogenated rosin, disproportionated rosin, polymerized rosin, etc.) with unsaturated fatty acid is modified with unsaturated fatty acid. Carboxyl group in unsaturated fatty acid modified rosin ester, unmodified rosin, modified rosin (hydrogenated rosin, disproportionated rosin, polymerized rosin, etc.), unsaturated fatty acid modified rosin, or unsaturated fatty acid modified rosin ester. Examples thereof include rosin alcohol, unmodified rosin, modified rosin, and metal salts of rosin (particularly rosin ester) containing various rosin derivatives obtained by reducing the amount of fatty acid. In addition, a rosin phenolic resin obtained by adding phenol to a rosin (such as unmodified rosin, modified rosin, and various rosin derivatives) in the presence of an acid catalyst may be used, followed by thermal polymerization. Rosin-based tackifier resins and their manufacture are well known to those of skill in the art. Therefore, these resins and their manufacture are not described in great detail herein.

Rosinic acid and rosinic acid-based resins are known to those of skill in the art and are known to many sources, such as DRT (France), Euro-Yser (Portugal), Harima Chemicals, Inc. (Japan) and Eastman Chemical Company (USA).

The rosin ester resin is commercially available, for example, from Eastman Chemical Company (Kingsport, TN, USA) under the trade name TACOLYN ™ 3509. TACOLYN ™ 3509 resin dispersion is an anionic, aqueous, solid 55%, solvent-free dispersion of stabilized rosin ester with low surface tension. The TACOLYN ™ 3509 resin dispersion has the following specifications: an average particle size typically 200 nm, a softening point (Hercules dropping method) of 68-78 ° C., and a total solid content of 54. -56%, viscosity at 25 ° C., Brookfield LVTD, 60 rpm 100-500 mPa. s, and the density is typically 1.05 g / mL.

The rosin dispersion is commercially available, for example, under the trade name AQUATAC ™ XR4343 from Arizona Chemical (FL, USA) and has the following specifications: ring-ball softening point at about 80 ° C. and solid content. It is about 60%, the pH is typically 8.5 and the viscosity is typically 500-700 cps at 21 ° C., 50 rpm, with a Blockfield # 3 spindle.

Synthetic hydrocarbon resins are polymerization products of the C9 or C9 / C5 by-product fractions derived from the decomposition or chemical treatment of petroleum. These types of resins are known in the art and are commercially available from many sources (eg, Eastman Chemical Company (Kingsport, TN, USA) under the trade name TACOLYN ™ 1070).

The synthetic terpene resin is a dispersion of terpene and phenol, or terpene and styrene or a styrene derivative. These types of resins are known in the art and are commercially available from many sources (eg, DRT (France), and Arizona Chemical (FL, USA)).

The tackifier may have a form composed of the tackifier resin alone, or may be dissolved or dispersed in a medium-like water. The tackifier of the type of aqueous dispersion can be prepared by dissolving or melting the tackifier resin and then dispersing it in water. An emulsifier may be used to disperse the tackifying resin in water. Any suitable type of emulsifier can be used. Non-limiting examples of anionic emulsifiers include anionic emulsifiers of the type of alkyl sulfates such as sodium lauryl sulfate, ammonium lauryl sulfate, and potassium lauryl sulfate, and polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate. Anionic emulsifiers of salt type, anionic emulsifiers of polyoxyethylene alkyl phenyl ether sulfate types such as polyoxyethylene lauryl phenyl ether ammonium sulfate and sodium polyoxyethylene lauryl phenyl ether sulfate, sulfonic acids such as sodium dodecylbenzene sulfonate. Examples include anionic emulsifiers of the salt type, anionic emulsifiers of the sulfosuccinate type such as disodium lauryl sulfosuccinate and disodium lauryl polyoxy-ethylene sulfosuccinate. Non-limiting examples of non-ionic emulsifiers include non-ionic emulsifiers of the type polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ethers and types of polyoxyethylene alkyl phenyl ethers such as polyoxyethylene lauryl phenyl ethers. Nonionic emulsifiers, polyoxyethylene fatty acid esters, nonionic emulsifiers such as polyoxyethylene-polyoxypropylene block polymers, combinations of any two or more of these monomers can be mentioned. In addition, a surfactant may be used to disperse the tackifier resin in water or other medium.

The amount of the emulsifier used is not particularly limited as long as it is possible to prepare the tackifier resin in the form of an emulsion. For example, the amount can be selected from the range of about 0.2 to 10% by weight, preferably 0.5 to 5% by weight, based on the total amount of the tackifier resin (solid substance).

The emulsifier used to prepare the tackifier of the aqueous dispersion type may be the same as or different from the emulsifier used to prepare the acrylate polymer or acrylate copolymer of the aqueous dispersion type described above.

The weight ratio between the acrylate polymer and the pressure-sensitive adhesive resin in the pressure-sensitive adhesive is not particularly limited, and can be selected according to the degree of adhesion that the pressure-sensitive adhesive should have. In some embodiments of the present disclosure, the dry weight ratio between the acrylate polymer (or acrylate copolymer) and the tackifier resin is from about 9: 1 to about 8: 1. Is. In other embodiments, the ratios are about 8: 1 to about 7: 1, about 7: 1 to about 6: 1, about 6: 1 to about 5: 1, about 5: 1 to about 4: 1, and about. 4: 1 to about 3: 1, about 3: 1 to about 2: 1, about 2: 1 to about 1: 1, about 1: 1 to about 1: 2, and about 1: 2 to about 1: 3. be.

The second polymer of the present disclosure is selected from the group consisting of ethylene-acrylic acid copolymers, polyethylene oxide, ethylene-vinyl acetate-vinyl acetate copolymers, maleated polyolefins, and combinations thereof. Ethylene-acrylic acid copolymers, like their manufacture, are well known to those of skill in the art. These copolymers are used in a myriad of applications. For example, these copolymers are used as additives in adhesives, coatings, and inks. Ethylene-acrylic acid copolymers are usually made by polymerization of ethylene and acrylic acid monomers using a free radical initiator. The acrylic acid content of the copolymer contributes to the polarity and adhesion of the copolymer and reduces its crystallinity. As the content of the acrylic acid monomer subunit in the polymer increases, the crystallinity of the ethylene-acrylic acid copolymer decreases. The amount of acrylic acid monomer subunit in the copolymer, or the acid value of the copolymer, is determined by Method ASTM D-1386. Polymers with a high acid value contain a high content of acrylic acid monomers. Commercial grades of ethylene-acrylic acid copolymers are available with an acid value of approximately 40-200 mg KOH / g. The acidic groups in the ethylene-acrylic acid copolymer provide a reactive site for the production of aqueous emulsions. The number average molecular weight (Mn) of ethylene-acrylic acid copolymers is generally in the range of 1,500 to 3,000, and their weight average molecular weight (Mw) is generally 2,000 to 6,000. It is a range. The molecular ethylene-acrylic acid copolymer is determined by gel permeation chromatography (GPC). The density of the polymer is determined by method ASTM D-1505 and is generally in the range 0.90 to 1.00 g / cc. The Mettler drop point of the polymer is generally in the range of 70 ° C to 110 ° C, as determined by Method ASTM D-3954. The viscosity of the ethylene-acrylic acid copolymer at 140 ° C. is generally in the range of 200-1,000 cps, as determined by a Brookfield rotational viscometer. The hardness of the ethylene-acrylic acid copolymer at 25 ° C. is generally in the range of 1-50 dmm, as determined by Method ASTM D-5.

Ethylene-acrylic acid copolymers are described, for example, as AC® 5120, Honeywell International Inc. It is commercially available from. AC® 5120 has the following specifications: an acid value of 112-130 mg KOH / g and a penetration hardness value at 25 ° C. of less than 15 dmm (typically 8 dmm), 140. The viscosity at ° C. is 600 cps, the Mettler is 92 ° C., and the density is 0.93 g / cc.

Ethylene oxide-vinyl acetate copolymers, like their manufacture, are well known to those of skill in the art. The ethylene-vinyl acetate-vinyl acetate copolymer contains polar groups such as carboxylic acids, hydroxyls, ketones, and ester groups in the polymer molecule. The polymer is made by oxidizing the ethylene-vinyl acetate copolymer with hot oxygen (typically provided from the air). Ethylene-vinyl acetate copolymer is a semi-crystalline material containing various polar groups in addition to carboxylic acid, all of which contribute to the adhesion and aqueous compatibility of the ethylene-vinyl acetate copolymer. These copolymers are used in a myriad of applications. For example, these copolymers are used as additives in adhesives, coatings, and inks. The acid content of the ethylene oxide-vinyl acetate copolymer, or the acid value of the copolymer, is determined by Method ASTM D-1386. Commercial grades of ethylene oxide-vinyl acetate copolymers are generally available with an acid value of about 8-30 mg KOH / g. The acidic groups in the copolymer provide reactive sites for making aqueous emulsions. The number average molecular weight (Mn) of polyethylene oxide is generally in the range of 1,500 to 4,000, and their weight average molecular weight (Mw) is generally in the range of 4,000 to 15,000. .. The molecular weights of both Mn and Mw of the ethylene oxide-vinyl acetate copolymer are determined by gel permeation chromatography (GPC). The density of the copolymer is determined by method ASTM D-1505 and is generally in the range of 0.85 to 1.00 g / cc. The Mettler drop point of the copolymer is generally in the range of 75 ° C to 110 ° C, as determined by Method ASTM D-3954. The viscosity of the copolymer at 140 ° C. is in the range of 250-1500 cps, as determined by a Brookfield rotational viscometer. The hardness of the polymer is determined by Method ASTM D-5 and is generally in the range of 3-80 dmm.

