Compositions providing barrier properties to paper, paperboard and textiles

Abstract

Compositions for providing barrier properties to substrates, such as liquid resistance and / or oil resistance and / or grease resistance, their preparation and use, and substrates and articles obtained therefrom, such as food containers, dishes, straws, bags (made of paper and textiles), cloths, and bowls. It has been found that substrates treated with the composition have improved properties in terms of liquid resistance, grease resistance and oil resistance even after a subsequent folding step, for example in a subsequent folding step in which food containers are obtained.

Description

Technical Field

[0001] This invention relates to compositions comprising copolymers containing styrene units and acrylate units and styrene-maleic anhydride copolymers, methods of manufacturing such compositions, and uses of such compositions to provide barrier properties (such as oil barrier, liquid barrier and / or grease barrier) and / or heat-sealing properties to substrates such as paper, paperboard or textiles. Background Technology

[0002] Packaging has become a crucial factor in food purchasing. The purpose of food packaging is for transportation and storage. Food packaging is an integral part of the sales and distribution process.

[0003] The primary function of food packaging is to protect food from external influences and damage. Plastics are the most common and widely used material for food packaging. Among plastics used in food packaging, polyolefins and polyesters are the most prevalent.

[0004] In recent years, due to global concern for the environment, plastic pollution has attracted worldwide attention. Plastic waste not only damages ecosystems and biodiversity but also threatens human life and health. Therefore, the packaging industry must abandon plastic packaging and seek more recyclable solutions.

[0005] As this trend continues, paper and paperboard packaging has become an alternative to the growing demand for sustainable and more environmentally friendly materials, thereby developing better solutions for renewable and recyclable packaging.

[0006] While paper and paperboard represent alternatives to this more sustainable packaging material, they lack the required barrier properties to provide protection against water, grease, oil, and other substances. Paper and paperboard have very low barrier properties because the material is highly porous, resulting in high permeability. They are composed of cellulose fibers extracted from trees, which are combined with additives to form a continuous entangled web that shapes the material's structure. Paperboard is a relatively thicker and heavier material than paper. It is widely used for secondary packaging, typically not in direct contact with food. Its primary applications are in box-shaped packaging and containers.

[0007] However, for paperboard to become a viable alternative, its barrier properties need to be improved. The first step is to develop paper and textile-based packaging using fibers treated with fluorinated compounds. However, fluorinated compounds are currently under pressure due to concerns about their persistence in the environment. More sustainable solutions than fluorinated compounds are still needed. Polyethylene (PE) also dominates as a barrier coating in packaging applications due to its properties, particularly its water resistance. However, recycling PE-coated packaging in standard recycling facilities can be challenging. Another issue is that the PE coating can contaminate the fibers during the repulping process, thus hindering fiber recycling in this way.

[0008] On the other hand, to resist oils and greases, early barrier coatings used in food packaging were made from synthetic polymer chemicals called per- and polyfluoroalkyl substances (PFAS). PFAS are a diverse class of compounds characterized by hydrophobic, fluorine-saturated carbon chains linked to hydrophilic functional groups. This structure gives PFAS the ability to readily repel water and fats. However, PFAS cannot be easily separated from paper, meaning that paper cannot be recycled or repulped. In addition to this limitation, the entire series of compounds has also been shown to have harmful effects on human health.

[0009] The paper and textile industries have been experimenting with surface treatments using waxes, acrylic copolymers, and mixtures of both, but without success to date; however, these compositions are known to exhibit weaknesses upon folding and significantly lose their barrier properties. Low-Tg acrylic copolymers have been tested in such applications, but their use is very limited due to the tackiness and adhesion problems caused by their low Tg.

[0010] Today, there is still a need in the market to find alternatives to plastic, solutions that can maintain good barrier properties even when folded.

[0011] The purpose of this invention

[0012] Therefore, the object of the present invention is to provide a composition that meets the above-mentioned requirements of the paper and textile industries in terms of barrier properties without using PFAS. Summary of the Invention

[0013] The inventors have discovered that the compositions according to the invention, when applied to the surface of a suitable substrate, provide good barrier properties (such as resistance to liquids, greases, or oils) and good heat-sealing properties.

[0014] Furthermore, it has been found that the resistances provided to the substrate treated with the composition according to the invention, compared to coatings known in the prior art, enable it to better withstand the folding process, i.e., the substrate exhibits satisfactory resistance even after subsequent folding steps.

[0015] Therefore, the compositions of the present invention are advantageous because, after being applied to a substrate, subsequent folding steps can be performed without loss of toughness.

[0016] Therefore, this objective is achieved by the composition according to the invention:

[0017] The composition I according to the invention for providing barrier properties, particularly liquid resistance, to a substrate comprises at least components (A) and (B2), wherein (A) is at least one copolymer comprising monomer units of: (A1) at least one monomer selected from styrene, methyl methacrylate, (meth)acrylonitrile, α-methylstyrene or mixtures thereof; and (A2) at least one monomer comprising acrylate units; and (B2) at least one styrene maleic anhydride ester.

[0018] In composition I according to the invention, component (A) is present in an amount of 30.0 wt% to 90.0 wt%; component (B2) is present in an amount of 2.0 wt% to 40.0 wt%; wherein the total dry mass percentage of components (A) and (B2) is 100 wt%.

[0019] The method for manufacturing composition I according to the invention comprises at least the following steps a): performing sub-steps i., ii., and optionally iii.: i.) providing component (B2) to a first reaction zone; ii.) providing at least monomers (A1) and (A2) to a second reaction zone to obtain a monomer mixture; optionally mixing the monomer mixture in the second reaction zone with the mixture in the first reaction zone; and copolymerizing the monomer mixture to obtain component (A); or providing component (A) directly; iii.) optionally mixing the composition obtained in step i. and / or the composition obtained in step ii. to provide a first copolymer mixture; wherein optionally, in any one of steps a)i., a)ii., or a)iii., one or more additional components may be added to the respective mixtures.

[0020] The composition II according to the invention for providing barrier properties to a substrate comprises at least components (A), (B1) and / or (B2) and (C), wherein (A) is at least one copolymer comprising monomer units of: (A1) at least one monomer selected from: styrene, methyl methacrylate, (meth)acrylonitrile, α-methylstyrene or mixtures thereof; and (A2) at least one monomer comprising acrylate units; and (B1) is at least one styrene-maleic anhydride copolymer and / or (B2) is at least one styrene-maleic anhydride ester; and (C) is at least one elastomer and / or at least one wax, preferably at least one plant wax.

[0021] In the composition according to the invention, at least one monomer (A1) is present in an amount of 20.0 to 75.0 wt%, and / or at least one monomer (A2) is present in an amount of 25.0 to 80.0 wt%, preferably in an amount of 25.0 to 65.0 wt%, and / or in an amount of 35.0 to 75.0 wt%, optionally, one or more other monomers (A3) may be present in the copolymer in an amount of up to 5 wt%, the copolymer comprising equal to 100 wt% of components (A1), (A2) and optionally (A3).

[0022] In the compositions according to the invention, at least one monomer (A2) is selected from alkyl acrylates or alkyl methacrylates other than methyl methacrylate, including methyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, decyl acrylate, dodecyl acrylate, isomers thereof, and combinations thereof; and / or one or more other monomers (A3) are selected from (meth)acrylamide, (meth)acrylic acid, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, divinylbenzene, ethylene glycol dimethacrylate, itaconic acid, N-hydroxymethyl (meth)acrylamide, 4-methyl-1,4-pentanediol dimethacrylate, propylene glycol dimethacrylate, trivinylbenzene, or mixtures thereof.

[0023] In composition II according to the invention, at least one elastomer is selected from the group consisting of ethylene / vinyl acetate, polybutadiene, natural latex, synthetic latex, styrene-butadiene emulsion or mixtures thereof; preferably wherein component (C) is natural latex or polybutadiene or mixtures thereof; and / or wherein the plant wax is selected from soybean wax, carnauba wax, palm oil, hydrogenated corn oil, hydrogenated coconut oil, hydrogenated castor oil, hydrogenated rapeseed oil or combinations thereof.

[0024] The compositions according to the invention may further comprise at least one other component selected from the following: nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers, or combinations thereof.

[0025] The compositions according to the invention may be dry compositions, preferably powders or granules; or liquid compositions containing a solvent (e.g., organic solvents or water), preferably wherein the compositions according to the invention are aqueous emulsions, aqueous suspensions, aqueous solutions, aqueous slurries or mixtures thereof.

[0026] In composition II according to the invention, component (A) is present in an amount ranging from 30.0 wt% to 90.0 wt%; components (B1) and / or (B2) are present in an amount ranging from 2.0 wt% to 40.0 wt%; component (C): at least one elastomer is present in an amount ranging from 1.0 wt% to 42.0 wt%, and / or at least one wax is present in an amount ranging from 1 wt% to 50 wt%, wherein the total dry mass percentage of components (A), (B1) and / or (B2) and (C) is 100 wt%.

[0027] The method of manufacturing composition II according to the present invention comprises at least the following steps a) and b): a) performing sub-steps i., ii., and optionally iii.: i.) providing components (B1) and / or (B2) to a first reaction zone; ii.) providing at least monomers (A1) and (A2) to a second reaction zone to obtain a monomer mixture; optionally mixing the monomer mixture in the second reaction zone with the mixture in the first reaction zone; and copolymerizing the monomer mixture to obtain component (A); or providing component (A) directly; iii.) optionally mixing the composition obtained in step i. and / or the composition obtained in step ii. to provide a first copolymer mixture; b) adding component I to the first copolymer mixture obtained in step a); wherein optionally, in any one of steps a)i., a)ii., a)iii., or b), one or more additional components may be added to the respective mixture.

[0028] Composition II according to the invention is particularly suitable for use as a barrier, especially an oil barrier and / or grease barrier. When (C) is at least one elastomer, the composition is also used for folding resistance; when (C) is at least one wax, the composition is also used as a liquid barrier on a substrate; preferably, the substrate is a cellulose-based substrate (preferably paper or paperboard) or a substrate based on a synthetic polymer (such as nylon); or a substrate based on a natural material (such as wool); or a mixture of two or more of these substrates.

[0029] Composition I according to the invention is particularly suitable for use as a liquid barrier or heat sealer on a substrate; preferably, the substrate is a cellulose-based substrate (preferably paper or paperboard) or a substrate based on a synthetic polymer (such as nylon); or a substrate based on a natural material (such as wool); or a mixture of two or more of these substrates.

[0030] The coated substrate according to the invention comprises a coating, wherein the coating of the substrate comprises or consists of composition I or composition II according to the invention; preferably, wherein the substrate is a cellulose-based substrate (preferably paper or paperboard) or a substrate based on a synthetic polymer (such as nylon); or a substrate based on a natural material (such as wool); or a mixture of two or more of these substrates; preferably, wherein the coated substrate further comprises an outer coating selected from: moisture barrier, oxygen barrier, heat sealant, gas barrier, aesthetic outer coating (e.g., printing, varnish or gloss-providing outer coating) or a combination thereof.

[0031] The method for manufacturing a coated substrate according to the present invention comprises the following steps: I) applying the composition according to the present invention onto a substrate; II) drying the composition according to the present invention on the substrate.

[0032] The article according to the invention and the method of manufacturing according to the invention, the article according to the invention comprising or consisting of a coated substrate according to the invention, wherein the coated substrate is subjected to measures selected from the group consisting of: cutting, folding, gluing, curing, dyeing or a combination thereof.

[0033] Articles according to the invention comprise or consist of a coated substrate according to the invention, wherein the article is a food or beverage container, plate, straw, bag, bowl, cloth, or bag (made of paper or textiles). Detailed Implementation

[0034] This invention relates to a composition (hereinafter also referred to as "Composition I") for providing barrier properties (particularly liquid barrier properties and heat-sealing properties) to a substrate, comprising at least components (A) and (B2), wherein

[0035] (A) is at least one copolymer comprising the following monomer units.

[0036] (A1) is at least one monomer selected from: styrene, methyl methacrylate, (meth)acrylonitrile, α-methylstyrene, or mixtures thereof; and

[0037] (A2) is at least one monomer containing an acrylate unit; and

[0038] (B2) is at least one styrene maleic anhydride ester.

