TW482818B - Method of manufacture of a laminate having gas barrier properties - Google Patents

Abstract

The invention relates to a method of laminating two substrates by coating at least one side of a substrate with a laminating adhesive, bringing a coated side of said substrate into contact with a second substrate to form a three layer film, and treating said three layer film with a free radical initiator, wherein said laminating adhesive is formed by mixing an ethylenically unsaturated acid and a polyamine.

Description

482818 A7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs B7 V. Description of the invention 纟) Field of the invention The invention relates to coatings containing polyamines, which are both barrier and adhesive, and can be used in packaging applications. BACKGROUND OF THE INVENTION Coatings containing silane compounds and itaconic acid can improve the gas, oil and odor barrier properties of organic polymer film substrates. Furthermore, the adhesion of the coating provided by the silane coating to the film surface and the improved barrier properties can also be greatly enhanced by exposing the coating film to electron beam radiation. A particularly useful barrier composition is contained in the United States patent No. 5,215,822, which mentions a methanol solution containing vinyl benzylamine silane (Dow Corning Z-6032), decomposing itaconic acid, and water; a low-density polyethylene film treated with corona The coating is dried with this solution, and then the coated film is subjected to electron beam irradiation to graft the coating to the film surface, which can further improve the barrier properties of the silane coating. However, although this coating can produce excellent gas barrier properties at low to moderate relative humidity, its breathability can be extremely increased at very high relative humidity. The inventors of the present case have surprisingly found that the combination of polyamine and ethylenically unsaturated acid can obtain excellent gas barrier properties at low to medium relative humidity, and excellent gas barrier properties at very high relative humidity. This acid group forms an amine salt with the amine, which can impart excellent barrier properties to the composition. This composition can be cross-linked to alter benign obstacles. No prior art has mentioned the invention. For example, US Patent No. (Please read the notes on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) -4- 818 818 A7 B7 Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Printing V. Description of Invention 6) No. 4'761, 435 discloses a combination of a UV-curable polyethylenically unsaturated composition and a polyamine resin, which can be used as an aryl ketone photosensitizer. The / 435 patent mentions that acid functionality is inappropriate in the composition (column 5 'line 24). The patentee in this case pointed out that the formation of amine salts should be avoided because the photosensitizer can react with amines but not with amine salts. This point is different from the present invention, which mentions that the formation of acid salts is desirable and can lead to excellent barrier properties. As another example, U.S. Patent No. 4,9 4 3,600 refers to a combination of a third amine resin, an allyl-terminated resin, and a maleate functional resin. Similarly, the patent The owner mentioned that the composition was formulated to reduce or eliminate carboxyl functional groups, which is different from the present invention. U.S. Patent No. 5,017,406 discloses a UV curable composition containing a reactive unsaturated compound, but does not mention a polyamine or an unsaturated acid as used in the present invention. JP (Kokai) Gazette 7-18221 (issued January 20, 1995) refers to a surface treatment composition for a gas barrier, which includes an aminosilane and a compound having an aromatic ring or a hydrogenated ring. The present invention is different from this because it does not require the addition of a cyclic compound having an aromatic ring, and the reference does not mention the addition of an ethylenically unsaturated acid. The present invention is different from the prior art in that neither of them mentions the addition of an ethylenically unsaturated acid to achieve gas barrier properties, nor does they mention a composition having both barrier and adhesive properties. Description of the invention (please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X29 * 7 mm) -5- Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 482818 