Ethylene-vinyl acetate copolymers are described, for example, under the trade name AC® 645P, Honeywell International Inc. It is commercially available from. AC® 645P has the following specifications: acid value is 12-16 mg KOH / g, hardness at 25 ° C is 4-7 dmm, and viscosity at 140 ° C (Blockfield) is 375 cps. The Mettler is 99 ° C. and the density is 0.94 g / cc.

Polyethylene oxide, like their manufacture, is well known to those of skill in the art. Polyethylene oxide contains polar groups such as carboxylic acids, ketones, hydroxyls, and ester groups, which contribute to polymer adhesion and aqueous compatibility. Polyethylene oxide is made by oxidizing polyethylene (low density, medium density, and high density types) with hot oxygen (typically provided as air). Polyethylene oxide is a semi-crystalline material. These polymers are used in a myriad of applications. For example, these copolymers are used as additives in adhesives, coatings, and inks. The acid content in these polymers, or the acid value of the polymers, is determined by the Method ASTM D-1386 method. Commercial grades of polyethylene oxide are generally available with an acid value of about 10-45 mg KOH / g. The acidic groups in the polymer provide reactive sites for making aqueous emulsions. The number average molecular weight (Mn) of polyethylene oxide is generally in the range of 800 to 6,000, and their weight average molecular weight (Mw) is generally in the range of 1,500 to 20,000. The molecular weight (both Mn and Mw) of polyethylene oxide is determined by gel permeation chromatography (GPC). The density of the polymer is determined by the method ASTM D-1505 and is generally in the range of 0.85 to 1.00 g / cc. The Mettler drop point of the polymer is in the range of 85 ° C to 145 ° C, as determined by Method ASTM D-3954. The viscosity of the polymer at 140 ° C. is generally in the range of 35-100,000 cps, as determined by a Brookfield rotational viscometer. The hardness of the polymer is determined by Method ASTM D-5 and is generally in the range of 0.5-100 dmm.

Polyethylene oxide polymers are described, for example, under the trade name AC® 655, Honeywell International Inc. It is commercially available from. AC® 655 has the following specifications: acid value is 14-17 mg KOH / g, hardness at 25 ° C is 2-3 dm, and viscosity at 140 ° C (Blockfield) is 210 cps. The Mettler is 107 ° C. and the density is 0.93 g / cc. Honeywell International Inc. Another polyethylene oxide polymer commercially available from is polyethylene oxide sold under the trade name AC® 656. AC® 656 has the following specifications: hardness at 25 ° C. is 8-12 dmm, Mettler is 98 ° C., density is 0.92 g / cc, 140. The Brookfield at ° C. is 185 cps and the acid value is 14-17 mg KOH / g.

Maleinated polyolefins, like their manufacture, are well known to those of skill in the art. Maleinated polyolefins contain polar groups in the polymer molecule. Maleic anhydrides can be made by grafting maleic anhydride on the polyolefin with a peroxide. Maleic polyolefins are semi-crystalline materials. They are used for a myriad of uses. For example, these polymers are used as additives in adhesives, coatings, and inks. Maleic anhydride contributes to polarity and adhesion and reduces crystallinity. The content of maleic anhydride in the polymer, or the number or acid value of their saponifications, is determined by the Method ASTM D-1386 method. Polymers with a high saponification number contain a high content of maleic anhydride. Commercial grades of maleated polyolefins are generally available in saponification numbers of about 5-100. The maleic anhydride group in the polymer provides a reactive site for making an aqueous emulsion of the polymer. The number average molecular weight (Mn) of maleated polyolefins is generally in the range of 2,000 to 6,000, and their weight average molecular weight (Mw) is generally in the range of 5,000 to 20,000. be. The molecular weight (both Mn and Mw) is determined by gel permeation chromatography (GPC). The density of the polymer is determined by method ASTM D-1505 and is generally in the range 0.90 to 1.00 g / cc. The Mettler drop point of the polymer is determined by Method ASTM D-3954 and is generally in the range of 100 ° C to 160 ° C. The viscosity of maleated polyethylene at 140 ° C. is generally in the range of 500 to 5,000 cps, as determined by a Brookfield rotational viscometer. The viscosity of maleated polypropylene at 190 ° C. is generally in the range of 300-3,000 cps, as determined by a Brookfield rotational viscometer. The hardness value of the polymer is in the range of 0.5 to less than 15 dmm, as determined by Method ASTM D-5.

Maleated polyolefins are described, for example, in Honeywell International Inc. It is commercially available from.

Non-limiting examples of processes for making combinations, mixtures, dispersions, or emulsions of acrylate polymers or acrylate copolymers, rosin esters, and second polymers of the present disclosure are described in the Examples below.

In some embodiments of the present adhesive composition, particularly the adhesive emulsion, the first polymer is present at a concentration of about 50% to about 99% by weight of the total dry weight of the composition and the tackifier is a composition. It is present at a concentration of about 0% to about 40% by weight of the total dry weight of the material, and the second polymer is present at a concentration of about 1% to about 17.5% by weight of the total dry weight of the composition. .. In other embodiments of the present disclosure, the first polymer is present at a concentration of about 59% to about 65% by weight of the total dry weight of the composition. In other embodiments of the present disclosure, the first polymer is present at a concentration of about 65% to about 75% by weight of the total dry weight of the composition. In other embodiments of the present disclosure, the first polymer is present at a concentration of about 75% to about 85% by weight of the total dry weight of the composition. In other embodiments of the present disclosure, the first polymer is present at a concentration of about 85% to about 99% by weight of the total dry weight of the composition. In some embodiments of the present disclosure, the tackifier is present at a concentration of about 0% to about 10% by weight of the total dry weight of the composition. In other embodiments of the present disclosure, the tackifier is present at a concentration of about 10% to about 20% by weight of the total dry weight of the composition. In other embodiments of the present disclosure, the tackifier is present at a concentration of about 20% to about 30% by weight of the total dry weight of the composition. In other embodiments of the present disclosure, the tackifier is present at a concentration of about 30% to about 40% by weight of the total dry weight of the composition. In some embodiments of the present disclosure, the second polymer is present at a concentration of about 1% to about 4% by weight of the total dry weight of the composition. In other embodiments of the present disclosure, the second polymer is present at a concentration of about 4% to about 8% by weight of the total dry weight of the composition. In other embodiments of the present disclosure, the second polymer is present at a concentration of about 8% to about 12% by weight of the total dry weight of the composition. In other embodiments of the present disclosure, the second polymer is present at a concentration of about 13% to about 17.5% by weight of the total dry weight of the composition. In other embodiments of the present disclosure, the second polymer is present at a concentration of about 17.5% by weight to about 30% by weight of the total dry weight of the composition.

In a further embodiment, the surface of the member to be bonded is coated with a suitable known or conventional surface treatment, such as a physical treatment such as corona discharge treatment or plasma treatment, undercoating, prior to application of the adhesive composition of the present disclosure. It may be subjected to chemical treatment such as treatment or backside treatment.

As used herein, the term "honeywell" refers to the following trademark names: AC® 5120, AC® 645P, AC® 655, and AC- Honeywell International Inc. at C® 656. Refers to polymer products such as those commercially available.

The following examples further illustrate this disclosure, but should not be construed as limiting the scope of this disclosure in any way.
Additional Embodiment:

The present disclosure also provides an article comprising a substrate and a topcoat composition disposed on the substrate. The substrate can be either known in the art or described herein. In various embodiments, the substrate is wood, metal, plastic, or the like. Alternatively, the substrate is thermoplastic polyolefin, polyethylene terephthalate, polytetrafluoroethylene, polyvinyl chloride, polypropylene, polyethylene, high density polyethylene, low density polyethylene, ethylene vinyl acetate, polyvinyl alcohol, acetal, acrylic, polyvinyl chloride, acrylonitrile. It can be a low surface energy substrate selected from butadiene styrene, polyurethane, epoxy, polyester, nylon, phenols, polyimide, alkyd enamel, and combinations thereof. In another embodiment, the substrate is a low surface energy substrate selected from high density polyethylene, low density polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, and combinations thereof. In a further embodiment, the substrate is polypropylene. In various embodiments, the substrate can be thermoplastic polyolefin (TPO).

Polypropylene and TPO can be used as roofing films for painting signs, logos on flat roofs. Typically, the adhesion of the paint to polypropylene and / or TPO is not sufficient. Accordingly, various embodiments of the present disclosure address this lack of adhesion and enhanced adhesion for roofing film membranes. Therefore, the substrate can be further defined as a roofing material, a roofing film film, and the like.