[0039] The present invention also relates to a composition (hereinafter referred to as "Composition II") for providing barrier properties (such as resistance to liquids and / or oils and / or greases) to a substrate, comprising at least components (A), (B1) and / or (B2) and (C), wherein

[0040] (A) is at least one copolymer comprising the following monomer units.

[0041] (A1) is at least one monomer selected from: styrene, methyl methacrylate, (meth)acrylonitrile, α-methylstyrene, or mixtures thereof; and

[0042] (A2) is at least one monomer containing an acrylate unit;

[0043] (B1) is at least one styrene-maleic anhydride copolymer, and / or

[0044] (B2) is at least one styrene maleic anhydride ester; and

[0045] (C) is at least one elastomer and / or at least one wax, preferably a plant wax.

[0046] If this document refers only to "the composition according to the invention", it always refers to compositions I and II.

[0047] The term "barrier property" refers to "resistance to liquids and / or oils and / or greases," meaning the ability of a substrate to withstand the absorption of liquids, vapors, greases, and / or oils into its fibrous matrix when in direct contact with them, thereby preventing loss of stability, shape, and other mechanical properties. The term "liquid barrier" refers to a substrate that has the ability to withstand the absorption of common liquids (such as water, hot coffee, or acidic liquids such as cola) and vapors (such as water vapor). The term "liquid barrier" is used interchangeably with the term "water barrier."

[0048] The term "substrate" refers to any material that should have resistance to liquids and / or oils and / or greases and / or heat-sealing properties. The substrate material can be selected from cellulose-based materials, synthetic polymer-based materials, or any other natural-based materials, or mixtures thereof. Suitable substrates include, but are not limited to, paper, paperboard, nonwovens, or textiles. The substrate can contain or consist of cellulose fibers and / or synthetic fibers and / or fibers of other natural sources. Suitable examples are, but are not limited to, cotton, polyester, polyamide, silk, wool, or mixtures thereof. The substrate thickness can vary widely, i.e., the area weight of the substrate to be treated with the composition according to the invention can be as low as 20 g / m². 2 Up to 500 g / m 2 or 30 g / m2 Up to 400 g / m 2 Within the range.

[0049] In addition, the substrate can be 30 g / m². 2 Up to 80 g / m 2 Thin paper, or paper with an area weight of 80 g / m² 2 Up to 110 g / m 2 Thick paper.

[0050] The substrate can also be cardboard, for example, with an area weight of 110 g / m². 2 Up to 180 g / m 2 The board padding, or the area weight of 180 g / m² 2 Up to 400 g / m 2 of thick plates.

[0051] The substrate can also be 50 g / m². 2 Up to 100 g / m 2 Nonwoven fabrics.

[0052] In addition, the substrate can be textiles, such as, but not limited to, cellulose-based textiles, fiber-based synthetic textiles, or mixtures thereof.

[0053] Furthermore, in any other method known in the prior art, the substrate may or may not undergo (pre)processing.

[0054] The term "(pre)treatment" does not imply limitation to using the invention as part of another method. Although the invention can be incorporated into any kind of method for treating substrates to improve their resistance to liquids, oils or greases, and heat-sealing properties.

[0055] The composition according to the invention comprises at least one copolymer as component (A), said copolymer comprising or consisting of at least monomer units (A1) and (A2).

[0056] The term "polymer" refers to any modified or unmodified, branched or unbranched polymer that comprises or consists of two or more monomer units that are different from each other.

[0057] The term "monomer" refers to a molecule that can react with the same and / or different monomer molecules to form a large polymer chain or three-dimensional network in a polymerization reaction.

[0058] At least one monomer (A1) of component (A) of the composition according to the invention comprises or consists of styrene, methyl methacrylate, (meth)acrylonitrile, α-methylstyrene, or mixtures thereof. Preferred monomer (A1) is styrene, methyl methacrylate, acrylonitrile, or mixtures thereof.

[0059] At least one monomer (A1) is present in at least one copolymer (component (A)) in an amount of at least 20.0 wt%, or at least 25 wt%, or at least 30.0 wt%, or at least 35.0 wt%, or at most 75 wt%, or at most 70 wt%, or at most 60.0 wt%, or at most 50.0 wt%, or at most 45.0 wt%, or 20.0 wt% to 75 wt%, or 25 wt% to 65 wt%, or 25.0 wt% to 60.0 wt%, or 30.0 wt% to 60.0 wt%, or 30.0 wt% to 50.0 wt%, or 30 wt% to 45 wt%, or 35 wt% to 60 wt%, or 35 wt% to 55 wt%, wherein the wt% is based on the total weight of the copolymer comprising equal to 100 wt% of components (A1) and (A2).

[0060] At least one monomer (A2) of component (A) of the composition according to the invention comprises or is composed of acrylate units CH2=CR 3 COO-R 2 Composition, where R 2 This represents a residue containing 1 to 40 carbon atoms, i.e., the alcohol moiety of an ester. In one embodiment, R 2 It is branched or unbranched or cyclic C1 to C 40 Alkyl groups, which may be saturated or unsaturated. In a preferred embodiment, R 2 Selected from branched, unbranched, or cyclic C2 to C3 groups 20 Alkyl, preferably C4 to C5 10 Alkyl group. In one embodiment, R 3 The following groups are selected: H, CH3, or C2H5. In a preferred embodiment, R 3 It is H, and R 2 It is C 4-10 alkyl.

[0061] The copolymer (component (A)) may contain different monomer units (A2), which may be selected from alkyl acrylates or alkyl methacrylates other than methyl methacrylate, including methyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, decyl acrylate, dodecyl acrylate, isomers thereof, and combinations thereof. Particularly preferred are butyl acrylate, 2-ethylhexyl acrylate, and / or isooctyl acrylate; most preferred are 2-ethylhexyl acrylate, butyl acrylate, or mixtures thereof; and even most preferred is 2-ethylhexyl acrylate.

[0062] At least one monomer (A2) may be present in at least one copolymer (component (A)) in an amount of at least 25 wt%, or at least 30 wt%, or at least 35 wt%, 40.0 wt%, or at least 50.0 wt%, or at least 55.0 wt%, or at most 80 wt%, or at most 75.0 wt%, or at most 70.0 wt%, or at most 65.0 wt%, or 25 wt% to 80 wt%, or 35 wt% to 75 wt%, or 30.0 wt% to 75.0 wt%, or 45.0 wt% to 75.0 wt%, or 40.0 wt% to 70.0 wt%, or 50.0 wt% to 70.0 wt%, or 50 wt% to 65.0 wt%, or 55 wt% to 70 wt%, wherein the wt% is based on the total weight of the copolymer comprising equal to 100 wt% of components (A1) and (A2).

[0063] In cases where at least one monomer (A1) comprises or consists of methyl methacrylate, at least one monomer (A2) may be a different acrylic monomer.

[0064] In addition, component (A) may contain or consist of styrene (monomer A1) and 2-ethylhexyl acrylate (monomer A2).

[0065] Component (A) may also comprise or consist of 20.0 wt% to 75.0 wt% of styrene (monomer A1) and 25.0 wt% to 80.0 wt% of 2-ethylhexyl acrylate (monomer A2), wherein the wt% is based on the total weight of the copolymer comprising equal to 100 wt% of components (A1) and (A2).

[0066] In addition, component (A) may contain or consist of styrene (monomer A1) and butyl acrylate (monomer A2).

[0067] In addition, component (A) may comprise or consist of 20.0 wt% to 75.0 wt% of styrene (monomer A1) and 25.0 wt% to 80.0 wt% of butyl acrylate (monomer A2), wherein the wt% is based on the total weight of the copolymer comprising equal to 100 wt% of components (A1) and (A2).

[0068] In addition, component (A) may contain or consist of methyl methacrylate (monomer A1) and 2-ethylhexyl acrylate (monomer A2).

[0069] Component (A) may also comprise or consist of 20.0 wt% to 75.0 wt% of methyl methacrylate (monomer A1) and 25.0 wt% to 80.0 wt% of 2-ethylhexyl acrylate (monomer A2), wherein the wt% is based on the total weight of the copolymer comprising equal to 100 wt% of components (A1) and (A2).

[0070] In addition, component (A) may contain or consist of methyl methacrylate (monomer A1) and butyl acrylate (monomer A2).

[0071] In addition, component (A) may comprise or consist of 20.0 wt% to 75.0 wt% of methyl methacrylate (monomer A1) and 25.0 wt% to 80.0 wt% of butyl acrylate (monomer A2), wherein the wt% is based on the total weight of the copolymer comprising equal to 100 wt% of components (A1) and (A2).

[0072] In addition, component (A) may contain or consist of acrylonitrile (monomer A1) and 2-ethylhexyl acrylate (monomer A2).

[0073] Component (A) may also comprise or consist of 20.0 wt% to 75.0 wt% of acrylonitrile (monomer A1) and 25.0 wt% to 80.0 wt% of 2-ethylhexyl acrylate (monomer A2), wherein the wt% is based on the total weight of the copolymer comprising equal to 100 wt% of components (A1) and (A2).

[0074] In addition, component (A) may contain or consist of acrylonitrile (monomer A1) and butyl acrylate (monomer A2).

[0075] In addition, component (A) may comprise or consist of 20.0 wt% to 75.0 wt% of acrylonitrile (monomer A1) and 25.0 wt% to 80.0 wt% of butyl acrylate (monomer A2), wherein the wt% is based on the total weight of the copolymer comprising equal to 100 wt% of components (A1) and (A2).

[0076] In addition, component (A) may contain or consist of styrene and methyl methacrylate (monomer A1) and 2-ethylhexyl acrylate (monomer A2).

[0077] In addition, component (A) may comprise or consist of 20.0 wt% to 75.0 wt% of styrene and methyl methacrylate (monomer A1) and 25.0 wt% to 80.0 wt% of 2-ethylhexyl acrylate (monomer A2).

[0078] The copolymer of component (A) of the composition of the present invention may optionally include one or more monomers (A3) in addition to monomers (A1) and (A2).

[0079] Non-limiting examples of these one or more additional monomers are (meth)acrylamide, (meth)acrylic acid, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, 4-methyl-1,4-pentanediol dimethacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, divinylbenzene, itaconic acid, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, trivinylbenzene, or mixtures thereof.

[0080] One or more optional monomers (A3) may be present in component (A) in an amount of at least 0.001 wt%, or at least 0.01 wt%, or at least 0.1 wt%, but in any case at most 5.0 wt%, or at most 4.0 wt%, or at most 3.0 wt%, or from 0.001 wt% to 5.0 wt%, or from 0.01 wt% to 4.0 wt%, or from 0.1 wt% to 3.0 wt%, wherein the wt% is based on the total amount of copolymers comprising equal to 100 wt% of components (A1), (A2) and optional (A3).

[0081] Component (A) may be present in the composition according to the invention in an amount of at least 30.0 wt%, or at least 35 wt%, or at least 40.0 wt%, or at least 45.0 wt%, or at most 90.0 wt%, or at most 80.0 wt%, or at most 75.0 wt%, or from 30.0 wt% to 90.0 wt%, or from 35.0 wt% to 80.0 wt%, or from 35.0 wt% to 75.0 wt%, or from 40.0 wt% to 80.0 wt%, or from 40.0 wt% to 75.0 wt%, wherein the sum of the dry mass percentages of all components present in the composition according to the invention is 100 wt%.

[0082] Molecular weight (M) of component (A) nThe molecular weight of component (A) can be at least 100,000 g / mol, or at least 200,000 g / mol, or at least 300,000 g / mol, or at least 400,000 g / mol, or at most 1,000,000 g / mol, or at most 900,000 g / mol, or at least 800,000 g / mol, or at least 700,000 g / mol, or can be in the range of 100,000 to 1,000,000 g / mol, or 200,000 to 900,000 g / mol, or 300,000 to 800,000 g / mol. The preferred molecular weight of component (A) is 200,000 to 900,000 g / mol, or 300,000 to 800,000 g / mol. The molecular weight (M) of component (A) is... n The measurements were performed after component (A) was dissolved in THF, under conditions with a maximum concentration of 50 g / 100 mL acetone. The solution was then injected into a gel permeation chromatography system, which separated the different chains according to their molecular weight. A UV detector could be used.