A7 B7 V. Description of the Invention &) This case relates to a method for laminating two substrates, which comprises coating at least one side of a substrate with a laminating adhesive, and coating the coated side of the substrate with a second substrate. The substrate is contacted to form a three-layer film, and the three-layer film is treated with a radical initiator, wherein the laminating adhesive is formed by mixing an ethylene-type unsaturated acid with a polyamine, wherein the polymer The amine optionally has a cross-linking agent reacting therein, and wherein the polyamine has four or more A, B, or C units, where: A is —R2 — N (R1) 2 units, and B is one R1 — N (R2) 2 units, and C is (—R2) 3N — units, where: R 1 is independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, arane And R 2 are independently selected from the group consisting of: 1 to 18 Linear or branched alkylene or substituted alkylene of carbon atoms, and alkylene or substituted alkylene having 6 to 18 carbon atoms. The invention can be used to laminate a variety of substrates used in packaging applications. The composition of the present invention can be used to provide a barrier layer that can improve the resistance of a material to the penetration of gases and odors to pass through it. For example, 30 micron, coated with biaxially oriented, corona treated polypropylene film according to AS TM D 3 9 8 5-8 1 is usually 1 50 0 when measured at 80% relative humidity. Oxygen permeability per cubic centimeter / square meter / day. When using the present invention, the paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm): '~ (Please read the precautions on the back before filling this page)

1T 482818 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ________ V. Invention Description 4) The oxygen transmission rate of the same film measured at 80% relative humidity can be reduced to less than 250 cm3 / m2 / day. DESCRIPTION OF THE PREFERRED EMBODIMENTS Although many different forms of embodiments of the present invention are possible, the preferred and various embodiments of the present invention will be described in detail herein. It must be understood, however, that this disclosure is to be considered an example of the principles of the invention and is not intended to limit the spirit and scope of the invention and / or the scope of patenting to the described embodiments. Polyamine The polyamine of the present invention is a polymer having four or more A, B or C units, a homopolymer or a copolymer polyamine, where A is -R2-N (R1) 2 units, B Is —R1 — N (R2) 2 units, and C is (—R2) 3N — units, where: R 1 is independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, Aralkyl, and alkaryl, and R 2 is independently selected from the group consisting of linear or branched alkylene or substituted alkylene having 1 to 18 carbon atoms And arylene or substituted arylene having 6 to 18 carbon atoms (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ) 482818 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, kl ____ V. Description of Invention 6) For example, R 1 or R 2 may be a hydroxyl-containing substituent. The amines of the present invention preferably have from about 150 to about 2'000, 000, more preferably from about 400 to about 400,000, and most preferably from about 600 to about 80,000. Molecular weight. The high degree of polymerization of the amine provides lower tack in the final composition. Lower molecular weight polyamines can be polymerized by methods known in the art to form higher molecular weight polyamines, such as with dialkyl halides (such as dichloroethylene) 'diisocyanates (such as toluene diisocyanate, hexamethylene Methyl diisocyanate), di (meth) acrylate (such as hexanediol diacrylate, pentaerythritol diacrylate), diepoxide (ethylene glycol diglycidyl ether), and so on. Polyamines that can be used in the present invention include polyvinylamine, amine-functional polyacrylamide, poly-DADMAC > polyvinylpyrrolidone copolymer, polyethylenimine and polyethylenimine / epichlorohydrin Copolymer reaction product. A preferred polyamine that can be used to achieve a variable viscosity is a polyamine called polyethylenimine, such as polyethylenimine, which can successfully obtain a wide range of molecular weights and different degrees of branching. Polyethyleneimines include a large family of water-soluble, i.e., hydrophilic, polyamines with different molecular weights and chemical modifications. As is generally known, the polymerization of ethyleneimine does not result in a polymer