The topcoat composition has a first side surface that is placed in direct contact on the substrate and a second side surface that is exposed to the environment on the outermost side. In other words, the first aspect of the topcoat composition is placed directly on the substrate so that there is no intermediate layer between them. For example, there is no binding layer or primer placed between the topcoat composition and the substrate. However, a corona treatment may be used to prepare the substrate for adhesion to the topcoat composition. In one embodiment, the first aspect of the topcoat composition is referred to as the bottom layer of the topcoat composition, which is placed in direct contact with the top layer of the substrate. The second aspect of the topcoat composition is exposed to the outermost, i.e., the environment. There are no other layers placed on the second side of the topcoat composition. In various embodiments, the second aspect of the topcoat is described as the top layer of the article exposed to the environment.

The topcoat composition comprises a first polymer, a second polymer and water. The topcoat composition may also contain any one or more of the additives described herein or known in the art. The first polymer may be any of the polymers described herein. The second polymer may also be any of the polymers described herein.

In one embodiment, the first polymer is an acrylic polymer, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resin, ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate, vinyl acetate copolymer, ethylene- (meth) acrylic. Acid ionomer, vinylidene chloride copolymer, ethylene- (meth) acrylate copolymer, polyester, natural rubber, neoprene, phenol polymer, polyurethane, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch, polysaccharides, 2 of them It is selected from the group consisting of one or more copolymers, two or more combinations thereof, and any two or more combinations thereof. In another embodiment, the first polymer is selected from acrylic polymers, ethylene-vinyl acetate copolymers, and combinations thereof. The first polymer may be an acrylic polymer. Alternatively, the first polymer may be an ethylene-vinyl acetate copolymer. Each of these polymers can be as described above.

In various embodiments, the topcoat composition is described as a commercially available paint, such as a paint inside or outside the house, a commercially available paint, comprising a second polymer added to the paint. Most typically, the paint is an external or commercial paint. For example, the first polymer may be a polymer found in any commercially available paint. Commercially available paints may be supplied by companies including, but not limited to, Benjamin Moore, Sherwin-Williams, Valspar, Behr, PPG, Glidden, Olympic, Dutch Boy and the like. In one embodiment, the topcoat composition comprises or is a commercially available paint to which a second polymer is added.

Now referring to the second polymer, in various embodiments, the second polymer, unlike the first polymer, is an ethylene-acrylic acid copolymer, polyethylene oxide, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl acetate. It is selected from the group consisting of copolymers, maleinated polyolefins, polyethylene homopolymers, polypropylene homopolymers, and combinations of any two or more thereof. The term "different" means that the first and second polymers are different at the molecular and molecular weight levels. However, it is still contemplated that both the first and second polymers can be of the same general type or genus. For example, both the first and second polymers can be ethylene-acrylic acid copolymers, but still differ because they have different physical properties such as weight average molecular weight.

In one embodiment, the second polymer is selected from ethylene-acrylic acid copolymers, ethylene oxide-vinyl acetate copolymers, maleated polyolefins, and combinations thereof. In another embodiment, the second polymer is an ethylene-acrylic acid copolymer. In a further embodiment, the second polymer is an ethylene oxide-vinyl acetate copolymer. In yet another embodiment, the second polymer is a maleated polyolefin. In yet another embodiment, the second polymer is polyethylene maleated. Further, the second polymer may be polypropylene maleated. Each of these polymers can be as described above.

The topcoat composition also contains water and can be described as a water-mediated coating or as a water-based coating. The amount of water may be any of those described herein and / or may be selected by one of ordinary skill in the art. In various embodiments, the water is 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, about 45 to about 50, or about, based on the total weight of the topcoat composition. It is present in the topcoat composition in an amount of about 50% by weight. In various non-limiting embodiments, all values and ranges of values, including between and above the above-mentioned values of both integers and decimals, are expressly herein for use in this specification. It is planned.

In addition, the topcoat composition may also contain a surfactant. Again, the surfactant can be any of those described herein. A single surfactant or two or more surfactants may be utilized. Surfactants can be utilized in any amount described herein.

In various embodiments, the topcoat composition has a particle size of about 10 nm to about 2000 nm and has a solid content of about 30, 35, 40, 45, or greater than 50% based on the total weight of the composition. Have. The solid content and / or particle size may be alternatives to any of those described herein. In other embodiments, the wet film has a thickness of about 25 to about 100, about 25 to about 75, about 25 to about 50, about 50 to about 100, or about 75 to about 100 micrometers, 100. Micrometer typically dries to about 50 micrometers.

In various non-limiting embodiments, all values and ranges of values, including between and above the above-mentioned values of both integers and decimals, are expressly herein for use in this specification. It is planned.

In still other embodiments, the substrate is corona treated. The corona treatment may be either known or described herein, such as in Examples.

The article may exhibit improved retention (eg, adhesion) of the topcoat to the substrate as compared to a topcoat that does not contain a second polymer. This can be reported as a percentage of topcoats removed or as a percentage of topcoats retained.

For example, the article is at least 4, 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 76, 80, 84, 88, It may exhibit 92, 96, or 100% topcoat retention (eg, adhesion). This can be surprising and superior, especially if comparative articles containing topcoats not of the present disclosure experience, for example, a low retention of zero. The tests used to determine retention are described in the Examples below, but any suitable ASTM test used for adhesion can be selected by one of ordinary skill in the art. In one embodiment, retention / adhesion describes the amount of topcoat that remains attached to the substrate after scoring, application of the tape, and then removal of the tape from the substrate. Typically, the adhesiveness of the tape removes a portion of the topcoat from the scored substrate. For example, 100% retention refers to the 100% topcoat remaining adhered to the substrate after removal of the tape. Typically, the test is performed using a 5x5 grid with 25 squares etched or scribed in the topcoat. Therefore, in such a test, if each square is removed, it is expressed as 4%. In various non-limiting embodiments, all values and ranges of values, including between and above the above-mentioned values of both integers and decimals, are expressly herein for use in this specification. It is planned.

Alternatively, topcoat retention / adhesion may be described / quantified as a percentage of topcoat removed. For example, 100% removal describes a scenario in which all of the topcoat is removed, which is not desirable. Using this type of quantification, the present disclosure shows that the amount of topcoat removed from the substrate is 0, 4, 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, Various embodiments are provided that are 48, 52, 56, 60, 64, 68, 72, 76, 80, 84, 88, 92, or 96%. This can be surprising and superior, especially if comparative articles containing topcoats not of the present disclosure experience, for example, 100% high removal. Again, the tests used to determine retention are described in the examples below, but any suitable ASTM test used for adhesion can be selected by one of ordinary skill in the art. Retention / adhesion typically describes the amount of topcoat that remains attached to the substrate after scoring, application of the tape, and then removal of the tape from the substrate. Typically, the adhesiveness of the tape removes a portion of the topcoat from the scored substrate. In various non-limiting embodiments, all values and ranges of values, including between and above the above-mentioned values of both integers and decimals, are expressly herein for use in this specification. It is planned.

The present disclosure also provides a method of forming an article. This method includes a step of preparing a substrate, a step of providing a topcoat composition, and a step of arranging the topcoat composition on the substrate to form an article. The topcoat composition can be cured using any mechanism known in the art. Typically, the test is performed using a 5x5 grid with 25 squares etched or scribed in the topcoat. Therefore, in such a test, if each square is removed, it is expressed as 4%.

The present disclosure further provides a cured article comprising a substrate and a cured topcoat having a first side surface placed in direct contact on the substrate and a second side exposed to the environment on the outermost side. do. The topcoat contains the cured product of the first polymer described above.

The present disclosure is also a method of forming an article comprising a substrate and a topcoat, wherein the topcoat is exposed to the environment on the first side surface and the outermost side where the topcoat is placed in direct contact with the substrate. Provides a method that has aspects of. The method comprises providing a substrate, water, and acrylic polymer, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resin, ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate, vinyl acetate copolymer, ethylene-. (Meta) ionomer acrylate, vinylidene chloride copolymer, ethylene- (meth) acrylate copolymer, polyester, natural rubber, neoprene, phenol polymer, polyurethane, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch, polysaccharides A step of providing an aqueous coating comprising a first polymer selected from the group consisting of two or more copolymers thereof, and two or more combinations thereof, and any two or more combinations thereof. include. The water-based coating can be as described above. For example, the water-based coating can also be described as any of the commercially available paints described above.

The method is also different from water, surfactants, and first polymers, ethylene-acrylic acid copolymers, polyethylene oxide, ethylene-vinyl acetate copolymers, ethylene-vinyl acetate-vinyl acetate copolymers, maleated polyolefins, polyethylene homopolymers, It comprises the steps of providing an emulsion of a homopolymer of polypropylene and a second polymer selected from the group consisting of any two or more combinations thereof. Emulsions are known in the art or can be formed using any of the methods described herein. Similarly, the emulsion is not particularly limited and may be of any kind recognized in the art. Further, the surfactant used in the emulsion may be any of those described herein. In various embodiments, the emulsion is described as a high solid-low surfactant emulsion containing, for example, up to about 50% by weight of solids and zero or less than about 5% by weight of surfactant. Alternatively, an emulsion may be formed using a more typical method, wherein the emulsion comprises from about 25 to about 30% by weight of solid and only a small percentage of its value is a surfactant.

The method also comprises combining the emulsion with the aqueous coating composition. The emulsion is typically added to the aqueous coating. Alternatively, an aqueous coating may be added to the emulsion. The step of adding may be performed in one step or several steps.