[0083] Furthermore, the glass transition temperature (Tg) of component (A) may be at least -40°C, or at least -30°C, or at least -20°C, or up to 40°C, or up to 30°C, or up to 20°C, or may be within the range of -40°C to 40°C, or -30°C to 30°C, or -20°C to 30°C, or -10°C to 30°C. The Tg of component (A) is determined according to the following method for defining component (B1).

[0084] One or more copolymers may be used as component (A) in the composition according to the invention.

[0085] Furthermore, the additional copolymer of component (A) may contain or consist of the same or (partially) different monomers, or be made of one or more additional monomers.

[0086] Preferably, the composition and / or component (A) according to the invention does not contain any fluorine-based compounds, such as PFAs.

[0087] Composition I according to the invention further comprises at least one styrene maleic anhydride ester as component (B2). Composition II according to the invention comprises at least one styrene maleic anhydride (SMA) copolymer as component (B1) and / or at least one styrene maleic anhydride ester as component (B2).

[0088] The advantage of using (esterified) SMA (i.e., components (B1) and / or (B2)) is that it can be used as a polymer surfactant, alone or in combination with other surfactants, during emulsion polymerization, thereby providing enhanced liquid barrier properties and heat-sealing properties for substrates that can be transformed into beverage containers and other food containers.

[0089] Esterified styrene-maleic anhydride copolymer (“e-SMA”; component (B2)) can be produced by esterifying SMA (i.e., component (B1)) using a standard esterification technique with alcohols, wherein the alcohol is an alkyl, aryl, cycloalkyl, arylalkyl, or alkylaryl monohydric alcohol, particularly C2 to C3. 20 Monohydric alcohols, particularly preferred aliphatic primary or secondary alcohols, such as ethanol, butanol, isobutanol, propanol, isopropanol, methanol, 2-ethylhexanol, isooctanol, or mixtures thereof. Ethanol, butanol, and isobutanol, or mixtures thereof, are preferred.

[0090] The esterification can be performed using at least 80 wt%, or at least 82 wt%, or at least 85 wt%, or up to 90 wt%, or up to 87 wt% of SMA (i.e., component (B1)) and at least 10 wt%, or at least 13 wt%, or up to 20 wt%, or up to 18 wt%, or up to 15 wt% of alcohol, wherein the wt% is based on the total amount (=100 wt%) of component (B1) and alcohol used in the esterification reaction. The wt% range of component (B1) and alcohol used in the esterification reaction can be 80 wt% to 90 wt%, or 82 wt% to 90 wt%, or 85 wt% to 90 wt% of component (B1) and 10 to 20 wt%, or 10 to 18 wt%, or 10 to 15 wt% of alcohol, wherein the wt% is based on the total amount (=100 wt%) of component (B1) and alcohol used in the esterification reaction.

[0091] The component (B2) used in the compositions according to the invention may be selected from SMA methyl ester, ethyl ester, or (secondary or iso)butyl ester. Such copolymers may contain p-nitrostyrene as a polymerization chain terminator.

[0092] The molecular weight (Mn) of the esterified styrene-co-maleic anhydride is at least 1000 g / mol, or at most 80,000 g / mol, or at most 50,000 g / mol, or at most 25,000 g / mol, or at most 10,000 g / mol, or at most 9,500 g / mol, or in the range of 1,000 g / mol to 80,000 g / mol, or 1,000 g / mol to 50,000 g / mol, or 1,000 g / mol to 25,000 g / mol, or 1,000 g / mol to 10,000 g / mol.

[0093] The glass transition temperature (Tg) of the esterified styrene-maleic anhydride copolymer is about 75°C to 130°C, preferably 90°C to 130°C, and even more preferably 95°C to 120°C. Tg is measured as disclosed herein with respect to component (B1).

[0094] Component (B2) may be present in composition I according to the invention in an amount ranging from at least 2.0 wt%, or at least 4.0 wt%, or at least 5.0 wt%, or at least 10.0 wt%, or at most 40.0 wt%, or at most 35 wt%, or at most 30 wt%, or at most 28 wt%, or at most 27.5 wt%, or at most 26 wt%, or in an amount ranging from 2.0 wt% to 40.0 wt%, or from 4.0 wt% to 28.0 wt%, or from 5.0 wt% to 27.5 wt%, or from 10.0 wt% to 26 wt%, wherein the sum of the dry mass percentages of components (A) and (B2) is 100 wt%.

[0095] Components (B1) and / or (B2) may be present in composition II according to the invention in amounts ranging from at least 2.0 wt%, or at least 4.0 wt%, or at least 5.0 wt%, or at least 10.0 wt%, or at most 40.0 wt%, or at most 35 wt%, or at most 30 wt%, or at most 28.0 wt%, or at most 27.5 wt%, or at most 26.0 wt%, or in amounts ranging from 2.0 wt% to 40.0 wt%, or from 4.0 wt% to 28.0 wt%, or from 5.0 wt% to 27.5 wt%, or from 10.0 wt% to 26 wt%, wherein the sum of the dry mass percentages of components (A), (B1) and / or (B2) and (C) is 100 wt%.

[0096] The components (B1) / (B2) of the composition according to the present invention may also contain at least maleic anhydride and styrene in different amounts.

[0097] Furthermore, the content of maleic anhydride monomer in the SMA copolymer of component (B1) / (B2) may be at least 20.0 wt%, or at least 21.0 wt%, or at least 22 wt%, or at least 25 wt%, or at most 35.0 wt%, or at most 33.0 wt%, or vary within the range of 20.0 wt% to 35.0 wt%, or 21.0 to 35.0 wt%, or 25.0 wt% to 35.0 wt%, wherein the wt% is based on the total weight of component (B1) or (B2) equal to 100 wt%.

[0098] The content of styrene monomer in the SMA polymer of component (B1) / (B2) may also be at least 60.0 wt%, or at least 62 wt%, or at least 65 wt%, or at least 73.0 wt%, or at most 80.0 wt%, or at most 79.0 wt%, or at least 75.0 wt%, or vary in the range of 60.0 wt% to 80.0 wt%, or in the range of 65.0 wt% to 79.0 wt%, or in the range of 65.0 wt% to 75.0 wt%, wherein the wt% is based on the total weight of component (B1) or (B2) equal to 100 wt%.

[0099] The molecular weight (Mn) of component (B1) can be at least 1000 g / mol, or at most 80,000 g / mol, or at most 50,000 g / mol, or at most 25,000 g / mol, or at most 10,000 g / mol, or at most 9,500 g / mol, or in the range of 1,000 g / mol to 80,000 g / mol, or 1,000 g / mol to 50,000 g / mol, or 1,000 g / mol to 25,000 g / mol, or 1,000 g / mol to 10,000 g / mol. The molecular weight (Mn) of (B1) or (B2) is measured after dissolving the (B1) or (B2) powder in acetone and / or THF at a maximum concentration of 50 g / 100 mL acetone. The solution is then injected into a gel permeation chromatograph, which separates the different chains according to their molecular weight. A UV detector can be used.

[0100] The Tg of component (B1) may also vary within the range of at least 85°C or at least 100°C, or at least 115°C, or at most 180°C, or at most 165°C, or at most 150°C, or within the range of 85°C to 180°C, or 100°C to 165°C, or 115°C to 150°C, or 115°C to 165°C, or 115°C to 130°C, or 110°C to 150°C, or 100°C to 150°C. The Tg of component (B1) or (B2) is measured using the DSC method (differential scanning calorimetry), starting from -85°C up to 200°C, heated in a ramp manner over 15 minutes.

[0101] The particularly suitable SMA used as component (B1) in composition II according to the invention contains 25.0 to 35.0 wt% maleic anhydride and 65.0 to 75.0 wt% styrene, wherein the wt% is based on the total weight (=100 wt%) of component (B1) and / or the molecular weight is in the range of 1,000 g / mol to 10,000 g / mol and / or the glass transition temperature is 110°C to 150°C, preferably 115°C to 130°C.

[0102] The particularly suitable e-SMA used as component (B2) in composition I according to the invention contains 25.0 to 35.0 wt% maleic anhydride and 65.0 to 75.0 wt% styrene, wherein the wt% is based on the total weight of component (B2) (=100 wt%), and is esterified using ethanol, butanol, isobutanol or a mixture thereof, wherein the wt% of SMA is 80 wt% to 90 wt% and the wt% of alcohol is 10 to 20 wt%, wherein the wt% is based on the total amount of SMA and alcohol used in the esterification reaction (=100 wt%), and / or the molecular weight is in the range of 1,000 g / mol to 10,000 g / mol and / or the glass transition temperature is 90°C to 130°C, even more preferably 95 to 120°C.

[0103] Furthermore, components (B1) and (B2) can be used as polymeric surfactants in the compositions according to the invention.

[0104] The suitable component (B1) was supplied by Polyscope under the trade name Xiran. ® For sale. Suitable component (B2) is supplied by Polyscope under the trade name Xiran. ® Selling for 1440.

[0105] Composition II according to the invention further comprises at least one elastomer and / or at least one wax, preferably at least one plant wax, as component (C).

[0106] The term "elastomer" refers to polymer compounds that exhibit viscoelasticity, weak intermolecular forces, low Young's modulus, and high fracture strain compared to other materials.

[0107] The term "wax" refers to an organic compound that is solid at atmospheric temperature but has a very low melting temperature (e.g., 35°C) without decomposing. Waxes are typically derived from compounds with long aliphatic alkyl chains (usually C10-C20). 36 To C 50 Higher fatty acid esters, or derived from polymers (700 < molecular weight < 10,000), which are insoluble in water but soluble in nonpolar organic solvents.

[0108] Wax has relatively low viscosity at temperatures slightly above its melting point.

[0109] Today, a wide variety of waxes are available on the market, typically categorized by their origin. Waxes can be further divided into natural waxes and synthetic waxes. Natural waxes can also be classified as fossil waxes (such as petroleum waxes) and non-fossil waxes (such as animal waxes and plant waxes).

[0110] Examples of natural waxes include, for example, beeswax, carnauba wax, corn wax, coconut wax and soybean wax, hydrogenated palm oil, hydrogenated corn oil, hydrogenated coconut oil, hydrogenated castor oil, hydrogenated rapeseed oil or mixtures thereof.

[0111] Examples of synthetic waxes include, for example, petroleum-derived paraffin wax, polyethylene wax, Fischer-Tropsch (FT) wax, and Montanwax. The most commonly used type of wax is petroleum-based paraffin wax.

[0112] Wax can be used in the form of an emulsion with a certain solid content (e.g., 40%).

[0113] The amount of at least one wax in the compositions IIw and IIew according to the invention may be at least 1.0 wt%, or at least 2.0 wt%, or at least 5.0 wt%, or at least 6.0 wt%, or at least 7.5 wt%, or at least 10.0 wt%, or at least 11 wt%, or at least 13 wt%, or at least 14 wt%, or at least 15 wt%, or at least 42.0 wt%, or at least 40 wt%, or at least 35.0 wt%, or at least 30.0 wt%, or at least 25.0 wt%, or at least 20.0 wt%, or at most 50 wt%, or at most 45 wt%, or in the range of 1.0 wt% to 50.0 wt%, or 5.0 wt% to 50.0 wt%, or 5.0 wt% to 45.0 wt%, or 10 wt% to 50 wt%, or 10 wt% to 45 wt%. Within the range of wt%, the sum of the dry mass percentages of components (A), (B1) / (B2) and (C) is 100 wt%.

[0114] Composition II according to the invention may contain only at least one elastomer as component (C), but not wax. Such a composition according to the invention will be referred to herein as "Composition IIe".

[0115] Composition II according to the invention may also contain only at least one wax as component (C), but not an elastomer. Such a composition according to the invention will be referred to herein as "Composition IIw".

[0116] Composition II according to the invention may contain at least one elastomer and at least one wax as components (C). Such a composition according to the invention will be referred to herein as "Composition IIew".

[0117] If this specification refers only to “composition II”, it means compositions IIe, IIw and IIew.

[0118] At least one elastomer may be selected from the non-limiting group consisting of: ethylene / vinyl acetate, polybutadiene, natural latex, synthetic latex, styrene-butadiene emulsion, or mixtures thereof. Natural latex or polybutadiene, or mixtures thereof, are preferred.