composed entirely of units having a linear structure, but a branching degree depending on the acid concentration and temperature in the polymerization. This degree of branching can be, for example, between 12 and 38%. The formula of polyethyleneimine can be expressed in the form of A'B or C units, where A is -R2_N (R1) 2 units, B is a R1-N (R2) 2 unit, and C is (a R2 ) 3N — Unit, where R1 is (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) -8- 482818 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative printed A7 B7 V. Description of the invention 6) Hydrogen, R 2 is a C Η 2 C Η 2-group. The ratio of A to B to C may be from about 1: 0.5: 0.5 to about 1: 2: 1, but more preferably from about 1: 1: 1 to about 1: 2: 1. Other substrates can be grafted to polyethyleneimine by methods well known in the art to change the coating's affinity to the substrate, or the tackiness. Examples of polyethyleneimine modification include reaction with ethylene oxide structures (ethylene oxide, propylene oxide) to introduce hydroxyl groups, reaction with cyanide and aldehyde followed by hydrolysis to introduce carboxylic acid groups. Stricken synthesisken ), Grafted phosphoric acid or sulfonic acid groups, and grafted lipophilic alkyl groups with alkylating agents such as dimethyl sulfate. Polyethyleneimine preferably has a molecular weight of about 600 to about 80,000. Polyethyleneimine has an optimum molecular weight of about 600 to about 25,000. Typical polyethylenimines are SZ-6 0 50, which are grafted with polyethylene oxide from Dow Corning Toray Silicone (Japan), and SP-103 and SP-110, each Polyethyleneimines having molecular weights of 600 and 1000 are available from Nippon Shokubai (Japan). Ethylene-type unsaturated acid A predetermined amount of an ethylene-type unsaturated acid is also added to the composition. '' Ethylene unsaturated acid '' means any acid having an ethylenically unsaturated acid group. The amount of the ethylene-based unsaturated acid may be up to about 80 parts by weight of the composition, and the most preferred is about 5 to about 75 parts by weight. The best ethylenically unsaturated acid that can be used in the present invention is decomposed itaconic acid; however, other acids such as fumaric acid, maleic acid, citraconic acid, acrylic acid, methacrylic acid, (please first Read the notes on the reverse side and fill in this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) -9- 482818 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ____ B7 V. Invention Description f ) Cinnamic acid, decomposition of monomethyl itaconic acid, vinylphosphonic acid, sorbic acid, methyl-trans-butenedioic acid, and ethylene sulfonic acid can also be used. The term ethylenically unsaturated acid, as used herein, is intended to include a mixture of one or more of the foregoing acids. Preferably, the molar ratio of the gram atom of nitrogen contained in the polyamine to the acid group contained in the acid is from about 10: 1 to about 1: 1, and more preferably from about 5 ·· 1 to about 1 : 1 0 and the best is about 2: 1 to about 1 ·· 4. In fact, the acid can be added to the solubility limit of the ethylenically unsaturated acid, which typically amounts to up to about 80 parts by weight of the composition. Solvent The composition of the present invention may be combined in the presence of a solvent, if necessary. Water, alcohols, and their blends are usually used as appropriate solvents because polyamines and ethylenically unsaturated acids are soluble in them. Another highly preferred solvent is a mono- or poly-diol, such as an alkylene oxide or an ether derivative of a polyalkylene oxide, which includes solvents such as ethylene glycol dimethyl ether. Preferably, the solvent must be non-toxic and not extend the drying time of the coating beyond commercially acceptable ones. The amount of the solvent may be about 20 to about 99 parts by weight and preferably about 60 to about 95 parts by weight of the composition. Preferred solvents are methanol, ethanol, n-propanol, isopropanol, butanol, and 1-methoxy-2-propanol (available from The Dow Chemical Company, Midland, Michigan, and Dowanol PM "). Selection of cross-linking agent Although polyamine and ethylenically unsaturated acid can be combined to form the composition of the present invention (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) -10- 482818 Printed by Kl ________ ^, a consumer cooperative of employees of the Central Standards Bureau of the Ministry of Economic Affairs Ⅴ) Description of the invention 