The method applies a combination of an emulsion and an aqueous coating composition to a substrate and has a top having a first side surface that is placed in direct contact on the substrate and a second side surface that is exposed to the environment on the outermost side. It further comprises the step of forming a coat. Optionally, the method may include the step of curing the topcoat. The curing step can be accomplished using any of the curing mechanisms described herein or in the art.

Example 1: Preparation of pressure-sensitive adhesive and pressure-sensitive adhesive label

The jacketed container was preheated to a temperature of 95-100 ° C. The temperature was controlled by an oil jacket containing oil at a temperature of about 115-120 ° C. Then 320 g of water was added to the container and the temperature was adjusted to 96-99 ° C. Stirring was started (using a Lightning RS500 saw blade), a small amount of potassium hydroxide was added and mixed with water for 5 minutes. Then, a small amount (less than about 2%) of the surfactant JPHOS® (registered trademark) 1066 (commercially available from J1 Technologies Ltd. (Manchester, UK)) containing an alkyl ether phosphoric acid ester and phosphoric acid is added. , Water was mixed for 5 minutes to form an aqueous phase emulsion. Trademark name AC® 5120, Honeywell International Inc. Commercially available ethylene-acrylic acid copolymers or copolymers from Honeywell International Inc. under the trade name AC® 656. A 25:75 mixture with a commercially available polyethylene oxide polymer was pre-melted with an additive (5% w / w industrial white oil) at a temperature of about 110-115 ° C. The material was then thawed and mixed with slow stirring. The stirring speed was then increased to 960-1000 RPM and the molten wax phase was added to the center of the mixer containing the aqueous phase (see above) over a period of 3-5 minutes. The temperature was maintained at 97-99 ° C. Therefore, a preliminary emulsion was formed at this stage and was mixed for an additional 5 minutes. 16 g of potassium hydroxide was added over a period of 1-2 minutes. At this stage, when potassium hydroxide was further added, a gradual increase in viscosity was observed. Mixing was continued for another 5 minutes. The average particle size of the obtained emulsion was in the range of 0.3 to 0.6 micrometer. The pH of this high viscosity emulsion was then adjusted without affecting the particle size. Specifically, a small amount of 85% acetic acid in an amount of 1% (v / v) of the total emulsion was added to 60 g of hot water (temperature was in the range of 80-90 ° C.) in a separate container. The resulting mixture was stirred. The dilute acetic acid was then added to the viscous emulsion (see above) over a period of 1-2 minutes. The emulsion became thinner and its viscosity was dramatically reduced. The final product was first cooled using a vessel jacket and then fast cooled to 35 ° C. in a sink or in-line cooler. When the temperature fell below 35 ° C, a small amount of biocide was added to the product. The product was then filtered through a 200 micrometer filter to produce emulsified polymer particles corresponding to the second polymer b) of the present disclosure. The final specifications of the emulsion of the second polymer b) were as follows: the solid content was about 56%, the viscosity was 350-1500 cps (60 RPM Brookfield no. 3 spindle) and the pH was 8. It was ~ 8.5 and the D50 particle size was 0.35 ~ 0.6 micrometer. Emulsions of the other waxes described herein (AC® 655, AC® 645P) can be prepared using a similar process.

The first polymer component (a) in the form of an acrylate polymer or copolymer emulsion is then provided, the pH is adjusted to 7.5-8.0, and the dispersed tackifier resin is stirred at low speed (200-400 RPM). It was added slowly over a period of 1 to 2 minutes. After 5 minutes, a wax emulsion (see above) was added over a period of 1-2 minutes and the resulting mixture was stirred for 5 minutes. A wetting agent (LUMITIN® ISC (BASF)) was added and optionally water was also added to reach the desired viscosity. The adhesive was adjusted to 300-800 cps with a 60 RPM Brookfield No. 3 spindle 60 RPM. Different adhesives were then applied to the labels according to procedures generally known in the art and the labels were tested as described elsewhere herein.

A first selected from the group consisting of acrylate polymers or copolymers of different relative concentrations, tackifier resins, and ethylene-acrylic acid copolymers, polyethylene oxide, ethylene-vinyl acetate-vinyl acetate copolymers, maleated polyolefins, and combinations thereof. Adhesives with the polymers of 2 were produced by using the appropriate amount of starting material. For example, about 14 to 28 parts (weight) of a commercially available acrylate copolymer from BASF Corporation (Charlotte, NC, USA) under 72 parts (weight) of the brand name ACRONAL® V215 to produce a total of 100 parts. ), A commercially available rosin ester resin from Eastman Chemical Company (Kingsport, TN, USA) under the trademark TACOLYN ™ 3509, and Honeywell International under the trademark name AC (registered trademark) 5120 of 0 to about 14 parts (weight). Inc. The adhesive according to Example 2 below was produced by combining with a commercially available ethylene-acrylic acid copolymer. The amount of these different components in the final adhesive can also be determined using generally known techniques that are standard in the art.
Example 2: Test of pressure-sensitive adhesive label

Shear resistance on stainless steel (shear), loop tack to low density polyethylene (Tack Poly) and loop tack to stainless steel (Tack SS), and peel adhesive to thick paper (Peel Card) and to low density polyethylene. For Peel Poly, pressure-sensitive adhesive tapes containing different adhesives as described in Example 1 above were tested. As shown in FIG. 1, the measurements were carried out as described above, except that stainless steel was replaced with low density polyethylene and cardboard as the adhesive. FIG. 1 shows a different pressure-sensitive adhesive containing a commercially available acrylate copolymer from BASF Corporation (Charlotte, NC, USA) under the trade name ACRONAL® V215, which is about 72% by weight (of the total weight of the adhesive). Shows the adhesive properties on the substrate. In addition, the pressure sensitive adhesive is a rosin ester resin commercially available from Eastman Chemical Company (Kingsport, TN, USA) under the trade name TACOLYN ™ 3509, in% of the indicated weight (of the total weight of the adhesive), and Trademark name AC® 5120, Honeywell International Inc. Contains a commercially available ethylene acrylic acid copolymer from. The units of measurement are Newton (about 2.5 cm: peeling and tacking) and time (shearing) per inch. The order in which the test results for different adhesives are shown in the histogram is the order in which the different adhesives are mentioned in the description of the figure below the histogram (left-to-right, top-to-bottom: this also applies to Figures 2-6. Corresponds to. The bars that reflect the shear adhesion of the two adhesives containing the highest amount of AC® 5120 product are shredded due to the small size of the histogram in this figure. FIG. 2 shows a large histogram that accurately reflects the shear adhesion of these adhesives. Shear adhesion was determined based on adhesion to stainless steel. Loop tack was determined based on adhesion to low density polyethylene (Tack Poly) or adhesion to stainless steel (Tack SS). Peel adhesion was determined based on adhesion to low density polyethylene (Peel Poly) or adhesion to cardboard (Peel Card).

The pressure-sensitive adhesive tape was then degraded for 3 days at 100% relative humidity at 50 ° C. and tested for loop tack on low density polyethylene and peel card on thick paper as described above. (Fig. 3).

Similar tests were performed with a pressure sensitive adhesive containing a commercially available acrylate copolymer from Organic Kimya (Turkey) under the name ORGAL AX1260 instead of the ACRONAL® V215 product (FIGS. 4 and 5). There are no data points for degraded adhesives containing 10% AC® 5120 wax products (FIG. 5).

Also, an acrylate copolymer commercially available from BASF Corporation (Charlotte, NC, USA) under the trade name ACRONAL® V215, which is about 65% by weight (of the total weight of the adhesive), about 25% by weight (of the total weight of the adhesive). % Brand name AQUATAC ™ XR4343 from Arizona Chemical (FL, USA) commercially available rosin dispersion, and trademark name AC® 5120 from Honeywell International Inc. Honeywell International Inc., commercially available from Ethylene-Acrylic Acid Copolymer under the trade name AC® 656. A similar test was performed with a pressure sensitive adhesive containing about 10% by weight (of the total weight of the adhesive) of a 25:75 mixture with a commercially available polyethylene oxide polymer. FIG. 6 shows the same measurement results as those at the bottom of FIG. SS represents stainless steel and LDPE represents low density polyethylene.