[0119] The amount of at least one elastomer in the compositions IIe and IIew according to the invention may also be at least 1.0 wt%, or at least 2.0 wt%, or at least 5.0 wt%, or at least 6.0 wt%, or at least 7.5 wt%, or at least 10.0 wt%, or at least 11 wt%, or at least 13 wt%, or at least 14 wt%, or at least 15 wt%, or at most 42.0 wt%, or at most 40 wt%, or at most 35.0 wt%, or at most 30.0 wt%, or at most 25.0 wt%, or at most 20.0 wt%, or in the range of 1.0 wt% to 42.0 wt%, or 5.0 wt% to 42.0 wt%, or 5.0 wt% to 40.0 wt%, or 5.0 wt% to 35.0 wt%, or 5.0 wt% to 30.0 wt%, or 5.0 to 25.0 wt%, or 5.0 to 20.0 wt%. Within the range of wt%, wherein the sum of the dry mass percentages of components (A), (B1) / (B2) and (C) is 100 wt%. In the compositions IIe and IIew according to the invention, the preferred amount of at least one elastomer is within the range of 1.0 wt% to 42.0 wt%, or 5.0 wt% to 42.0 wt%, or 5.0 wt% to 30.0 wt%, or 5.0 wt% to 25.0 wt%, or 5.0 wt% to 20.0 wt%, wherein the sum of the dry mass percentages of components (A), (B1) / (B2) and (C) is 100 wt%.

[0120] The glass transition temperature T of at least one elastomer g The temperature range can be at least -90°C, or at least -80°C, or at least -70°C, or up to -50°C, or up to -60°C, or a range from -50°C to -90°C, or from -60°C to -80°C. The glass transition temperature Tg is determined using the same method disclosed above, employing DSC (differential scanning calorimetry), measured from -85°C up to 200°C, with heating in a ramp manner over 15 minutes.

[0121] The compositions IIe and IIew according to the present invention may contain two or more elastomers, such as one, two, three or four elastomers.

[0122] At least one elastomer may also comprise or consist solely of natural latex, and is present in amounts of 1.0 wt% to 42.0 wt%, or 1.0 wt% to 40.0 wt%, or 1.0 wt% to 20.0 wt%, or 5.0 wt% to 42.0 wt%, or 5.0 wt% to 40.0 wt%, or 5.0 wt% to 30.0 wt%, or 5.0 wt% to 25.0 wt%, or 5.0 wt% to 20.0 wt%, wherein the sum of the dry mass percentages of components (A), (B1) / (B2) and (C) is 100 wt%.

[0123] At least one elastomer may also comprise or consist solely of polybutadiene, and is present in amounts of 1.0 wt% to 42.0 wt%, or 1.0 wt% to 40.0 wt%, or 1.0 wt% to 20.0 wt%, or 5.0 wt% to 42.0 wt%, or 5.0 wt% to 40.0 wt%, or 5.0 wt% to 30.0 wt%, or 5.0 wt% to 25.0 wt%, or 5.0 wt% to 20.0 wt%, wherein the sum of the dry mass percentages of components (A), (B1) / (B2) and (C) is 100 wt%.

[0124] In addition, at least one elastomer may contain only natural latex and polybutadiene in amounts of 1.0 wt% to 42.0 wt%, or 1.0 wt% to 40.0 wt%, or 1.0 wt% to 20.0 wt%, or 5.0 wt% to 42.0 wt%, or 5.0 wt% to 40.0 wt%, or 5.0 wt% to 30.0 wt%, or 5.0 wt% to 25.0 wt%, or 5.0 wt% to 20.0 wt%, wherein the sum of the dry mass percentages of components (A), (B1) / (B2) and (C) is 100 wt%.

[0125] At least one elastomer may also comprise natural latex and polybutadiene, as well as other elastomers known in the art.

[0126] Composition II according to the invention may comprise or consist of: component (A) in an amount ranging from 30.0 wt% to 90.0 wt%; component (B1) / (B2) in an amount ranging from 2.0 wt% to 40.0 wt%; and component (C) in an amount ranging from 1.0 wt% to 42.0 wt% if component (C) is an elastomer, and / or in an amount ranging from 1.0 wt% to 50.0 wt% if component (C) is a wax; wherein the wt% of components (A), (B1) / (B2) and (C) is based on the total dry weight of composition II, which sums to 100 wt%.

[0127] The compositions according to the invention may also contain one or more additional components known in the art and are used in the composition applied to a substrate to provide any resistance. Non-limiting examples of such additional components are nonionic surfactants, ionic surfactants, transfer agents, buffers, inert salts, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers, or combinations thereof.

[0128] Optionally, the compositions according to the invention may contain one or more nonionic surfactants, such as, but not limited to, alcohol ethoxylates, ethylene oxide-propylene oxide block copolymers, alcohol alkoxylates, fatty acid ethoxylates, fatty amine ethoxylates, or mixtures thereof.

[0129] Optionally, the compositions according to the invention may contain one or more ionic surfactants, such as, but not limited to, fatty acid salts, alkylbenzene sulfonates (e.g., sodium dodecylbenzene sulfonate), alkyl sulfonates, fatty alcohol sulfates (e.g., sodium dodecyl sulfate), alkyl ether sulfates (e.g., sodium dodecyl polyoxyethylene ether sulfate), or mixtures thereof.

[0130] In addition, one or more optional nonionic and / or ionic surfactants may be present in amounts of at least 0.01 wt%, or at least 0.05 wt%, or at least 0.1 wt%, or at least 0.25 wt%, or at most 5.0 wt%, or at most 4.0 wt%, or 0.01 wt% to 5.0 wt%, or 0.05 wt% to 5.0 wt%, or 0.1 wt% to 5.0 wt%, or 0.1 to 4.0 wt%, or 0.25 wt% to 5.0 wt%, wherein the wt% is based on the total dry weight (=100 wt%) of the compositions according to the invention.

[0131] Composition I according to the invention may comprise or consist of components (A) and (B2) and one or more additional components (preferably at least one nonionic surfactant and / or ionic surfactant other than component (B2)).

[0132] Composition I according to the invention may also comprise or consist of components (A) and (B2) and one or more additional components, but does not contain nonionic surfactants and / or ionic surfactants other than component (B2).

[0133] Composition II according to the invention may comprise or consist of components (A), (B1) and / or (B2) and (C) and one or more additional components (preferably at least one nonionic surfactant and / or ionic surfactant in addition to components (B1) / (B2)).

[0134] Composition II according to the invention may further comprise or consist of components (A), (B1) and / or (B2) and (C) and one or more additional components, but does not contain nonionic surfactants and / or ionic surfactants other than components (B1) / (B2).

[0135] The compositions according to the invention may contain one or more pH adjusters, such as, but not limited to, ammonium hydroxide, sodium hydroxide, potassium hydroxide, or mixtures thereof.

[0136] The compositions according to the invention can be dry compositions, such as powders or granules or mixtures thereof.

[0137] Composition I according to the invention may be a dry mixture containing only components (A) and (B2).

[0138] Composition II according to the invention may be a dry mixture containing only components (A), (B1) and / or (B2) and (C).

[0139] The composition I according to the invention may also be a dry mixture comprising or consisting of components (A) and (B2) in amounts as defined above with respect to each component, for example, the amount of component (A) is from 30.0 wt% to 90.0 wt%, and the amount of component (B2) is from 2.0 wt% to 40.0 wt%, wherein the total dry wt% of components (A) and (B2) is 100 wt%.

[0140] Composition II according to the invention may also be a dry mixture comprising or consisting of components (A), (B1) and / or (B2) and (C) in amounts as defined above with respect to each component, for example, the amount of component (A) is 30.0 wt% to 90.0 wt%, the amount of components (B1) and / or (B2) is 2.0 wt% to 40.0 wt%, and component (C): if (C) is at least one elastomer, the amount is 1.0 wt% to 42.0 wt% and / or wherein (C) is at least one wax, the amount is 1.0 wt% to 50 wt%, wherein the total dry wt% of components (A), (B1) and / or (B2) and (C) is 100 wt%.

[0141] Composition I according to the invention may also be a dried mixture comprising components (A) and (B2) and other additional components in dried form, such as, but not limited to, nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers, or combinations thereof.

[0142] Composition II according to the invention may also be a dry mixture comprising components (A), (B1) and / or (B2) and (C) and other additional components in a dry form, such as, but not limited to, nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers or combinations thereof.

[0143] Furthermore, composition I according to the invention may be a dry mixture comprising or consisting of: component (A) in an amount of 30.0 wt% to 90.0 wt%, component (B2) in an amount of 2.0 wt% to 40.0 wt%, and one or more additional components in a dry form, such as, but not limited to, nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers, or combinations thereof, preferably at least one nonionic surfactant in an amount of 0.01 wt% to 5 wt%, wherein the wt% is based on the total dry weight of components (A) and (B2) of composition I according to the invention.

[0144] Furthermore, composition II according to the invention may be a dry mixture comprising or consisting of: component (A) in an amount of 30.0 wt% to 90.0 wt%, component (B1) and / or (B2) in an amount of 2.0 wt% to 40.0 wt%, and component (C): if (C) is at least one elastomer in an amount of 1.0 wt% to 42.0 wt% and / or wherein (C) is at least one wax in an amount of 1.0 wt% to 50.0 wt%, and one or more additional components in a dry form, such as, but not limited to, nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers or combinations thereof, preferably at least one nonionic surfactant in an amount of 0.01 wt% to 5 wt%, wherein the wt% is based on the total dry weight of components (A), (B1) and / or (B2) and (C) of the composition according to the invention.

[0145] The compositions according to the invention can also be designed as liquid compositions comprising at least one solvent, such as, but not limited to, organic solvents and / or water. The compositions according to the invention can then be designed as emulsions, suspensions, solutions, slurries, or mixtures thereof. If the solvent contains or consists of water, the compositions according to the invention can be considered aqueous compositions. Preferably, the compositions according to the invention are aqueous compositions.

[0146] The composition according to the invention may be a liquid composition comprising at least one solvent in an amount of 30.0 wt% to 100 wt%, or 35.0 wt% to 80 wt%, or 40 wt% to 60 wt%, wherein the wt% is based on the total weight of the composition according to the invention; or the composition according to the invention is a liquid composition and comprises at least one solvent in an amount of 50.0 wt% to 300 wt%, or 50.0 wt% to 250 wt%, or 50 wt% to 150 wt%, wherein the wt% is based on the total dry weight of the components of the composition according to the invention.

[0147] Composition I according to the invention may also be a liquid composition comprising or consisting of components (A) and (B2) and a solvent, wherein the solvent is an organic solvent or water, preferably water.

[0148] Composition II according to the invention may also be a liquid composition comprising or consisting of components (A), (B1) and / or (B2) and (C) and a solvent, wherein the solvent is an organic solvent or water, preferably water.

[0149] Furthermore, composition I according to the invention may be a liquid composition comprising or consisting of: component (A) in an amount of 15.0 wt% to 80.0 wt%; component (B2) in an amount of 2.0 wt% to 40.0 wt%; and at least one solvent, which is an organic solvent or water, preferably water, in an amount of 30.0 wt% to 100 wt%, wherein the wt% is based on the total weight of the composition.

[0150] Furthermore, composition II according to the invention may be a liquid composition comprising or consisting of: component (A) in an amount of 15.0 wt% to 80.0 wt%; component (B1) and / or (B2) in an amount of 2.0 wt% to 40.0 wt%; component (C) in an amount of 2.5 wt% to 24.0 wt%; and at least one solvent, which is an organic solvent or water, preferably water, in an amount of 30.0 wt% to 100 wt%, wherein the wt% is based on the total weight of the composition.

[0151] Composition I according to the invention may be a liquid composition comprising or consisting of: component (A) in an amount of 30.0 wt% to 90.0 wt%, and component (B2) in an amount of 2.0 wt% to 40.0 wt%; and at least one solvent, which is an organic solvent or water, preferably water, in an amount of 50.0 wt% to 300 wt%, wherein the wt% is based on the total dry weight of components (A) and (B2) of composition I according to the invention.