不过 However, those who are better have added a cross-linking agent to improve the barrier properties, reduce the dehumidification effect, and improve the table It is believed that higher crosslinking densities can lead to these improved properties. As used herein, the term "crosslinking agent" is defined to mean that the polyamine chain can be extended and / or crosslinked. The cross-linking agent may be an organic cross-linking agent or better, a reactive silane cross-linking agent, or a mixture thereof. Although the organic cross-linking agent only uses a polyamine and an ethylenically unsaturated acid, it can be combined to form the compound. Invention composition However, it is preferable to add a compound capable of further extending and crosslinking the polyamine chain. It is considered that a higher degree of polymerization and crosslinking of the polyamine is desirable to provide improved barrier properties and appearance of the barrier coating of the present invention. Compounds that can be used to extend and crosslink polyamine chains include, but are not limited to, polyfunctional acrylates, methacrylates, epoxides, isocyanates, thiocyanates, acid halides, anhydrides, esters, alkanes Halides, aldehydes, or combinations thereof. Specific examples include, but are not limited to, hexanediol diacrylate, glycidyl methacrylate, ethylene glycol diglycidyl ether, and toluene diisocyanate. Polyamines can be chain-extended and cross-linked before or after the composition is coated on a substrate. Compounds that can be used to extend and cross-link polyamine-coated chains include acid-catalyzed condensation with nitrogen atoms contained in polyamines Reacting substances, such as tri-methanol-based phenols, aldehydes such as formaldehyde and glyoxal, p-quinone, and a mixture of formaldehyde and reactive methylene compounds that can undergo the Mannich reaction. Ethylene unsaturated acids can be combined with Polyamine can be added to ethylene irrespective of the addition (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 Regulation (210X 297 mm) -11-482818 A7 B7 V. Invention Note 6) Cross-linking occurs by copolymerizing polyfunctional compounds of unsaturated acid type. Such compounds include polyfunctional acrylates and methacrylates. In addition, the ethylenic unsaturated acid can also be added by adding acrylates and methacrylic acid. Ester-functional silane and direct cross-linking agent in a cross-linked polyamine structure. The acrylate and methacrylate functional silane compounds such as acryloxypropyltrimethoxysilane and methacryloxypropyltrimethoxy Silane can be added to the composition of the present invention after the ethylenically unsaturated acid to crosslink the polyamine. Hydrolyzing and condensing an alkoxy group or an alkoxy group after coating can form a polyfunctional polymer material which can be copolymerized with an ethylenically unsaturated acid. The organic cross-linking agent is preferably a polyamine / organic cross-linking agent ratio of about 100: 1 to about 1:10, more preferably a ratio of about 10: 1 to about 1: 1 and most The best is added in a ratio of about 5: 1 to about 2: 1. The best compound for reactive silane crosslinker is also a functional group that can react with nitrogen atoms on polyamines before adding an ethylenically unsaturated acid to the composition of the present invention. (Please read the precautions on the back before filling this page) and those who have trialkoxy or trisoxy groups which can be hydrolyzed and condensed using the selected aqueous solvent after being coated with the composition of the present invention. Since the silane part of the molecule is terminated with a hydroxyl group or an alkoxy group, it can be condensed with an alkoxy part contained in other silicone terminal molecules to form a Si-10-Si group. S i —〇—S i bonds can increase the crosslinking density of the composition. Reactive silanes may have the general formula QS i R m (〇R) 3 m, where Q is a compound containing one or more acrylates, aldehydes, methacrylates, acrylamide, methacrylamide, isocyanate, isocyanate The thiocyanate, anhydride, epoxy group, and acid paper sizes are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 71 I " " 482818 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs kl ______ B7 five Description of the invention 彳 〇) Chloride, linear or branched halogenated alkyl group, and any group of halogenated aryl group, and IIL is 0, 1, or 2, and R is a group having 1 to 4 carbon atoms. In particular, reactive silanes include