The above measurements show that the adhesive containing the AC® 5120 wax product had significantly better shear resistance than the adhesive without it. As can be seen in FIGS. 1 and 2, for example, an adhesive containing 14% AC® 5120 wax product had a shear resistance of approximately 120 hours, but not. The adhesive had a shear resistance of only about 8 hours. After degradation, adhesives containing the AC® 5120 wax product appeared to have significantly better performance than adhesives without it.
Example 3: Other Pressure Sensitive Adhesive

Trademark names AC® 645P and AC® 655, Honeywell International Inc. Also prepare pressure sensitive adhesives containing commercially available polymer products from. These pressure sensitive adhesives are manufactured according to the information provided in Example 1 and tested as above.
Example 4: Pressure-sensitive adhesive containing no rosin

A pressure-sensitive adhesive that does not contain a rosin tackifier resin is also prepared. These adhesives are acrylate polymers or acrylate polymers comprising a polymerization monomer selected from the group consisting of acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, octyl acrylate, styrene, vinyl acetate, and combinations of two or more thereof. A first polymer that is a copolymer and a second polymer selected from the group consisting of ethylene-acrylic acid copolymers, polyethylene oxide, ethylene-ethylene oxide-vinyl acetate copolymers, maleated polyolefins, and combinations of two or more thereof. Contains only. These pressure sensitive adhesives are manufactured according to the information provided in Example 1 and tested as described above.
Example 5: Heat Seal Adhesive

Two aqueous heat seal adhesives are prepared for evaluation. Sample A (control) is an ethylene-vinyl acetate emulsion (60% solid). Sample B is a blend of 90% ethylene-vinyl acetate emulsion (Sample A) and 10% low molecular weight ethylene-acrylic acid copolymer (AC® 5120 from Honeywell) emulsion (53% solid). Is. The emulsion is coated on 2 mils of aluminum foil and dried in a ventilation oven at 105 ° C. to give a coating of 30 gm. The coated foil is cut into small individual pieces (1 inch x 6 inches), which are then heat-sealed to uncoated aluminum foil at 60 psi using a residence time of 2 seconds and a temperature of 80 ° C. do. After adjusting at 72 ° F. and 50% relative humidity for 24 hours, the laminate is stripped at a rate of 12 inches / minute in a tensile tester. Measure and record the peeling force. Sample B exhibits 25% higher peeling adhesion than Sample A.
Example 6: Rheology of Aqueous Acrylic Pressure Sensitive Adhesive

ACRONAL® V215 (BASF) is a common water-based acrylic pressure-sensitive adhesive that is supplied in 69% solid form and is widely used in the manufacture of self-adhesive labels and tapes. ACRONAL® V215 is combined with a 40% solid emulsion of ethylene-acrylic acid (EAA) copolymer with 15 wt% acrylic acid and a number average molecular weight of approximately 2000 daltons for stable water-based adhesion. Agent compositions A, B, C and D were obtained. The sample was cast into a silicone rubber molding die and dried to obtain a dry adhesive portion suitable for rheology evaluation.

Dynamic mechanical analysis using the TA Instruments AR2000 Leometer equipped with a parallel plate shape of stainless steel (diameter 8 mm and measurement gap 1000 μm) with a vibration frequency of 1.0 Hz and a maximum strain applied of 0.050%. Was carried out. In each measurement, a fixed temperature gradient (2.5 ° C./min) was applied to the sample to allow evaluation of the viscous properties of the sample, which correlates with temperature.

The results are presented in Table 1, which contains data at -25, 0, and 25 ° C.

The viscoelastic balance of adhesives A, B, C, and D (as described by the tandelta value) was found to be consistent with pressure sensitive performance, however, adhesives B, C, and D. It was found that the elastic modulus and viscosity of the adhesive A were significantly higher than those of the adhesive A. Therefore, the adhesives B, C, and D provide excellent bonding and load bearing performance as a result of including the ethylene-acrylic acid copolymer.
Example 7: Adhesive performance of aqueous vinyl acetate ethylene acrylic acid ester adhesive

MOWILITH® LDM1365 (Celanese) is an aqueous copolymer dispersion based on vinyl acetate, acrylic acid ester, and ethylene (VAE) supplied in 60% solid form. It is a widely used raw material in the formulation of adhesives for the paper and packaging markets. MOWILITH® LDM1365 was combined with an ethylene-acrylic acid copolymer emulsion, wetting agent, and water to give approximately 55% solid water-based adhesive compositions X and Y. An emulsion of ethylene-acrylic acid copolymer was prepared in 53% solid, which featured a copolymer with 15% by weight acrylic acid and a number average molecular weight of approximately 2000 daltons. The wetting agent, JMULSE® 1444B3 (J1 Technologies), was included in 0.7% of the aqueous mixture. For testing, an adhesive coating was prepared on a 25 μm polyester film with a constant dry coating weight (24 gsm). Peeling, loop tack, probe tack, and shear characteristics of these coatings were evaluated according to well-established test methods; see Table 2.

It has been found that the characteristics of the modified adhesive (Y) are superior to those of the unmodified product (X).
Example 8: Rheology of Aqueous Vinyl Acetate Ethylene Acrylic Acid Adhesive

Dynamic mechanical analysis was performed to determine the viscoelastic characteristics of the adhesives X and Y (described in Example 7). The sample was cast into a silicone rubber molding die and dried to obtain a dry adhesive portion suitable for the test. Measurements were performed using a TA Instruments AR2000 leometer fitted with a parallel plate shape of stainless steel (diameter 8 mm and measurement gap 1000 μm) at a vibration frequency of 1.0 Hz and a maximum strain applied of 0.025%. .. In each measurement, a fixed temperature gradient (1.0 ° C./min) was applied to the sample to allow evaluation of the characteristics of the sample that correlate with temperature. The results are presented in FIG.

The inclusion of the ethylene-acrylic acid copolymer in the adhesive did not alter the viscoelastic balance (as indicated by the tandelta value), however, the elasticity and viscosity of the adhesive Y was that of the adhesive X. It was found to be significantly higher than the one. Therefore, the adhesive Y provides excellent bonding and load bearing performance as a result of its modification.
Example 9: Adhesive performance of the tackled water-based adhesive

The effect of incorporating the ethylene-acrylic acid copolymer emulsion into the tackled water-based acrylic pressure-sensitive adhesive was considered. Adhesive bases are ACRONAL® V215 (BASF), water-based acrylic pressure-sensitive adhesives, EMULTROLL® E177 (Concentrol Chemical Specialties), aqueous dispersions of rosin ester tackifiers, and JMULSE®. It was formulated with 1444B3 (J1 Technologies), a wetting agent, to which an emulsion of an ethylene-acrylic acid copolymer was added. The adhesive-based composition is ACRONAL® V215 (100.0 parts by weight), EMULTROL® E177 (40.5 parts by weight), and JMULSE® 1444B3 (1.3 parts by weight). there were. The adhesive base was combined with an ethylene-acrylic acid copolymer emulsion prepared in 53% solid, featuring a copolymer having 15% by weight acrylic acid and a number average molecular weight of approximately 2000 daltons. Then, a pressure-sensitive laminate was prepared. Wet adhesive was applied to a silicone coated release liner and dried in a laboratory oven to obtain a uniform (20 gsm) dry adhesive coating, which was laminated with 80 g of face paper. The resulting laminate was adjusted to 23 ± 1 ° C./50 ± 5% Rhes and then tested according to a well-established procedure; see Table 4.

It was found that the peeling, tacking and shearing performance of the modified adhesives (L and M) was superior to that of the unmodified adhesive (K).
Example 10: Adhesive performance of water-based acrylic adhesive

Adhesive HKJ23 (Adhesivos) is an aqueous acrylic copolymer dispersion supplied in about 53.5% solid. It is a widely used raw material in the formulation of adhesives for paper, polyolefin labels, and decal markets. Adhesivos HKJ23 was combined with an ethylene-acrylic acid copolymer emulsion and an ethylene-acrylic acid copolymer (25%) / polyethylene oxide (75%) dispersion to give an approximately 55% solid water-based adhesive composition. An emulsion of ethylene-acrylic acid copolymer was prepared in 53% solid, which featured a copolymer with 15% by weight acrylic acid and a number average molecular weight of approximately 2000 daltons. Emulsions of ethylene-acrylic acid copolymer (25% by weight) and polyethylene oxide (75% by weight) were prepared as approximately 50% solids and their number average molecular weight was determined to be approximately 1,300. The formulations are listed in Table 5A. For testing, an adhesive coating was prepared on a 25 μm polyester film with a constant dry coating weight (24 gsm). Their exfoliation, loop tack, and shear characteristics were evaluated according to well-established test methods; see Table 5B.

プロセスの説明： It was found that the characteristics of the modified adhesives (Q, R, S, and T) were superior to those of the unmodified product (P).
Example 11: Process formulation for preparing EAA emulsions, AC® 5120 emulsions

Process description:

The wax and industrial white oil were pre-blended and kept in an oven at 110-115 ° C. overnight. Prior to use, the wax / oil was mixed in the formulation for 5 minutes using a simple lab mixer.

The emulsion vessel was preheated before starting the process. The oil temperature was set to 120 ° C. After adding hot water, the dispersion container was stabilized for 15 minutes. Hot water at 95 ° C. + was added to the vessel and the stirrer blade was set to operate at 580 RPM. This was mixed for 15 minutes. The first KOH was added and mixed for 5 minutes. JMULSE® 3527 (J1) was added and mixed for 5 minutes. The temperature at this stage was confirmed and found to be usually 92-95 ° C. Wax / industrial white oil was added to a steady stream at a temperature of 110-115 ° C over a period of 4-5 minutes. It was found that the temperature rose at this stage and it was important to adjust the heating oil to compensate for the temperature rise or loss. The mixer speed was increased to 960 RPM to add the wax. It was found that the temperature after the addition of wax was usually 97-99 ° C. After the waxing was complete, the product was held for 5 minutes. The temperature at this stage was 95-99 ° C. The second KOH was added slowly over 2-3 minutes. At this stage, the need for emulsions increased significantly. Upon completion of KOH addition, the product was held at 960 RPM for 10 minutes. The temperature was maintained at 95-99 ° C (must be kept boiling). At the end of the process, a solution of acetic acid and boiling water was added. The water temperature was at least 85 ° C. This was added to the steady flow over 2-3 minutes and cooling was set to reduce the emulsion temperature below 45 ° C. This usually takes 45 minutes. After mixing for 5 minutes, the speed of the disperser was reduced to 580 RPM. When the temperature dropped below 50 ° C., JMULSE® 1444B3 was added to the steady flow. Cooling was continued until the product reached 45 ° C., then the product was discharged. The final emulsion was cooled to 30-35 ° C. in a closed container, filtered through a 100 mesh and placed in a sealed sample container.