[0152] Composition II according to the invention may also be a liquid composition comprising or consisting of: component (A) in an amount of 30.0 wt% to 90.0 wt%; component (B1) and / or (B2) in an amount of 2.0 wt% to 40.0 wt%; component (C) in an amount of 1.0 wt% to 42 wt%; and at least one solvent, which is an organic solvent or water, preferably water, in an amount of 50.0 wt% to 300 wt%, wherein the wt% is based on the total dry weight of components (A), (B) and (C) of composition II according to the invention.

[0153] In particular, composition I according to the invention may be a liquid composition comprising or consisting of: component (A) in an amount of 30.0 wt% to 80.0 wt%, component (B2) in an amount of 2.0 wt% to 40.0 wt%, and water in an amount of 100.0 wt% to 200.0 wt%, wherein the wt% is based on the total dry weight of components (A) and (B2) of composition I according to the invention.

[0154] In particular, composition II according to the invention may be a liquid composition comprising or consisting of: component (A) in an amount of 30.0 wt% to 80.0 wt%; component (B1) and / or (B2) in an amount of 2.0 wt% to 40.0 wt%; component (C) in an amount of 1.0 wt% to 50.0 wt%; and water in an amount of 100.0 wt% to 200.0 wt%, wherein the wt% is based on the total dry weight of components (A), (B1) and / or (B2) and (C) of composition II according to the invention.

[0155] In particular, composition I according to the invention may be a liquid composition comprising or consisting of: component (A) in an amount of 20.0 wt% to 40.0 wt%; component (B2) in an amount of 5.0 wt% to 15.0 wt%; and at least one solvent, which is an organic solvent or water, preferably water, in an amount of 30.0 wt% to 80 wt%, wherein the wt% is based on the total weight of composition I.

[0156] In particular, composition II according to the invention may be a liquid composition comprising or consisting of: component (A) in an amount of 20.0 wt% to 30.0 wt%; component (B1) and / or (B2) in an amount of 5.0 wt% to 15.0 wt%; component (C) in an amount of 1.0 wt% to 10.0 wt%; and at least one solvent, which is an organic solvent or water, preferably water, in an amount of 30.0 wt% to 80 wt%, wherein the wt% is based on the total weight of composition II.

[0157] Furthermore, composition I according to the invention may also be a liquid composition comprising or consisting of: components (A) and (B2), at least one solvent, which is an organic solvent or water, preferably water, and one or more other additional components, such as, but not limited to, nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers, or combinations thereof.

[0158] Furthermore, composition II according to the invention may also be a liquid composition comprising or consisting of: components (A), (B1) and / or (B2) and (C), at least one solvent, which is an organic solvent or water, preferably water, and one or more other additional components, such as, but not limited to, nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers or combinations thereof.

[0159] Composition I according to the invention may also be a liquid composition comprising or consisting of: component (A), in an amount of 30.0 wt% to 90.0 wt%; component (B2), in an amount of 2.0 wt% to 40.0 wt%; at least one solvent, which is an organic solvent or water, preferably water, in an amount of 50.0 wt% to 300 wt%; and at least one or more nonionic or ionic surfactants other than component (B2), in an amount of 0.01 wt% to 5.0 wt%, wherein the wt% is based on the total dry weight of components (A) and (B2) of composition I according to the invention.

[0160] Composition II according to the invention may also be a liquid composition comprising or consisting of: component (A) in an amount of 30.0 wt% to 90.0 wt%; component (B1) and / or (B2) in an amount of 2.0 wt% to 40.0 wt%; component (C) in an amount of 1.0 wt% to 42.0 wt%; at least one solvent, which is an organic solvent or water, preferably water, in an amount of 50.0 wt% to 300 wt%; and at least one or more nonionic or ionic surfactants other than components (B1) / (B2) in an amount of 0.01 wt% to 5.0 wt%, wherein the wt% is based on the total dry weight of components (A), (B1) and / or (B2) and (C) of composition II according to the invention.

[0161] The composition I according to the invention may also be a liquid mixture comprising or consisting of: component (A), in an amount of 30.0 wt% to 90.0 wt%; and component (B2), in an amount of 2.0 wt% to 40.0 wt%; at least one solvent, which is an organic solvent or water, preferably water, in an amount of 50.0 wt% to 300 wt%; and at least one or more nonionic surfactants and / or ionic surfactants other than component (B2), in an amount of 0.08 wt% to 5.0 wt%, wherein the wt% is based on the total dry weight of components (A) and (B2) of the composition I according to the invention.

[0162] Composition II according to the invention may also be a liquid mixture comprising or consisting of: component (A), in an amount of 30.0 wt% to 90.0 wt%; component (B1) and / or (B2), in an amount of 2.0 wt% to 40.0 wt%; component (C), in an amount of 1.0 wt% to 50.0 wt%; at least one solvent, which is an organic solvent or water, preferably water, in an amount of 50.0 wt% to 300 wt%; and at least one nonionic or ionic surfactant other than component (B1) / (B2), in an amount of 0.08 wt% to 5.0 wt%, wherein the wt% is based on the total dry weight of components (A), (B1) and / or (B2) and (C) of composition II according to the invention.

[0163] Furthermore, composition I according to the invention may also be a liquid mixture comprising: component (A) in an amount of 15.0 wt% to 80.0 wt%; component (B2) in an amount of 2.0 wt% to 40.0 wt%; at least one solvent, which is an organic solvent or water, preferably water, in an amount of 30.0 wt% to 100.0 wt%; and at least one nonionic surfactant and / or ionic surfactant other than component (B2) in an amount of 0.005 wt% to 5.0 wt%, wherein the wt% is based on the total weight of composition I.

[0164] Furthermore, composition II according to the invention may be a liquid mixture comprising: component (A) in an amount of 15.0 wt% to 80.0 wt%; component (B1) and / or (B2) in an amount of 2.0 wt% to 40.0 wt%; component (C) in an amount of 2.5 wt% to 24.0 wt%; at least one solvent, which is an organic solvent or water, preferably water, in an amount of 30.0 wt% to 100.0 wt%; and at least one nonionic surfactant and / or ionic surfactant other than component (B1) / (B2) in an amount of 0.005 wt% to 5.0 wt%, wherein the wt% is based on the total weight of composition II.

[0165] Furthermore, composition I according to the invention may be a liquid mixture comprising or consisting of: component (A) in an amount of 20.0 wt% to 80.0 wt%; component (B2) in an amount of 4.0 wt% to 40.0 wt%; at least one solvent, which is an organic solvent or water, preferably water, in an amount of 50.0 wt% to 250.0 wt%; and at least one nonionic surfactant or ionic surfactant in an amount of 0.01 wt% to 2.5 wt%, wherein the wt% is based on the total weight of composition I.

[0166] Furthermore, composition II according to the invention may be a liquid mixture comprising or consisting of: component (A), in an amount of 20.0 wt% to 80.0 wt%; component (B1) and / or (B2), in an amount of 4.0 wt% to 40.0 wt%; component (C), in an amount of 5.0 wt% to 24.0 wt%; at least one solvent, which is an organic solvent or water, preferably water, in an amount of 50.0 wt% to 250.0 wt%; and at least one nonionic surfactant or ionic surfactant in an amount of 0.01 wt% to 2.5 wt%, wherein the wt% is based on the total weight of composition II.

[0167] Furthermore, all the dry or liquid compositions disclosed according to the invention may additionally include compounds remaining from the copolymerization reaction of the contained copolymer. The term "compound remaining from the copolymerization reaction of the contained copolymer" refers to any monomer, oligomer, salt, solvent, reagent, degradation product, byproduct, or combination thereof derived from the (co)polymerization reaction carried out to obtain component (A), (B1), (B2), or (C).

[0168] The present invention also relates to a method II for manufacturing composition II according to the invention, comprising at least the steps a) and b):

[0169] a) Perform sub-steps i, ii, and optionally iii:

[0170] i. Provide components (B1) and / or (B2) to the first reaction zone;

[0171] ii. Provide at least monomers (A1) and (A2) to the second reaction zone to obtain a monomer mixture; optionally, mix the monomer mixture in the second reaction zone with the mixture in the first reaction zone; and copolymerize the monomer mixture; or provide component (A) directly;

[0172] iii. Optionally, the composition obtained in step i. and / or the composition obtained in step ii. are mixed to provide a first copolymer mixture;

[0173] a) Add component (C) to the copolymer mixture obtained in step a);

[0174] Optionally, in any one of steps a)i., a)ii., a)iii., or b), one or more additional components may be added to the respective mixture.

[0175] This invention relates to a method I for manufacturing composition I, comprising at least step a):

[0176] a) Perform sub-steps i, ii, and optionally iii:

[0177] i) Provide component (B2) to the first reaction zone;

[0178] ii) Provide at least monomers (A1) and (A2) to the second reaction zone to obtain a monomer mixture; optionally mix the monomer mixture in the second reaction zone with the mixture in the first reaction zone; and copolymerize the monomer mixture; or provide component (A) directly;

[0179] iii) Optionally, the composition obtained in step i. and / or the composition obtained in step ii. are mixed to provide a first copolymer mixture;

[0180] Optionally, in any one of steps a)i., a)ii., or a)iii., one or more additional components may be added to the respective mixture.

[0181] Unless otherwise stated, when "method" is mentioned, it refers to method I for manufacturing composition I according to the invention and method II for manufacturing composition II according to the invention. Definitions, scopes, methods of determination, etc., disclosed above and below also apply to methods for manufacturing compositions according to the invention.

[0182] The term "reaction zone" refers to any reaction chamber known in the art suitable for carrying out various reactions, such as, but not limited to, containers, beakers, reactors, flasks, or combinations thereof.

[0183] In step a) of the method according to the invention, steps i., ii. and optional iii are performed.

[0184] In step i, components (B1) / (B2) of the composition according to the invention are provided to the first reaction zone.

[0185] Optionally, one or more additional components may be added before, during, and / or after providing components (B1) / (B2) of the composition according to the invention. Suitable additional components are known in the art and may be selected from the non-limiting group consisting of, for example, nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers, or combinations thereof.

[0186] Furthermore, components (B1) / (B2) of the composition according to the invention may be added in a dry form in step i; or in the form of a liquid mixture (e.g., in combination with at least one solvent, such as water)).

[0187] In addition, components (B1) / (B2) may be provided in dry form in an amount of 80.0 wt% to 100 wt%, optionally together with a nonionic surfactant and / or ionic surfactant in an amount of 0.0 wt% to 20.0 wt%, wherein the wt% is based on the total weight of the components provided in step i.

[0188] In addition, components (B1) / (B2) may be provided in the form of a liquid composition in an amount of 2.0 wt% to 40.0 wt%, optionally together with 0.01 wt% to 2.5 wt% of a nonionic surfactant and / or an ionic surfactant and 70.0 wt% to 90.0 wt% of at least one solvent (preferably containing or composed of water), wherein the wt% is based on the total weight of the components provided in step i.

[0189] Furthermore, the mixture containing components (B1) / (B2) of the composition according to the invention in the first reaction zone can be pre-tempered to a temperature of at least 20°C, or at least 30°C, or at least 40°C, or at most 120°C, or at most 100°C, or at most 90°C, or 20°C to 120°C, or 30°C to 100°C, or 40°C to 90°C, or 80°C, or room temperature, by any technical means known in the art.

[0190] In step ii., at least monomers (A1) and (A2) are provided in at least one solvent (preferably containing or composed of water) and provided to a second reaction zone to obtain a monomer mixture.

[0191] Optionally, one or more additional components may be added before, during, and / or after the provision of at least monomers (A1) and (A2) to the second reaction zone. Suitable additional components are known in the prior art and may be selected from the non-limiting group consisting of: for example, nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers, or combinations thereof.

[0192] At least one thickener may be selected from cellulose, hydrophobically modified alkali-swellable emulsion (HASE), hydrophobically modified polyurethane (HEUR), hydrophobically modified polyether (HMPE), alkali-swellable emulsion (ASE), and special clay (i.e., hydrated magnesium aluminosilicate), or mixtures thereof.

[0193] At least one plasticizer may be selected from C8 to C9. 12 Phthalate esters of alcohols and C8 to C8 esters 12Adipate esters of alcohols, preferably di(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, di(2-ethylhexyl) phthalate, diisononyl phthalate and diisodecyl phthalate, or mixtures thereof.