their molecules such as T-propenyloxypropyltrimethoxysilane, 7 / -methacrylic oxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxy Silane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, r-isocyanatopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl Tri- (2-epoxycyclohexyl) silane, ethyltrimethoxysilane, chloropropyltriethoxysilane, chloropropylethyldimethoxysilane, methyldimethoxysilane and epoxy Propoxypropylmethyldimethoxysilane. The best reactive Shi Xi Yuan is a chloropropyltrimethoxy sand house available from the Dow Corning Corporation under the name SZ-6 0 7 6 and available from the Dow Corning Corporation under the name SZ-6 3 7 6 Chloropropyltriethoxysilane, and 7-trimethoxysilylpropyl, epoxypropyl ether, available from the Dow Corning Corporation under the name Z-6040. It may be necessary to neutralize the polyamine after the crosslinking agent has reacted therein, for example by adding sodium methoxylate and filtering off the resulting precipitate. The reactive silane is preferably based on a polyamine / reactive silane weight ratio of about 100: 1 to about 1:10, more preferably a ratio of 10: 1 to 1: 1 and the best is about 5 ; Add in a ratio of 1 to about 2: 1. Coating weight Coatings can be applied by any desired amount, however, the preferred coating is applied at a coating weight of up to about 20 g / m2, the best (please read the precautions on the back before filling in this Page) This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -13- 482818 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention h) The coating weight is approximately 〇 · 5 to about 10 g / m2. The coating weight can be determined using gravimetric comparison. The coating can be applied to the substrate by any conventional method, such as by spray coating, roll coating, sieve coating, stencil coating 'dip coating, and direct, lithographic, and reverse gravure coating. Substrate

The substrate can be configured on a wide variety of substrates including, but not limited to, polyolefins such as oriented polypropylene (0 PP), cast polypropylene, polyethylene and polyethylene copolymers, polystyrene, polyester, such as Polyethylene terephthalate (PET), or polyethylene naphthalate (PEN); polyolefin copolymers, such as ethylene / vinyl acetate, ethylene / acrylic acid, and ethylene / vinyl alcohol (EVOH); Polyvinyl alcohol and its copolymers; polyamides such as nylon, and MXD 6; polyimide, polyacrylonitrile, polyvinyl chloride, polyvinyl chloride, polyvinylidene chloride, and polyacrylates, ions Polysaccharides, such as regenerated cellulose; and silicones, such as rubber or sealants, other natural or synthetic rubber, cellophane or clay coated paper, cardboard or kraft paper; and metal-treated polymer films and vapor-deposited metals Oxide-coated polymer films, such as A 10x, S iOX, or T iOX, the substrates can be in the form of films or sheets, but are not mandatory. The substrate may be a copolymer, a laminate, a coextrusion, a blend, a coating, or a combination of any of the substrates listed above depending on the compatibility of the materials with each other. In addition, the substrate can also be made of polyethylene, polypropylene, polystyrene, polyamide, PET, EVOH, various types of materials, or laminates containing these materials. This paper applies the Chinese National Standard (CNS) A4 specification. (210X297 male f) -14- (Please read the precautions on the back before filling this page)-Yikou 482818 Printed A7 B7 printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. The form of the rigid container . The aforementioned substrate may also be pretreated by corona treatment, plasma treatment, acid treatment, and flame treatment before coating, all of which are known in the art. In addition, the composition of the present invention can be used in a wide variety of packaging containers such as pouches, tubes, bottles, vials, pouches in boxes, upright pouches, herringbone top cartons, thermoformed trays, brick-packs, boxes, cigarettes Used as a barrier layer on top of packaging and the like. Of course, the invention is not limited to packaging applications, but can be used in any application that requires gas or taste barrier properties, such as tires, buoys, inflatable devices, and the like. A primer can be applied on any of the above substrates. The primer can be applied to the substrate by methods known in the art, such as spray coating, roll coating, screen coating, crescent coating, dip coating, and direct, lithographic and gravure coating. Suitable primers