A biocide was added to the final product. This was diluted 10/1 with water for addition.

If the product appears to be very viscous at this stage, additional water may be added to prevent film formation. If some film formation occurs during the final step, the product may be refiltered.

specification:
Solid content 54-56%
pH 7.5-8.5
60 RPM, no. Viscosity 350-800 Cps with 3 spindles, Brookfield
Particle size, typically 0.3 / 0.4 micrometer x 50
Example 12: PCP002, AC® 5656 / AC® 5120 process for preparing an emulsion.

プロセスの説明 Formulation

Process description

The two wax components (AC® 656 and AC® 5120) were pre-blended with industrial white oil and held overnight in an oven at 110-115 ° C. Prior to use, the wax / oil was mixed in the formulation for 5 minutes using a simple lab mixer. The emulsion vessel was preheated before starting the process. The oil temperature was set to 120 ° C. After adding hot water, the dispersion container was stabilized for 15 minutes.

Hot water at 95 ° C. + was added to the vessel and the stirrer blade was set to operate at 580 RPM. This was mixed for 15 minutes. KOH was added and mixed for 5 minutes. The first JPHOS® 1066 was added and mixed for 5 minutes. The temperature at this stage was confirmed and found to be usually 92-95 ° C. Wax / industrial white oil was added to a steady stream at a temperature of 110-115 ° C over a period of 4-5 minutes. It was found that the temperature rose at this stage and it was important to adjust the heating oil to compensate for the temperature rise or loss. The mixer speed was increased to 960 RPM to add the wax. It was found that the temperature after the addition of wax was usually 97-99 ° C. After the waxing was complete, the product was held for 5 minutes. The temperature at this stage was 95-99 ° C. The second JPHOS® 1066 was added slowly over 2-3 minutes. At this stage, the VIS of the emulsion increased.

Upon completion of the second JMULSE® addition, the product was retained at 960 RPM for 10 minutes. The temperature was maintained at 95-99 ° C (must be kept boiling). Cooling was then applied and the product was cooled to 85-88 ° C. with continued high speed mixing. At the end of the process, a solution of acetic acid and boiling water was added. The water was at least 85 ° C. This was added to the steady flow over 2-3 minutes and cooling was set to reduce the emulsion temperature below 45 ° C. This usually takes 45 minutes. After mixing for 5 minutes, the speed of the disperser was reduced to 580 RPM. When the product temperature dropped below 50 ° C., JMULSE® 1444B3 was added to the steady flow. The product continued to cool to 45 ° C. and then drained. The final emulsion was cooled to 30-35 ° C. in a closed container, filtered through a 100 mesh and placed in a sealed sample container. A biocide was added to the final product. This was diluted 10/1 with water for addition. If the product appears to be very viscous at this stage, additional water may be added to prevent film formation. If some film formation occurs during the final step, the product may be refiltered.

Product specifications:
Solid content 50-52%
pH 7.5-8.5
60 RPM, no. Viscosity 350-800 cps with 3 spindles, Brookfield
Particle size, typically 0.7 micrometer x 50
Example 13: Emulsion test of Example 11, Example 12, and AC® polymer additive in Chimigraf flexo ink formulation.

40 parts of pigment (BLUE206HC CUAT from Chimigraf) and 60 parts of varnish (also VARNISH COMPLEMENT 07 from Chimigraf) are mixed and stirred with a Speed Mixer at 3000 rpm for 2 minutes to control flexo from Formulation A (Chimigraf). Ink compounding) was produced. 5 to 25 parts of the emulsion of Example 11 (SFAC® 5120 emulsion), the emulsion of Example 12, or the other AC (5 and 25%, respectively) added to Formulation A. Formulations BK (see table below) were made by adding a (registered trademark) polymer emulsion and mixing at 3000 rpm for 30 seconds at high speed.
Example 14: Adhesion 1 hour and 4 hours after coating (tape test)

Adhesion tests were performed by grid scoring onto the sample and by crimping SCOTCH® 610 adhesive tape onto the grid scoring and then pulling it off at two different speeds (low speed and high speed). Samples were graded from 0 to 5 (0 removed no material, 5 removed most of the material). The sample was air dried for 1 hour and tested, then dried for an additional 3 hours for a total of 4 hours and tested again. The photograph (FIG. 7) shows an example showing poor adhesion. Blue spots (Fig. 7B) were lifted from the blue printed matter onto the transparent tape, and white spots (Fig. 7A) were lifted from the printed matter onto the blue film as a result of the blue movement onto the transparent tape. there were.
Example 15: Sutherland frictional resistance before and after immersion in water.

追加の観察： A 400-cycle Sutherland friction test was performed using a sample taped to the floor and a course white typing paper taped to a 4-pound test weight. The samples were air dried for 24 hours, then the starting sample was run, the samples were placed separately in a bucket of water at 2 ° C. for 4 hours, placed in a bucket of water at ambient temperature for 24 hours, and then tested. Samples were graded on a scale of 0-5 (0 for colorless and 5 for more ink) for the amount of ink transferred to the paper. Most samples were thin (2) to very white (1), adding points to severe muscle.

Additional observations:

All samples passed the nail scratch test.

Some minor mix / compatibility issues with Formula E using 25% AC® 5120 emulsion (Example 11) and Formula B using 5% Example 12 emulsion were samples. Can cause streaks with some spots and rubbing.

Some samples have powdery peeling on adhesion tests, which is believed to be the pigment on the surface of the film.
Example 16: Emulsion of ethylene acrylic acid copolymer without surfactant

Example 16 is an oil-in-water emulsion of a single ethylene acrylic acid copolymer formulated in 40% by weight of the copolymer. The copolymer has 15% by weight acrylic acid and has a number average molecular weight of approximately 2000 Dalton. Surfactant-free copolymer emulsions were simply made by partially converting the copolymer to soap through the use of bases. Ammonia hydroxide was used in this particular embodiment, however, many other inorganic and organic bases are preferred. The formulations of Example 16 are shown in Table 6. Table 6: Emulsion formulation of Example 16

An emulsion was prepared by combining an ethylene acrylic acid copolymer (40.00 parts), a 30% ammonium hydroxide solution (2.00 parts), and water (38.00 parts) in a reactor. The reactor was closed and the product temperature was raised to 95 ° C. using continuous high shear mixing. The product temperature and shear environment were maintained for 10 minutes. Separately, water (20.00 parts) was heated to 95 ° C. and then poured into the reactor.

The product temperature and shear environment were maintained for an additional 10 minutes.

The product was cooled to room temperature with continuous mixing. The resulting product had a pH of 8.7, a Brookfield viscosity of 220 cp, and showed a narrow particle size distribution centered around 0.2 μm.
Example 17: Emulsion of a mixture of ethylene acrylic acid copolymers containing no surfactant

Example 17 is an oil-in-water emulsion of a mixture of ethylene acrylic acid copolymers blended in 35% by weight of the copolymer. The first copolymer (EAA1) has 10% by weight acrylic acid and has a number average molecular weight of approximately 1100 daltons. The second copolymer (EAA2) has 20% by weight acrylic acid and has a number average molecular weight of approximately 2250 daltons. Surfactant-free copolymer emulsions were made by partially converting the copolymer to soap through the use of bases. In this example, an organic base, 2-amino-2-methyl-1-propanol, was used, however, many other inorganic and organic bases are preferred. The formulations of Example 17 are listed in Table 7.

Ethylene Acrylic Acid Copolymer EAA1 (29.75 parts), Ethylene Acrylic Acid Copolymer EAA2 (5.25 parts), 2-Amino-2-methyl-1-propanol (2.64 parts), and Water (32.36 parts) Emulsions were prepared by combining and combined in a reactor.

The reactor was closed and the product temperature was raised to 95 ° C. using continuous high shear mixing. The product temperature and shear environment were maintained for 10 minutes.

Separately, water (30.00 parts) was heated to 95 ° C. and then poured into the reactor.

The product temperature and shear environment were maintained for an additional 10 minutes.

The product was cooled to room temperature with continuous mixing. It was found that the characteristics of the resulting product were similar to those of the emulsion of Example 16.
Example 18: Emulsion of ethylene acrylic acid copolymer

Example 18 is an oil-in-water emulsion of a single ethylene acrylic acid copolymer formulated in 52.75% by weight of the copolymer. The copolymer has 15% by weight acrylic acid and has a number average molecular weight of approximately 2000 Dalton. The emulsion is stabilized through the combination of copolymer soap and anionic surfactant. Copolymer soaps are made in-situ using potassium hydroxide with a 45% aqueous solution for preparation to facilitate its use and accurate addition, and the anionic surfactant is JPHOS® 1066. (J1 Technologies (Manchester, UK)). The formulations of Example 18 are shown in Table 8.