[0194] Monomer (A1) may be supplied in amounts from 20.0 wt% to 75.0 wt%, and monomer (A2) may be supplied in amounts from 80.0 wt% to 25.0 wt%, wherein the wt% is based on the total weight of monomers (A1) and (A2) supplied in step ii.

[0195] The monomer (A1) may be provided in an amount of 20.0 wt% to 75.0 wt%, and the monomer (A2) may be provided in an amount of 80.0 wt% to 25.0 wt% together with at least one solvent (preferably containing or composed of water) in an amount of 10.0 wt% to 35.0 wt%, wherein the wt% is based on the total weight of the components provided in step ii.

[0196] In addition, monomer (A1) may be provided in an amount of 20.0 wt% to 75.0 wt%, and monomer (A2) may be provided in an amount of 80.0 wt% to 25.0 wt% together with at least one solvent (preferably containing or composed of water) in an amount of 10.0 wt% to 30.0 wt% and a nonionic surfactant and / or ionic surfactant in an amount of 0.01 wt% to 5.0 wt%, wherein the wt% is based on the total weight of the components provided in step ii.

[0197] Furthermore, a monomer mixture comprising at least monomers (A1) and (A2) of the composition according to the invention can be preheated to a temperature of at least 0°C, or at least 10°C, or at least 20°C, or at most 80°C, or at most 60°C, or at most 40°C, or 0°C to 80°C, or 10°C to 60°C, or 20°C to 40°C, or below 25°C, by any technical means known in the art.

[0198] Further optionally, in step ii, one or more additional monomers (A3) may be added before, during and / or after providing monomers (A1) and (A2) to the monomer mixture.

[0199] Optionally, the monomer mixture in the second reaction zone can be combined with the mixture obtained in step i.

[0200] Further in step ii., with or without the mixture obtained in step i., the comonomer mixture is copolymerized to obtain component (A). Preferably, the mixture from step i. is present in the copolymerization process of the monomer mixture from step ii.

[0201] The copolymerization in step ii. can be carried out at temperatures ranging from 0°C to 95°C, or from 10°C to 90°C, or from 20°C to 90°C, or from 40°C to 80°C for a time ranging from 0.25 h to 24 h, or from 0.5 h to 18 h, or from 1 h to 12 h, or from 1 h to 8 h.

[0202] Copolymerization may require an initiator to initiate the reaction. Initiators suitable for this reaction are not limited and can be found in the prior art, such as, but not limited to, thermal, radiation, or initiator compounds capable of being used as chain reaction initiators.

[0203] The term "chain reaction initiator" refers to any compound known in the art that can be used to initiate polymer chain reactions through any known mechanism, such as, but not limited to, the formation of free radicals, charged atoms, etc. Non-limiting examples are sodium persulfate, azobisisobutyronitrile (AIBN), ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, or combinations thereof.

[0204] An initiator compound mixture comprising at least one solvent (preferably water or composed of water) and at least one initiator can be prepared in a third reaction zone, and the initiator compound mixture can be added to a mixture in a second reaction zone after complete homogenization.

[0205] An initiator compound mixture comprising 80.0 wt% to 99.5 wt% of at least one solvent (preferably containing or composed of water) and 0.5 wt% to 20.0 wt% of at least one initiator (preferably sodium persulfate) can be prepared in the third reaction zone, wherein the wt% is based on the total weight of the components provided in the third reaction zone.

[0206] In addition, the initiator compound mixture can be preheated to a temperature of at least 0°C, or at least 10°C, or at least 20°C, or at most 80°C, or at most 60°C, or at most 40°C, or 0°C to 80°C, or 10°C to 60°C, or 20°C to 40°C, or below 25°C.

[0207] The initiator compound mixture can be added entirely to the mixture in the second reaction zone at once, or added in batches over the duration of copolymerization. Alternatively, the initiator compound mixture and the monomer mixture in the second reaction zone can be added simultaneously in batches or entirely to the mixture in the first reaction zone.

[0208] In addition, the mixture generated by mixing the initiator compound mixture and the mixture in the second reaction zone can be allowed to stand for an additional time frame within the range of 0°C to 95°C, or 10°C to 90°C, or 20°C to 90°C, or 40°C to 80°C for 0.25 h to 24 h, or 0.5 h to 18 h, or 1 h to 12 h, or 1 h to 8 h.

[0209] Optionally, prior to copolymerization in step ii., a homogenization step may be performed to homogenize all reagents present in the mixture in the second reaction zone.

[0210] Preferably, the copolymer is designed as an emulsion polymerization. Preferably, components (B1) / (B2) are used as polymer surfactants in the copolymer, and the copolymer is preferably designed as an emulsion polymerization. Preferably, nonionic and / or ionic surfactants are absent in the copolymer.

[0211] Furthermore, the copolymer mixture obtained after copolymerization in step ii. of the method according to the invention can be completely dried by any technical means known in the prior art.

[0212] Instead of providing at least monomers (A1) and (A2) and a subsequent copolymerization reaction, the already synthesized component (A) can be provided directly in step ii. of the method according to the invention.

[0213] In step iii, optionally, a mixing step is performed after sub-steps i. and ii. of method II according to the invention, wherein the mixture of components (B1) and / or (B2) in the first reaction zone and the mixture of components (A) in the second reaction zone are combined and optionally homogenized.

[0214] The mixture obtained in step iii. can be a dry mixture or a liquid mixture.

[0215] In step b) of method II according to the invention, component (C) is added to the copolymer mixture obtained from step a) of method II according to the invention.

[0216] Optionally, one or more additional components, such as nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers, or combinations thereof, may be added before, during, and / or after the component (C) is provided to the copolymer mixture.

[0217] Component (C) of the composition II according to the invention, either in dry form or as a liquid mixture, may also be added, for example, together with at least one solvent (preferably containing or composed of water).

[0218] Component (C) of composition II according to the present invention may also be added in the form of an aqueous emulsion, an aqueous suspension, an aqueous solution, an aqueous slurry, or a mixture thereof.

[0219] In addition, component (C) of composition II according to the invention can be provided in a dried form.

[0220] A liquid mixture comprising 10.0 wt% to 40.0 wt% of component (B1) / (B2), 0.01 wt% to 2.5 wt% of surfactant, and 70.0 wt% to 90.0 wt% of at least one solvent (preferably comprising or composed of water) can be prepared in a first reaction zone, wherein the wt% is based on the total weight of the components provided in the first reaction zone; and a mixture comprising 20.0 wt% to 75.0 wt% of monomer (A1), 80.0 wt% to 25.0 wt% of monomer (A2), 10.0 wt% to 30.0 wt% of at least one solvent (preferably comprising or composed of water), and 0.01 wt% to 5.0 wt% of surfactant can be prepared in a second reaction zone, wherein the wt% is based on the total weight of the components provided in the second reaction zone;

[0221] In the case of method II according to the invention, a mixture comprising 80.0 wt% to 99.5 wt% of at least one solvent (preferably comprising or composed of water) and 0.5 wt% to 20.0 wt% of at least one initiator (preferably sodium persulfate) is prepared in the third reaction zone, wherein the wt% is based on the total weight of the components provided in the third reaction zone; and

[0222] The mixture in the first reaction zone is preheated to a temperature in the range of 40°C to 90°C and added to the mixture in the second reaction zone. Then, the mixture in the third reaction zone is added in batches over a period of 1 h to 8 h at a temperature in the range of 40°C to 90°C. In the case of method II according to the invention, component (C) in the form of an aqueous dispersion is provided to obtain the liquid composition according to the invention.

[0223] Furthermore, a dry mixture comprising 80.0 wt% to 99.99 wt% of component (B1) / (B2) and 0.01 wt% to 20.0 wt% of surfactant can be prepared in the first reaction zone, wherein the wt% is based on the total weight of the components provided in the first reaction zone; and a mixture comprising 20.0 wt% to 75.0 wt% of monomer (A1) and 80.0 wt% to 25.0 wt% of monomer (A2), 10.0 wt% to 30.0 wt% of at least one solvent (preferably comprising or composed of water) and 0.01 wt% to 5.0 wt% of surfactant can be prepared in the second reaction zone, wherein the wt% is based on the total weight of the components provided in the second reaction zone;

[0224] In the third reaction zone, a mixture is prepared comprising 80.0 wt% to 99.5 wt% of at least one solvent (preferably comprising or composed of water) and 0.5 wt% to 20.0 wt% of at least one initiator (preferably sodium persulfate), wherein the wt% is based on the total weight of the components provided in the third reaction zone; and

[0225] The mixture in the first reaction zone is preheated to a temperature ranging from 40°C to 90°C and added to the mixture in the second reaction zone. Then, the mixture in the third reaction zone is added in batches over a period of 1 to 8 hours at a temperature ranging from 40°C to 90°C.

[0226] After the reaction, dry it completely; and

[0227] In the case of method II according to the invention, 1 to 50 wt% of component (C) in dried form is provided to obtain the dried composition according to the invention, wherein the wt% is based on the total dry mass percentage of components (A), (B1) / (B2) / (C) being 100 wt%.

[0228] Furthermore, a dry mixture comprising 80.0 wt% to 99.99 wt% of component (B1) / (B2) and 0.01 wt% to 20.0 wt% of surfactant can be prepared in the first reaction zone, wherein the wt% is based on the total weight of the components provided in the first reaction zone; and

[0229] Component (A) is prepared in the second reaction zone; and

[0230] The mixtures contained in the first and second reaction zones are combined and mixed together; and

[0231] In the case of method II according to the invention, component (C) in a dried form is added to obtain the dried composition according to the invention as defined above.

[0232] The present invention also relates to the use of compositions according to the invention or compositions manufactured by the method according to the invention as barrier materials on a substrate as defined above. Definitions, scopes, methods of measurement, etc., disclosed above and below also apply to the use of compositions according to the invention.

[0233] In particular, the present invention also relates to the use of composition I according to the invention or composition I manufactured by method I according to the invention as a liquid barrier or heat sealant on a substrate, wherein the substrate is as defined above, and in particular, wherein the substrate is a food or beverage container, such as: hot and cold beverage containers, soup containers, ice cream cups and other food packaging.

[0234] As used in the context of this application, the terms "heat seal" or "heat-sealing" refer to the contact between two surfaces when a heat-sealing agent (i.e., composition I according to the invention) is applied to a molten and hot-pressed substrate surface. Therefore, heat sealing is a method of adhering two materials to each other by heat and pressure for a certain period of time. This step is referred to as the wetting phase that occurs in the sealing area. Within a short time, a bond is rapidly formed between the two surfaces through the melting of the coating. After this step, the coating cures, fixing the surfaces together and thus enhancing the seal strength. The sealing property of the coating lies in its ability to act as its own bond-forming agent without any additional hot-melt adhesive. A good seal will impart complete paper fiber tear resistance, which is crucial for ensuring food safety and quality.

[0235] The present invention also relates to the use of the composition IIe according to the invention or the composition IIe manufactured by method II according to the invention as a barrier (particularly as an oil barrier and / or grease barrier and / or liquid barrier and / or heat seal on a substrate, wherein the substrate is as defined above.

[0236] The present invention also relates to the use of the composition IIw according to the invention or the composition IIw manufactured by method II according to the invention as a barrier (particularly as a liquid barrier on a substrate and / or a heat sealant), wherein the substrate is as defined above.

[0237] Typical applications of Composition II according to the invention include packaging paper, paper trays, and food packaging. The coated product, when applied to paper and paperboard, constitutes a product that can be used as a food contact surface.

[0238] The present invention also relates to the use of the composition IIEw according to the invention or the composition IIEw manufactured by the method according to the invention as a barrier (particularly as an oil barrier and / or grease barrier and / or liquid barrier and heat sealant on a substrate), wherein the substrate is as defined above.

[0239] The present invention also relates to a method for manufacturing a coated substrate, comprising the following steps:

[0240] I) Applying the composition according to the invention or the composition manufactured according to the invention to a substrate;

[0241] II) Dry the composition according to the invention or the composition manufactured according to the invention on the substrate.

[0242] The definitions, scope, and measurement methods disclosed above and below also apply here.