include, but are not limited to, carbodiimide, polyethylenimine, and silanes, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and amines. Propyltriethoxysilane. Optimal laminated structure (where C 0 represents the coating composition of the present invention), 0 PP / Co / 〇PP, OPP / Co / PE, me tOPP / Co / OPP > me tOPP / Co / PET, metal oxidation Material is coated with PET / Co / PE, metal oxide is coated with PP / Co / PE, metal oxide is coated with PET / Co / PP, metal oxide is coated with PP / Co / PP, and PE / Co / PE . This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) _ 15 (Please read back & precautions before filling out this page), τ 482818 A7 B7 Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention 纟 3) The hardened laminate is preferably hardened with a radical generator such as ultraviolet light, electron beam 'or r radiation or a chemical radical generator such as azo compound and peroxide. A low energy electron beam is a preferred method of hardening because it is cheaper than an r-source such as cobalt M-60. Its advantage over UV radiation as a hardening system is its ability to generate free radicals without the need for a photoinitiator. It also imparts higher cross-link density and chemical graft yield to coatings coated on substrates. Various types of electron beam accelerators such as van de Graaf-type 'resonant transformer type, linear type, and Dynamatron-type can be used as the electron beam source. Electron beams emitted from them having an energy of about 5 to about 2000 keKe, preferably about 50 to about 300 keV, can be used in the range of about 0.1 to about 10 Mrads (M r) Dose of radiation. The optimal dose is about 150 Ke V, at least 5 M r. If the substrate is processed in a vacuum, a low electron beam voltage can be used. A commercially available electron beam source is Electrocure CB-150 available from Energy Sciences, Inc. (Wilmington, MA). If one or more light initiators are added before hardening, the laminate can also be hardened with ultraviolet light. There are no particular restrictions on the photoinitiator as long as they can generate free radicals by absorbing light energy. The ultraviolet light-sensitive photo-initiator or initiator blend used in the UV curing of the composition of the present invention includes 2-hydroxy-2 -methyl-1 -phenyl-propane-1 -one (Darocure 1173) , Sold by EM Chemicals; and 2,2-dimethoxy-2-ethylanisole (Irgacure 651), sold by Ciba-Geigy Corporation, Hawthorne, New York. For the purpose of the present invention, it has been found that about 0.5 · 5 to about 5% by weight based on the total solids in the composition as described herein (please read the precautions on the back before filling this page) Applicable to China National Standard (CNS) A4 specification (210X 297 mm) -16-Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 482818 A7 ______________ B7 V. Description of the invention ") The initiator can promote the hardening of the composition. Use other types of free radical generators known to those skilled in the art, such as promoted peroxides, azo compounds, etc. In addition, if a crosslinking agent is added to the composition, other hardening methods may be required For example, if a reactive silane crosslinker is added, the composition can be hardened by a condensation reaction that requires the presence of water. This moisture can be present in the coating solution itself, or can be added via steam or placed in a high humidity cabinet. The reaction can be accelerated by heat, for example, heating in an oven at a temperature of up to about 140 ° C, preferably about 60 ° C to about 120 ° C and most preferably about 90 ° C to about 1 The temperature is 10 ° C. The heating time is temperature-dependent and the coating can reach the non-sticking time within 1 to 10 seconds. This heating step can be used to evaporate the solvent and accelerate the condensation reaction between silanol groups. The particular crosslinking system used may require additional hardening chemistry, all of which are known in the art. The key factor in determining whether a particular formulation is accepted as a laminating adhesive is whether the composition exhibits the lowest Adhesiveness. If the laminating adhesive has at least the minimum required adhesiveness, it is included in the scope of the present invention. The adhesiveness can be achieved by maximizing the ratio of the above components, or by adding Adhesives, such as polyfunctional acrylates. Preferred embodiments In the preferred embodiment of the present invention, 8 parts of sodium methoxide solution (30% solids in methanol) are added to 1,000 parts of s Z — 6050 (50% solids, in isopropyl alcohol (IPA)) to prepare the paper according to the Chinese National Standard (CNS) A4 specifications (~ (Please read the precautions on the back before filling this page)