Emulsions were prepared by combining ethylene acrylic acid copolymers (52.75 parts) and water (28.50 parts) and combined in a reactor. The reactor was closed and the product temperature was raised to 110 ° C. using continuous high shear mixing. The product temperature and shear environment were maintained for 10 minutes.

An aliquot of 45% potassium hydroxide solution (0.50 part) was injected into the reactor. JPHOS® 1066 (1.08 part) was injected into the reactor. The remaining 45% potassium hydroxide solution (2.20 parts) was injected into the reactor. The product temperature and shear environment were maintained for 20 minutes.

A dilute acetic acid solution was prepared separately from water (14.87 parts) and glacial acetic acid (0.10 parts) and heated to 95 ° C.

Then a hot dilute acetic acid solution was injected into the reactor.

The product temperature and shear environment were maintained for an additional 10 minutes.

The product was cooled to room temperature with continuous mixing.

The resulting product had a pH of 7.9, a Brookfield viscosity of 3000 cp, and showed a narrow particle size distribution centered around 0.2 μm.
Example 19: Emulsion of a mixture of ethylene acrylic acid copolymer and mineral oil

The inclusion of mineral oil in adhesives, inks, or coating compositions is often economically or technically advantageous. This example shows the preparation of an emulsion of a mixture of ethylene acrylic acid copolymer and mineral oil.

Example 19 is an oil-in-water emulsion of ethylene acrylic acid copolymer and mineral oil blended with 49.90% by weight copolymer and 2.85% by weight of oil. The copolymer has 15% by weight acrylic acid and has a number average molecular weight of approximately 2000 Dalton. The mineral oil selected was SIPMED® 15 (SIP (London, UK)). The emulsion is stabilized through the combination of copolymer soap and anionic surfactant. Copolymer soaps are made in-situ using potassium hydroxide with a 45% aqueous solution for preparation to facilitate its use and accurate addition, and the anionic surfactant is JPHOS® 1066. (J1 Technologies (Manchester, UK)). The formulations of Example 19 are shown in Table 9.

Emulsions were prepared by combining ethylene acrylic acid copolymers (49.90 parts), SIMMED® 15 (2.85 parts), and water (28.50 parts) and combined in a reactor.

The reactor was closed and the product temperature was raised to 110 ° C. using continuous high shear mixing. The product temperature and shear environment were maintained for 10 minutes.

An aliquot of 45% potassium hydroxide solution (0.50 part) was injected into the reactor. JPHOS® 1066 (1.08 part) was injected into the reactor.

The remaining 45% potassium hydroxide solution (2.20 parts) was injected into the reactor.

The product temperature and shear environment were maintained for 20 minutes.

A dilute acetic acid solution was prepared separately from water (14.87 parts) and glacial acetic acid (0.10 parts) and heated to 95 ° C.

Then a hot dilute acetic acid solution was injected into the reactor.

The product temperature and shear environment were maintained for an additional 10 minutes.

The product was cooled to room temperature with continuous mixing.

It was found that the characteristics of the resulting product were similar to those of Emulsion Example 18.
Example 20: Emulsion of a mixture of ethylene acrylic acid copolymer and polyethylene oxide homopolymer

Example 20 is an oil-in-water emulsion of an ethylene acrylic acid copolymer and a polyethylene oxide homopolymer. It is formulated with 10.73% by weight copolymer and 32.17% by weight polyethylene oxide and contains 3.23% by weight mineral oil. The copolymer has 15% by weight acrylic acid and has a number average molecular weight of approximately 2000 Dalton. Polyethylene oxide has a number average molecular weight of approximately 1200 daltons and an acid value of 15 mg KOH / g. The mineral oil selected was SIPMED® 15 (SIP (London, UK)). The emulsion is stabilized through the combination of copolymer soap and anionic surfactant. Copolymer soaps are made in-situ using potassium hydroxide with a 45% aqueous solution for preparation to facilitate its use and accurate addition, and the anionic surfactant is JPHOS® 1066. (J1 Technologies (Manchester, UK)). Wetting and biocides are also included in the formulation. The wetting agent was JMULSE® 1444B3 (J1 Technologies (Manchester, UK)). The biocide was ACTICIDE® MBS (Thor Specialities (Northwich, UK)). The formulations of Example 20 are shown in Table 10.

Emulsion is prepared by combining ethylene acrylic acid copolymer (10.73 parts), polyethylene oxide homopolymer (32.17 parts), SIMMED® 15 (3.23 parts), and water (22.00 parts). And combined in the reactor. The reactor was closed and the product temperature was raised to 110 ° C. using continuous high shear mixing. The product temperature and shear environment were maintained for 10 minutes. An aliquot of 45% potassium hydroxide solution (0.30 parts) was injected into the reactor. JPHOS® 1066 (1.67 parts) was injected into the reactor.

The remaining 45% potassium hydroxide solution (1.80 parts) was injected into the reactor.

The product temperature and shear environment were maintained for an additional 20 minutes.

Dilute acetic acid solutions were prepared separately from water (26.76 parts) and glacial acetic acid (0.10 parts).

Then a cold dilute acetic acid solution was injected into the reactor.

The product temperature and shear environment were maintained for an additional 10 minutes. The product was cooled to 40 ° C. or lower with continuous mixing.

JMULSE® 1444B3 (0.34 parts) and ACTICIDE® MBS (0.90 parts) were added with continuous mixing.

The product was then cooled to room temperature with continuous mixing.

The resulting product had a pH of 8.1, a Brookfield viscosity of 800 cp, and showed a narrow particle size distribution centered around 0.2 μm.
Example 21: Emulsion of a mixture of ethylene acrylic acid copolymer and rosin ester

The inclusion of rosin esters in adhesives, inks, or coating compositions is often economically or technically advantageous. This example shows the preparation of an emulsion of a mixture of ethylene acrylic acid copolymer and rosin ester.

Example 21 is an oil-in-water emulsion of ethylene acrylic acid copolymer and rosin ester blended with 38.75% by weight copolymer and 12.95% by weight rosin ester. The copolymer has 15% by weight acrylic acid and has a number average molecular weight of approximately 2000 Dalton. The rosin ester selected was SYLVATAC® RE85 (Arizona Chemical (Almere, The Netherlands)). The emulsion is stabilized through the combination of copolymer soap and anionic surfactant. Copolymer soaps are made in-situ using potassium hydroxide with a 45% aqueous solution for preparation to facilitate its use and accurate addition, and the anionic surfactant is JPHOS® 1066. (J1 Technologies (Manchester, UK)). The formulations of Example 21 are shown in Table 11.

Emulsions were prepared by combining ethylene acrylic acid copolymers (38.75 parts), SYLVATAC® RE85 (12.95 parts), and water (28.00 parts) and combined in a reactor.

The reactor was closed and the product temperature was raised to 110 ° C. using continuous high shear mixing. The product temperature and shear environment were maintained for 10 minutes. An aliquot of 45% potassium hydroxide solution (0.50 part) was injected into the reactor. JPHOS® 1066 (3.10 parts) was injected into the reactor. The remaining 45% potassium hydroxide solution (2.14 parts) was injected into the reactor. The product temperature and shear environment were maintained for 20 minutes. A dilute acetic acid solution was prepared separately from water (14.46 parts) and glacial acetic acid (0.10 parts) and heated to 85 ° C. The dilute acetic acid solution was then injected into the reactor.

The product temperature and shear environment were maintained for an additional 10 minutes. The product was cooled to room temperature with continuous mixing.

The resulting product had a pH of 8.5, a Brookfield viscosity of 1500 cp, and showed a narrow particle size distribution centered around 0.2 μm.
Additional Examples:

All paints and additives were calculated at a filling level of 15% based on the material solid and then mixed using Speed Mixer, DAC 150 FVZ K for a total of 6 minutes in 3 cycles at 2 minute intervals. Each film (ie, substrate) was washed with IPA prior to coating. The film was then coated with Behr semi-gloss and outer flatness using a 3 mil drawdown bar. After the film was dried, the coating was scratched horizontally and vertically with a stitch pattern using a razor blade. Typically, the test is performed using a 5x5 grid with 25 squares etched or scribed in the topcoat. Therefore, in such a test, if each square is removed, it is expressed as 4%. The tape was then pressed firmly onto the stitched portion using 3M 610 Scotch tape and then consistently stripped from each film sample. The percentage of paint removed is then recorded and listed in Table 12 below. These percentages can be described as retention or adhesion of the topcoat to the substrate, as first introduced above. Alternatively, any suitable ASTM test may be selected and used by one of ordinary skill in the art.

The visual results for semi-glossy white # 5450 are shown in FIGS. 8A-K.

Visual results for external flat # 4450 are shown in FIGS. 9A-E.

Numerical results of the percentage of paint removed are listed in Table 12 below, all values are percentages. Further, the term "CT4X" refers to four corona treatments of polypropylene.

Polypropylene is commercially available from Film Tech.