[0243] Therefore, the term "apply" includes any technical means known in the art for applying a composition (especially a liquid composition) to a substrate, such as, but not limited to, coating, spraying, brushing, dipping, or combinations thereof.

[0244] In step I) of the method for manufacturing a coated substrate according to the invention, the composition according to the invention or the composition manufactured according to the invention is applied to a suitable substrate.

[0245] If the composition according to the invention or the composition manufactured by the method according to the invention is a liquid composition, it can be used directly in step I. If the composition according to the invention or the composition manufactured by the method according to the invention is a dry composition, at least one solvent (preferably containing water or composed of water) needs to be added.

[0246] Step I can be applied once or multiple times.

[0247] In addition, the composition and / or substrate may be subjected to temperature conditioning before, during, or after step I.

[0248] In step II, the treated substrate is dried by any technical means known in the prior art, such as, but not limited to, hot air drying, IR radiation, drying by contact with a hot metal cylinder, or a combination thereof.

[0249] Furthermore, the present invention relates to coated substrates manufactured according to the present invention, which comprise or consist of compositions according to the present invention, or compositions comprise or consist of compositions manufactured according to the methods of the present invention. Definitions, scopes, methods of measurement, etc., as disclosed above and below, also apply herein.

[0250] This invention also relates to coated substrates comprising an outer coating selected from any outer coating known in the prior art. Non-limiting examples of outer coatings are moisture barriers, oxygen barriers, heat sealants, gas barriers, aesthetic outer coatings (e.g., printed, varnished, or gloss-providing outer coatings), or combinations thereof. The definitions, scopes, and methods of measurement disclosed above and below also apply herein.

[0251] Furthermore, the present invention relates to a method for manufacturing an article comprising or consisting of a coated substrate according to the invention or a coated substrate manufactured according to the method of the invention, wherein the coated substrate is subjected to measures selected from the group consisting of: cutting, folding, gluing, curing, dyeing, or combinations thereof. Definitions, scopes, methods of measurement, etc., as disclosed above and below also apply herein.

[0252] Furthermore, the present invention relates to articles comprising or composed of a coated substrate according to the invention or a coated substrate manufactured according to the method of the invention, wherein said articles are food containers, plates, straws, bags, bowls, cloths, bags (made of paper or textiles). Definitions, scopes, methods of measurement, etc., as disclosed above and below also apply herein.

[0253] Articles including coated substrates according to the invention or coated substrates manufactured according to the method of the invention can be textiles, such as, but not limited to, clothing articles or bags.

[0254] Example

[0255] The invention will be described in more detail below; however, the invention is not limited to the specific embodiments described below.

[0256] Test program

[0257] Liquid barrier properties were determined according to the TAPPI T441 test method (Cobb test).

[0258] Liquid barrier properties are determined according to the TAPPI T441 standard test method (Cobb test). The amount of liquid that a given area of ​​the sample can absorb after a specific time period is measured.

[0259] Cut the test sample paper into 12.5 x 12.5 mm specimens. Pre-weigh the specimen on a balance and place it in the Cobb apparatus while it is dry. Once the test sample paper is in place, pour a fixed amount of liquid (e.g., water, cola, oil, or hot coffee) (100 ml (± 5 ml)) into the cylindrical container. Start the timer simultaneously. Unless otherwise specified, drain the remaining liquid after 60 seconds. Place the test sample paper (wet side up) between two sheets of blotting paper placed on a flat, rigid surface and remove excess liquid by moving the manual pressure roller back and forth on the pad once without applying any additional pressure to the roller. Samples showing signs of leakage around the clamping area should be discarded. If any liquid penetrates the sheet and reaches the rubber pad, the test is unacceptable. If this occurs, reduce the time to 30 seconds. Then weigh the (wet) test sample.

[0260] The Cobb value is calculated using the following equation:

[0261] Cobb [g / m 2 ] = (W 湿 –W 干 ) x 100

[0262] A high Cobb value indicates that the substrate can easily absorb and retain moisture. A low Cobb value indicates that the substrate can resist penetration and retain moisture. Typical target Cobb values ​​for the packaging industry are:

[0263] - Water absorption (approximately room temperature): ≤ 20 g absorbed water / m²

[0264] - Cola absorbability (approximately room temperature): ≤ 20 g absorbed water / m²

[0265] - Hot coffee absorbency (approximately 80°C): ≤ 20 g absorbed water / m²

[0266] - Oil absorption (approximately room temperature): ≤ 20 g absorbent oil / m²

[0267] Determination of oil / grease barrier properties (according to Tappi T559 standard test method)

[0268] Oil resistance / grease resistance can also be determined according to the Tappi standard T559 KIT test. A value of 1 indicates poor / no oil / grease resistance, while a value of 12 indicates best / high oil / grease resistance.

[0269] Determination of blocking temperature

[0270] The adhesion temperature is determined as follows: Two test samples (25 mm * 297 mm) of treated substrate are prepared and placed in an overlapping relationship with the treated surfaces facing each other in the HT-IXS thermal tack tester. The standard test is performed at a residence time of 10 s and a pressure of 1 bar. Both clamps are heated to a variable temperature. The "adhesion temperature" is the highest temperature at which the device measures no adhesion (i.e., no strength between the two strips).

[0271] Determination of heat-sealing performance

[0272] Heat-sealing performance was determined as follows: Two test samples (25 mm * 297 mm) of treated substrate were prepared and placed in an overlapping relationship with the treated surfaces facing each other in the HT-IXS heat tack tester. The standard test was performed at a dwell time of 10 s and a pressure of 2 bar. Both clamps were heated to a variable temperature. The “heat-sealing temperature” corresponds to the temperature measured by the device that provides sufficient strength to form a seal between the two sheets of paper.

[0273] For the tests reported below, a weight of 250 g / m³ was used. 2 The coating amount is 8-9 g / m 2 The sealing area is a cardboard sheet with a diameter of 1.2 cm × 3.5 cm. The tensile speed is set to 50 mm / s. Heat seal strength is reported in Newtons (N), and is the strength required to separate the test strips from each other after sealing. A value of ≥ 3 N is considered sufficient heat seal strength.

[0274] Product stability test

[0275] 100 g of the corresponding sample was stored in a 125 mL glass flask at 50 °C. Visible phase separation of the sample was checked every 24 h. In the second stability test, 100 g of the corresponding sample was filtered through a 150 µm nylon filter. The weight of the coarse particles (grits) remaining on the filter was weighed and expressed in ppm relative to the total weight of the corresponding product. The results can be found in Table 5 below.

[0276] Preparation and performance determination of composition I according to the present invention

[0277] General preparation procedure

[0278] 300 g of demineralized water was introduced into reactor (reactor 1). Optionally, component (B2) was added and dissolved in the demineralized water with ammonium hydroxide. The mixture was then heated to 80°C. In Comparative Example 1, 2 g of dodecyl sulfate was added instead of component (B2). In Examples 1 to 3 and 9 of the Invention, 1 g of dodecyl sulfate was added together with component (B2).

[0279] In another reactor (reactor 2), dodecyl sulfate (omitted in Examples 5 to 7 of the invention) is dissolved in demineralized water, and then monomers (A1) and (A2) are added. The monomer mixture is stirred until homogeneous and kept below 25°C.

[0280] In the third reactor (reactor 3), 1 g of sodium persulfate was dissolved in 39 g of demineralized water. The solution was also kept at a temperature below 25°C.

[0281] When the internal temperature of reactor 1 reaches 80°C, the mixture contained in reactor 2 is metered into the mixture in reactor 1, while the contents of reactor 3 are simultaneously metered into reactor 2. The metering is carried out over 5 hours. At the end of the metering, the pump is flushed with 8 g of demineralized water. The internal temperature is maintained at 80°C for 1 hour. The resulting copolymer dispersion is then cooled to room temperature.

[0282] Table 1 lists the compounds used and their quantities.

[0283] The results of liquid resistance tests, as well as heat-sealing performance, adhesion temperature, and stability, can be found in Tables 2 and 3.

[0284] Table 1: Comparative Examples and Inventive Examples of Composition I

[0285]

[0286]

[0287] * % indicates wt% based on the total weight of the aqueous composition.

[0288] # Component (B2): 25.0 to 35.0 wt% maleic anhydride and 65.0 to 75.0 wt% styrene, wherein wt% is based on the total weight of component (B2) (=100 wt%), esterified using ethanol, butanol, isobutanol or mixtures thereof, with a molecular weight in the range of 1,000 g / mol to 10,000 g / mol and a glass transition temperature of 90°C to 130°C; the wt% of SMA and alcohol in the esterification is 80 wt% to 90 wt% and 10 to 20 wt%, respectively, wherein wt% is based on the total amount of SMA and alcohol used in the esterification reaction (=100 wt%).

[0289] Coating process

[0290] All comparative compositions and inventive examples of Composition I were applied to white cardboard using an automatic coating machine at a speed of 250 mm / s, with a coating weight of 5 g / m². 2The samples were dried using an IR lamp at 110°C. The results obtained from the tests described herein (i.e., liquid resistance, heat-sealing strength, and tack temperature) can be found in the comparative examples in Table 2. The results of the stability tests can be found in Table 3.

[0291] result

[0292] Table 2: Results of liquid resistance test, heat sealing performance, and adhesion temperature

[0293]

[0294] Table 3: Results of the stability tests conducted

[0295]

[0296] Preparation and performance determination of composition IIe according to the present invention

[0297] General preparation procedure:

[0298] 300 g of demineralized water was introduced into reactor (reactor 1). Optionally, component (B1) was added and dissolved in the demineralized water with ammonium hydroxide. The mixture was then heated to 80°C. In Comparative Examples 1, 3, and 4, 2 g of dodecyl sulfate was added instead of SMA. In Inventive Example 1, 1 g of dodecyl sulfate was added together with SMA.

[0299] In another reactor (reactor 2), 10 g of dodecyl sulfate (omitted in Example 6 of the invention) was dissolved in demineralized water, and then at least monomers (A1) and (A2) were added. The monomer mixture was stirred until homogeneous and kept below 25°C.

[0300] In the third reactor (reactor 3), 1 g of sodium persulfate was dissolved in 39 g of demineralized water. The solution was also kept at a temperature below 25°C.

[0301] When the internal temperature of reactor 1 reaches 80°C, the mixture contained in reactor 2 is metered into the mixture in reactor 1, while the contents of reactor 3 are simultaneously metered into reactor 2. The metering is carried out over 5 hours. At the end of the metering, the pump is flushed with 8 g of demineralized water. The internal temperature is maintained at 80°C for 1 hour. The resulting copolymer dispersion is then cooled to room temperature.

[0302] The copolymer dispersion was prepared at room temperature, and then component I was added. Table 4 lists all the compounds used and their amounts.

[0303] In the case of the comparative example of compound IIe, the results of the tests on liquid resistance, grease resistance and oil resistance, as well as the adhesion temperature, can be found in Table 5, while in the case of the inventive example of compound IIe, they can be found in Table 6.

[0304] Table 4a: Comparative examples and inventive compositions of compound IIe.

[0305]

[0306] Table 4b: Continued from Table 4a.

[0307]

[0308] * % indicates wt% based on the total weight of the aqueous composition.

[0309] Comparative Examples 1, 3, and 4 were prepared using 2 g of dodecyl sulfate, but without SMA.

[0310] x Example 1 of the invention is prepared by adding 1 g of dodecyl sulfate together with SMA to reactor 1.

[0311] # Invention Example 6 was prepared without adding any nonionic or ionic surfactants.

[0312] a Component (B1): 25.0 to 35.0 wt% maleic anhydride and 65.0 to 75.0 wt% styrene, where wt% is based on the total weight of component (B1) (=100 wt%); molecular weight in the range of 1,000 g / mol to 10,000 g / mol, and glass transition temperature in the range of 110°C to 150°C.

[0313] Coating process

[0314] Unless otherwise reported, all comparative compositions and inventive examples of composition IIe were applied to office white paper using an automatic coating machine at a speed of 250 mm / s, with a coating weight of 5 g / m². 2 The samples were dried using an IR lamp at 110°C. The results obtained from the tests described herein (i.e., liquid resistance, oil resistance, and adhesion temperature) can be found in the comparative examples in Table 5 and the inventive examples in Table 6.

[0315] Folding general program

[0316] All the toughnesses discussed below were measured before and after the subsequent folding process to obtain data on the foldability of the substrate treated with the compositions described in Table 4. Folding was performed on a large blotting paper using a 10 kg pressure roller. The substrate was folded twice, once longitudinally and once intersecting longitudinally. Figure 1 shows the blotting paper and pressure roller, as well as the results of the folding.

[0317] Table 5: Results of water and oil resistance tests and determination of adhesion temperature for comparative examples.

[0318]

[0319] In summary, the low SMA ratios in Examples 1 to 3 resulted in undesirable tacky compositions, where the compositions bonded even at low temperatures when combined with styrene-acrylate copolymers. However, adding SMA alone also failed to produce satisfactory compositions, as all toughness decreased after folding the treated substrate, thus insufficient to form the final molded article. Similar findings can be observed with prior art acrylic copolymer-based compositions, which exhibit inadequate toughness after folding.

[0320] Furthermore, it is evident from Comparative Examples 2, 3, 8, and 9 that the addition of an elastomer (such as natural latex) produces higher folding resistance. However, the elastomer itself cannot provide sufficient resistance.

[0321] Table 6: Results of water resistance and oil resistance tests and determination of adhesion temperature of the invention examples.

[0322]

[0323] Compared to the comparative examples discussed above, all inventive examples of composition IIe exhibited low water absorption in the Cobb test and high oil / grease resistance in the KIT test. Furthermore, the bonding temperature was sufficiently high to meet industrial requirements. Moreover, the inventive examples of composition IIe showed improved durability in the tests even after subsequent folding processes.

[0324] In summary, all inventive examples of the composition IIe according to the present invention provide good water and oil / grease resistance as well as a sufficiently high adhesion temperature, thereby achieving the objectives of the present invention.

[0325] Table 7: Results of stability tests on all samples.

[0326]

[0327] The product stability test results shown in Table 7 clearly demonstrate that components such as wax or a high proportion of natural latex cause stability issues. However, all the inventions exhibit satisfactory storage performance at 50°C, making them suitable for coating applications.

[0328] Preparation and performance determination of composition IIw according to the present invention

[0329] General preparation procedure

[0330] 340 liters of demineralized water were introduced into reactor (reactor 1). 80 to 110 kg of component (B1) in powder form (the same as used in the preparation of composition IIe) was added. The temperature was raised to 40°C and 30 kg of ammonium hydroxide (aqueous solution) was added. The mixture was then heated to 80°C. Demineralized water was added to adjust the concentration to 20%. 480 kg of the mixture thus prepared was used below.

[0331] In another reactor (reactor 2), monomers (monomer A1: 35 to 60 wt% styrene, methyl methacrylate and / or acrylonitrile; monomer A2: 40 to 65 wt% 2-ethylhexyl acrylate; wt% based on total monomer amount (=100 wt%)) (total amount 200 to 250 kg). The monomer mixture is stirred until homogeneous and kept below 25°C.

[0332] In the third reactor (reactor 3), 2.2 kg of ammonium persulfate was dissolved in 9 kg of demineralized water. The solution was also kept at a temperature below 25°C.

[0333] When the internal temperature of reactor 1 reaches 80°C, the mixture contained in reactor 2 is metered into the mixture in reactor 1, while the contents of reactor 3 are simultaneously metered into reactor 2. This metering process is carried out over 5 hours. At the end of the metering process, the pump is flushed with 80 kg of demineralized water. The internal temperature is maintained at 80°C for 1 hour. The resulting copolymer dispersion is then cooled to 35°C.

[0334] Then, while stirring, add 200 to 250 kg of soybean wax emulsion (40% solids content). Then allow the resulting composition IIw to cool to room temperature.

[0335] Coating process

[0336] Unless otherwise reported, the composition IIw of the present invention is applied to white cardboard using an automatic coating machine at a speed of 250 mm / s, with a coating weight of 0 to 14 g / m. 2 They were then dried using an IR lamp at 110°C. The best results obtained from the tests described in this paper are shown in the table below.

[0337] result

[0338] Table 8: Oil Absorption Determination Based on TAPPI T441 (Cobb Test)

[0339]

[0340] Table 9: Oil resistance / grease resistance determined by KIT test

[0341]

Claims

1. A composition for providing barrier properties, particularly liquid resistance, to a substrate, comprising at least components (A) and (B2), wherein (A) is at least one copolymer comprising monomer units of: (A1) is a monomer selected from at least one of the following: styrene, methyl methacrylate, (meth)acrylonitrile, α-methylstyrene, or mixtures thereof; and (A2) at least one monomer comprising an acrylate unit; and (B2) is at least one styrene maleic anhydride ester.

2. The composition according to claim 1, wherein component (A) is present in an amount ranging from 30.0 wt% to 90.0 wt%; Component (B2) is present in amounts ranging from 2.0 wt% to 40.0 wt%; wherein the total dry mass percentage of components (A) and (B2) is 100 wt%.

3. A method for manufacturing a composition according to at least one of claims 1 or 2, comprising at least the following step a): a) Perform sub-steps i, ii, and optionally iii: i.) Provide component (B2) to the first reaction zone; ii.) Provide at least the monomers (A1) and (A2) to the second reaction zone to obtain a monomer mixture; optionally combine the monomer mixture in the second reaction zone with the mixture in the first reaction zone; and copolymerize the monomer mixture to obtain component (A); or provide component (A) directly; iii.) Optionally, the composition obtained in step i. and / or the composition obtained in step ii. are mixed to provide a first copolymer mixture; Optionally, in any one of steps a)i., a)ii., or a)iii., one or more additional components may be added to the respective mixture.

4. A composition for providing barrier properties to a substrate, comprising at least components (A), (B1) and / or (B2) and (C), wherein (A) is a copolymer comprising at least one of the following monomer units: (A1) is a monomer selected from at least one of the following: styrene, methyl methacrylate, (meth)acrylonitrile, α-methylstyrene, or mixtures thereof; and (A2) at least one monomer comprising an acrylate unit; and (B1) is at least one styrene-maleic anhydride copolymer and / or (B2) is at least one styrene maleic anhydride ester, and (C) is at least one elastomer and / or at least one wax, preferably at least one plant wax.

5. The composition according to at least one of claims 1 to 4, wherein at least one monomer (A1) is present in an amount of 20.0 to 75.0 wt%, and / or at least one monomer (A2) is present in an amount of 25.0 to 80.0 wt%, preferably wherein at least one monomer (A1) is present in an amount of 25.0 to 65.0 wt%, and / or at least one monomer (A2) is present in an amount of 35.0 to 75.0 wt%, optionally, wherein one or more other monomers (A3) may be present in the copolymer in an amount of up to 5 wt%, the copolymer comprising equal to 100 wt% of components (A1), (A2) and optionally (A3).

6. The composition according to at least one of claims 1 to 5, wherein at least one monomer (A2) is selected from alkyl acrylates or alkyl methacrylates other than methyl methacrylate, including methyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, decyl acrylate, dodecyl acrylate, isomers thereof, and combinations thereof; and / or one or more other monomers (A3) are selected from (meth)acrylamide, (meth)acrylic acid, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, divinylbenzene, ethylene glycol dimethacrylate, itaconic acid, N-hydroxymethyl (meth)acrylamide, 4-methyl-1,4-pentanediol dimethacrylate, propylene glycol dimethacrylate, trivinylbenzene, or mixtures thereof.

7. The composition according to at least one of claims 4 to 6, wherein the at least one elastomer is selected from the group consisting of ethylene / vinyl acetate, polybutadiene, natural latex, synthetic latex, styrene-butadiene emulsion, or mixtures thereof; preferably wherein component (C) is natural latex or polybutadiene or mixtures thereof; and / or wherein the plant wax is selected from soybean wax, carnauba wax, beeswax, corn wax, coconut wax, palm oil, hydrogenated corn oil, hydrogenated coconut oil, hydrogenated castor oil, hydrogenated rapeseed oil, or combinations thereof.

8. The composition according to at least one of claims 1 to 7, wherein the composition may contain at least one other component selected from: nonionic surfactants, ionic surfactants, pH adjusters, preservatives, dyes, pigments, defoamers, thickeners, waxes, wetting agents, plasticizers, or combinations thereof.

9. The composition according to at least one of claims 1 to 8, wherein the composition is a dry composition, preferably a powder or granules; or wherein the composition is a liquid composition comprising a solvent such as an organic solvent or water, preferably wherein the composition is an aqueous emulsion, an aqueous suspension, an aqueous solution, an aqueous slurry, or a mixture thereof.

10. The composition according to at least one of claims 4 to 9, wherein component (A) is present in an amount ranging from 30.0 wt% to 90.0 wt%; Components (B1) and / or (B2) are present in amounts ranging from 2.0 wt% to 40.0 wt%. Component (C): The at least one elastomer is present in an amount ranging from 1.0 wt% to 42.0 wt%, and / or the at least one wax is present in an amount ranging from 1 wt% to 50 wt%. The total dry mass percentage of the components (A), (B1) and / or (B2) and (C) is 100 wt%.

11. A method for manufacturing a composition according to at least one of claims 4 to 10, comprising at least the steps a) and b): a) Perform sub-steps i, ii, and optionally iii: i.) Provide components (B1) and / or (B2) to the first reaction zone; ii.) Provide at least the monomers (A1) and (A2) to the second reaction zone to obtain a monomer mixture; optionally combine the monomer mixture in the second reaction zone with the mixture in the first reaction zone; and copolymerize the monomer mixture to obtain component (A); or provide component (A) directly; iii.) Optionally, the composition obtained in step i. and / or the composition obtained in step ii. are mixed to provide a first copolymer mixture; b) Add component (C) to the first copolymer mixture obtained in step a); Optionally, in any one of steps a)i., a)ii., a)iii., or b), one or more additional components may be added to the respective mixture.

12. Use of the composition according to at least one of claims 4 to 10 or the composition made according to the method of claim 11 as a barrier, particularly an oil barrier and / or a grease barrier, wherein if (C) is at least one elastomer, the composition is also used for anti-folding; and if (C) is at least one wax, the composition is also used as a liquid barrier on a substrate; preferably, wherein the substrate is a cellulose-based substrate, preferably paper or paperboard, or a substrate based on a synthetic polymer such as nylon; Or based on natural materials such as wool; or mixtures of two or more of these substrates; and use of the composition according to at least one of claims 1, 2, 5 and 6, 8 and 9 or the composition made by the method according to claim 3 as a liquid barrier or a heat sealant on a substrate; preferably, said substrate is a cellulose-based substrate, preferably paper or paperboard, or a substrate based on a synthetic polymer such as nylon; or a substrate based on a natural material such as wool; or mixtures of two or more of these substrates.

13. A coated substrate, wherein the coating of the substrate comprises or consists of a composition according to at least one of claims 1 to 10 or a composition made according to the method of claim 3 or 11; preferably, wherein the substrate is a cellulose-based substrate, preferably paper or paperboard, or a substrate based on a synthetic polymer such as nylon; or a substrate based on a natural material such as wool; or a mixture of two or more of these substrates; preferably, wherein the coated substrate further comprises an outer coating selected from: moisture barrier, oxygen barrier, heat sealant, gas barrier, aesthetic outer coating such as printing, varnish or gloss-providing outer coating, or a combination thereof.

14. A method for manufacturing a coated substrate according to claim 13, comprising the following steps: I) Applying the composition according to at least one of claims 1 to 10 or the composition prepared by the method according to claim 3 or 11 to a substrate; II) Drying the composition according to at least one of claims 1 to 10 or the composition manufactured according to the method of claim 3 or 11 on the substrate.

15. A method of manufacturing an article comprising or consisting of a coated substrate according to claim 13 or a coated substrate manufactured by the method according to claim 14, wherein the coated substrate is subjected to measures selected from the group consisting of: cutting, folding, gluing, curing, dyeing, or combinations thereof.

16. An article comprising or consisting of a coated substrate as described in claim 13 or a coated substrate manufactured according to the method of claim 14, or an article manufactured according to the method of claim 15, wherein the article is a food or beverage container, plate, straw, bag, bowl, cloth, or bag (made of paper or textiles).

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