P1 is an example of a second polymer, a maleated polypropylene having about 25.6% solid and made of anionic surfactant. It has a Meter drop point (ASTM D-3954) at about 141 ° C, a hardness less than about 0.5 dmm (ASTM D-5), a density of about 0.94 g / cc (ASTM D-1505), and about 190 ° C. It has a viscosity of 350 cps (Blockfield), a saponification number of about 87 mg KOH / g, about 72% MAH binding%, and about 63 mg KOH / g bound SAP #.

P2 is an example of a second polymer, a maleated polypropylene having about 39% solid and made with a nonionic surfactant. It has a Meter drop point (ASTM D-3954) at about 141 ° C, a hardness less than about 0.5 dmm (ASTM D-5), a density of about 0.94 g / cc (ASTM D-1505), and about 190 ° C. It has a viscosity of 350 cps (Blockfield), a saponification number of about 87 mg KOH / g, about 72% MAH binding%, and about 63 mg KOH / g bound SAP #.

P3 is an example of a second polymer, an ethylene oxide-vinyl acetate copolymer made with an anionic surfactant, having a solid of about 25%. It has a Meter drop point (ASTM D-3954) at about 99 ° C, a hardness of about 5 dmm (ASTM D-5), a density of about 0.94 g / cc (ASTM D-1505), and a viscosity of about 375 cps at 140 ° C. (Blockfield), and an acid value of about 13 (SAP = 56) mg KOH / g (ASTM D-1386).

P4 is an example of a second polymer, an ethylene oxide-vinyl acetate copolymer made of a nonionic surfactant with a solid of about 39%. It has a Meter drop point (ASTM D-3954) at about 99 ° C, a hardness of about 5 dmm (ASTM D-5), a density of about 0.94 g / cc (ASTM D-1505), and a viscosity of about 375 cps at 140 ° C. (Blockfield), and an acid value of about 13 (SAP = 56) mg KOH / g (ASTM D-1386).

P5 is an example of a second polymer, an ethylene acrylic acid copolymer emulsion having about 40% solid. It has a viscosity of about 100 cps and a pH of about 8 at 25 ° C.

P6 is an example of a second polymer, an ethylene-acrylic acid copolymer having an approximately 40% solid. It has a drop point of about 92 ° C., a hardness of about 7 dmm at 25 ° C., a density of about 0.93 g / ml, a viscosity of about 1100 cps at 140 ° C., and an acid value of about 135 mg KOH / g.

P7 is an example of a second polymer, an ethylene-acrylic acid copolymer having an approximately 40% solid. It has a drop point of about 90 ° C., a hardness of about 10 dmm at 25 ° C., a density of about 0.93 g / ml, a viscosity of about 1000 cps at 140 ° C., and an acid value of about 150 mg KOH / g.

P8 is an example of a second polymer, an ethylene-acrylic acid copolymer having an approximately 40% solid. It has a drop point of about 76 ° C., a hardness of about 50 dmm at 25 ° C., a density of about 0.93 g / ml, a viscosity of about 625 cps at 140 ° C., and an acid value of about 185 mg KOH / g.

This data shows that the semi-glossy white color resulted in 100% paint removal with or without corona treatment. All of the corona treatments P2, P5, and P7 also resulted in 100% paint removal. P5 and P7 without corona treatment also resulted in 100% paint removal. Corona treatment P4 resulted in 88% paint removal, while corona treatment P6 also resulted in 80% paint removal. Corona treatment P8 results in 48% paint removal. Corona treatments P1 and P3 were the two best and resulted in only 4% paint removal. Therefore, these results show special unexpected results, indicating excellent adhesion to low energy substrates such as polypropylene.

The external flat white color, with or without corona treatment, resulted in 100% paint removal. P3 corona treatment resulted in 100% removal. Corona treatment P4 resulted in 96% removal. Corona treatment P8 resulted in 68% paint removal. The best performance was corona treatment P1 which resulted in only 4% paint removal. Overall, at semi-gloss, P3 resulted in 4% paint removal, P8 resulted in 48% paint removal, and 15% filling provided the best adhesion. On the outer flat and semi-glossy, P1 had only 4% paint removal with a 15% fill and presented the best overall adhesion. Therefore, these results show special unexpected results, indicating excellent adhesion to low energy substrates such as polypropylene.

Although at least one exemplary embodiment has been presented in the above detailed description, it should be appreciated that there are a huge number of modifications. It should also be understood that the exemplary embodiment or embodiments are merely exemplary and are not intended to limit scope, applicability, or configuration in any way. Rather, the detailed description described above will provide those skilled in the art with a convenient roadmap to implement the exemplary embodiments. It is understood that various changes can be made to the functions and configurations of the elements described in the exemplary embodiments without departing from the scope set forth in the accompanying "Claims".

Claims (10)

With a base material that has been optionally corona-treated,
With topcoat composition, including
The topcoat composition has a first side surface that is placed in direct contact with the substrate and a second side surface that is exposed to the environment on the outermost side.
The top coat composition
(A) Acrylic polymer, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resin, ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate, vinyl acetate copolymer, ethylene- (meth) acrylic acid ionomer, vinylidene chloride copolymer, ethylene -(Meta) acrylate copolymers, polyesters, natural rubbers, neoprenes, phenol polymers, polyurethanes, vinyl acetates, polyvinyl alcohols, styrene butadiene rubbers, caseins, dextrins, starches, polysaccharides, two or more copolymers thereof, and theirs. A first polymer, selected from the group consisting of two or more combinations, and any two or more combinations thereof.
(B) Unlike the first polymer, ethylene-acrylic acid copolymer, polyethylene oxide, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl acetate copolymer, maleated polyolefin, polyethylene homopolymer, polypropylene homopolymer, and them. An article comprising a second polymer, as well as (c) water, selected from the group consisting of any two or more combinations of. The substrate is thermoplastic polyolefin, polyethylene terephthalate, polytetrafluoroethylene, polyvinyl chloride, polypropylene, polyethylene, high density polyethylene, low density polyethylene, ethylene vinyl acetate, polyvinyl alcohol, acetal, acrylic, polyvinyl chloride, acrylonitrile butadiene. The article according to claim 1, which is a low surface energy base material selected from styrene, polyurethane, epoxy, polyester, nylon, phenols, polyimide, alkyd enamel, and a combination thereof. The article according to claim 1, wherein the base material is a low surface energy base material selected from high-density polyethylene, low-density polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, and a combination thereof. The article according to claim 1, wherein the base material is polypropylene. The article according to any one of claims 1 to 4, wherein the first polymer is selected from an acrylic polymer, an ethylene-vinyl acetate copolymer, and a combination thereof. The article according to any one of claims 1 to 5, wherein the second polymer is selected from an ethylene-acrylic acid copolymer, an ethylene oxide-vinyl acetate copolymer, a maleated polyolefin, and a combination thereof. The article according to any one of claims 1 to 5, wherein the second polymer is polyethylene maleated or polypropylene maleated. 13. The article described. With a base material that has been optionally corona-treated,
A cured topcoat composition comprising a first side surface placed in direct contact on the substrate and a second side exposed to the environment on the outermost side, wherein the cured topcoat is an acrylic polymer. Acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resin, ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate, vinyl acetate copolymer, ethylene- (meth) acrylic acid ionomer, vinylidene chloride copolymer, ethylene- (meth) acrylate polymer , Polyester, natural rubber, neoprene, phenol polymer, polyurethane, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch, polysaccharides, two or more copolymers thereof, and combinations of two or more of them. And an ethylene-acrylic acid copolymer, which comprises a cured product of a first polymer selected from the group consisting of any two or more combinations thereof, wherein the first polymer is different from the first polymer. A second selected from the group consisting of polyethylene oxide, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl acetate copolymer, maleated polyolefin, polyethylene homopolymer, polypropylene homopolymer, and any combination of two or more thereof. A cured article that is cured in the presence of a polymer. A method of forming an article comprising a substrate and a topcoat composition, wherein the topcoat composition is exposed to the environment on the first side surface and the outermost side where the topcoat composition is placed in direct contact with the substrate. The above method has two sides.
The step of providing the base material and
Water, as well as acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene-vinyl acetate copolymers, modified ethylene-vinyl acetate, vinyl acetate copolymers, ethylene- (meth) acrylic acid ionomers, vinylidene chloride copolymers, ethylene -(Meta) acrylate copolymers, polyesters, natural rubbers, neoprenes, phenol polymers, polyurethanes, polyvinyl acetates, polyvinyl alcohols, styrene butadiene rubbers, caseins, dextrins, starches, polysaccharides, two or more copolymers thereof, and theirs. A step of providing an aqueous coating comprising a first polymer selected from the group consisting of two or more combinations and any two or more combinations thereof.
Unlike water, surfactants, and the first polymer, ethylene-acrylic acid copolymer, polyethylene oxide, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl acetate copolymer, maleated polyolefin, polyethylene homopolymer, polypropylene homo. A step of providing an emulsion of a polymer and a second polymer selected from the group consisting of any two or more combinations thereof.
The step of combining the emulsion and the aqueous coating composition, and
The second aspect of applying the combination of the emulsion to the aqueous coating composition to the substrate and exposing it to the environment on the first side surface and the outermost side, which is placed in direct contact with the substrate. And the process of forming a topcoat composition with aspects of
A method comprising optionally curing the topcoat composition to form a cured topcoat.

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