Order 482818 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention 彳 5) Neutralized SZ-6050. Neutralization produced 3.68 parts of NaCl, which was removed by centrifuging the solution. Then, 1 1 4 · 7 parts of decomposed itaconic acid were added to 100 parts of the neutralized S Z-6 0 50. The resulting solution was diluted with 3 1.76 parts of IPA and 37.26 parts of water to obtain a solution containing 15% solids. Next, a humectant in an amount of 0.1% by weight of the total composition, Triton X-100 100-100 (quoted) was added. Thereafter, the solution was coated on a 30-micron-thick "Rayopp (R)" oriented polypropylene film obtained from UCB Films and subjected to corona treatment for 10 minutes to dry. A second sheet of oriented polypropylene film was then applied to the coated film with a roller to prepare a laminate. Then, E B was irradiated at 170 kV, 10 Mrads to harden the obtained laminate. The solution was applied to the laminate to obtain a coating weight of 4-4 · 5 g / m 2. Optional additives Various optional additives can be added to the composition to improve various properties as needed. These additives can be added as needed and in any amount as long as they do not degrade the performance of the barrier coatings described herein. Their additives include anti-blocking agents and anti-slip agents such as stearylamine, oleylamine or polar additives such as epoxide, propionate, methylpropionate, polyhydric alcohol, glycidyl alcohol, formazan Glycidyl acrylate, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, or polyamines such as polyethylenimine and other silanes. Wetting agents such as polyethoxylated phenol can also be added. This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -18- Clothing (please wash and read the back. Note on the front and then fill out this page) 482818 A7 B7 V. Description of Invention (6) Ministry of Economy The oxygen permeability of each film printed by the Central Bureau of Standards Consumer Consumption Example is expressed in units of cubic centimeters per square meter per 24 hours, and its dry and dry systems are compared with 0% at MOCON Oxtran Model 100. Measured under humidity and its "wetness" was measured with MOCON Model 2/20 ΜΗ at 80-82% relative humidity. For comparison, a polypropylene film with a permeation rate of about 15 square meters per square meter for 4 hours is used. In the following examples, PEI is a 700 molecular weight polymer obtained from Aldrich Chemical Co., and itaconic acid (I TA) is also obtained from Aldrich Chemical Co. ,, Ecocoterge E0-100 " are from Eastman Color and Chemical Co. The electron beam was generated by a Pilot Electrocurtain electron beam machine provided by Energy Sciences, Inc. Oriented stretch polypropylene (OPP) films are available from UCB Films. Z — 6040, r-trimethoxysilylpropyl, epoxypropyl ether, obtained from Dow Corning Corporation, Midland, Mi o SZ — 6 0 5 0 is polyethylenimine grafted with silane , Available from Dow Corning Toray Silicone Corp. (Japan), and by adding 40 · 5 parts of 1000 molecular weight polyethylenimine (SP-110, available from Nippon Shokubai, Japan) to 4 9 · In 3 parts of isopropanol, heat to 80-90 ° C; then add 10 · 2 parts of chloropropyltrimethoxysilane and heat at 80-90 ° C for two hours; then use this solution with N a Me0 was prepared by neutralization and filtration. This solution was coated with a RK applicator and left to dry at room temperature for 10 minutes. A second film was then applied to the coated film with a roller to prepare a laminate. After that, use the EB at 170 K e V, 10 〇 Mrad, (please read the precautions on the back before filling this page),-

T This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -19- A7 __B7 _____ V. Description of the invention 彳 7) or use ϋν (dose = ι1 millijoules / cm2) to harden. Using 11 & κ ~ rod coating solution under the same conditions (30% solids content, 1 ρα +) to obtain a coating weight of 4-4 · 5 g / m 2. In Table 1 below, the mole ratios and preparation methods of the respective compositions are listed. (Please read the notes on the back before filling in this page j

Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) 482818 A7 B7 V. Description of Invention 彳 8) Table 1 Compound substrate hardened dry air permeability wet air permeability (cubic centimeter (cubic centimeter / square meter / square meter / day) meter / day) NSZ-6050 / ITA (l: 23) + X- 100 * OPP / OPP EB 10 8.33 + NSZ-6050 / ITA (l: 23) OPP / OPP uv Not meas. 7.8 + NSZ-6050 / ITA (l: 23) OPP / metO EB 10 12 + PP NSZ-6050 / ITA (l: 23) + BCEA OPP / OPET EB 0.65 0.81 + NSZ-6050 / ITA (l: 23) + X-100 OPP / PE EB 88 8.2-NSZ-6050 / ITA (l: 23) + X-100 PE / PE EB 187 30 + NSZ-6050 / ITA (l: 23) OPPSiOx / EB < 0.5 1.9 + 〇PP NSZ-6050 / ITA (l: 23) OPETSiOx EB < 0.5 < 0.01 + / PE NSZ-6050 / Z- OPP / OPP EB 33 1.14 + 6076 / ITA (l: l: 23) ** PEI (25000) / Z- OPP / OPP EB 3 0.73 + 6040 / ITA (l: 0.5: 581) PEI (700) / Z- OPP / OPP EB 4.5 8.9 + 6040 / ITA (l: l: 16) + X-100 PEI / ITA (1: 581) OPP / OPP EB 54 3.36 + PEI (700) / GM /ITA(1:0.5:16) OPP / OPP EB 6 2.97 + SZ-6050 / ITA (l: 16) OPP / OPP EB 2 26.1 + AM8 / Z-6076 / ITA (l: 0.25: 14) EB 110 149 + AM8 / Z-6076 / ITA (l: 0.75: 14) EB 0.7 77 + * The table is neutralized ** Coated on the base coating film (Z-6020 is in IPA / water (1: 1) 1% by weight solution) "+" table shows excellent adhesion phenomenon and table shows poor adhesion phenomenon. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -21-(Please read the notes on the back and fill in this page) 482818 A7 B7 V. Description of invention 彳 9) Preparation of nsZ-6050 / ITA (1: 2 to 10 g of neutralized SZ — 6050 / isopropanol (I PA) solution (45% solids 3 1 · 76 g IP 15% solids solution) was added 11.47 g of 1 buta It is obtained by diluting the obtained solution with A and 37.26 g of water. In some cases, as shown in Table 2, it is diluted with water by 100%. In another example, ethyl ethyl ester (BCEA 1 0 % By weight. BC SZ — within 6050

After release, a humectant, Triton X-100 (VVX.) Was printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Wet Economic Affairs to print N: 2 3 IPA 1 1. Grams of water P: 0.8 8. 8 8. P: 1 6 5 Z-6 0): Add 7 g of decomposition clothing to 50 0) and add it to 1 0 EI (2 5 5: 581 6 8 g IP 6 8 g water thin EI (7 0): 2 · The addition amount of emollient is 0.1% of the total composition, as shown in Table 2, acrylic acid / 3-cyano) is added as the addition amount, and the EA system whose amount is the composition is before the addition of IPA Add to the neutralized 〇50 / Z — 6076 / ITA (1: 1 gram SZ-6060 solution (50% solids, 10 grams Z — 6 0 7 6 to form the first solution. Please read the notes on the back Further on this page order Kangaconic acid dissolved in 1 • 4 grams of IPA and 18 ·

Gram the first solution. 000) / Z-6040 / ITA (1) •• Dissolve 0.04 g of Z-6040 in A. Add 7.77 grams of PEI. After releasing this solution, add 2 3 · 49 grams of decomposition clothing 0) / Z-6040 / ITA (1: 1 36 grams of Z-6040 dissolved in 50 grams of I PA This paper is a Chinese national standard ((: Deng) six 4 Specifications (210 \ 297 mm) -22- 482818 Μ B7 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China Five Invention Briefing Sessions 0) 1 I and 50 grams of water 〇 7 grams of 7 0 0 molecular weight PEI to form The first 1 I— · solution 〇 Then dissolve 20 • 8 g of I Τ A in 3 5 • 4 g of IPA 1 1 I and 3 5 • 4 g of water and then add this solution to the first solution. 1 1 After adding humectant Triton X-1 0 0 (VV X-1 0 0 // • Read first 1 I read 1 I) 〇 The amount of humectant added is 0 • 1% by weight of the total composition. 5 1 Ρ EI / I Τ A (1: 5 8 1) * Dissolve 7 • 7 7 grams of Igu 1 IPEI in 8 8 • 6 8 grams of IPA. Use 8 8 • 6 8 grams of water to dilute 1 ft 1 After releasing this solution, add 2 3 • 4 9 grams of decomposed itaconic acid 〇 Fill in SZ — 6 0 5 0 / ITA (1 1 6) Add 5 • 3 2 pages 1 1 g of decomposed itaconic acid to 10 g of neutralized SZ — 6 0 Dilute this solution with 2 3 • 5 7 g of water and 16 7 g 1 IIPA in 50 solution (1 130% solids). Order IPEI (7 0 0) / G Μ / I Butan A ( 1: 0 • 5: 1 1 1 1 6): Dissolve 0 • 1 7 5 g of epoxypropyl methacrylate in 1 1 2 0 • 1 8 g of IPA and add 1 • 7 5 g of PEI 〇 Dilute this solution with 1 I 2 0 • 18 grams of water 〇 Then add 5 ginseng 2 grams of decomposed itaconic acid f 1 〇 | 1 Μ 8 / Z — 6 0 7 6 / ITA (1 0 • 2 5 1 1 1 4) • 8 grams of Αί 5 tramol AM?! (Μ [W 7 6 2 :) and 2 grams of Z — 6 0 7 6 are mixed in 10 grams of IPA and refluxed at 90 ° C for 2 4 hours 〇 Use 1 • 36 grams of sodium methoxide 1 (30%, 1 I solution in methanol) to neutralize 15 After the solution was grammed, a solution of 45% solid content in IPA 1 1 I / Μ 〇Η (1 ·· 0 • 0 8 W t W t) was used. 1 1 I 7 • 9 8 g of water and 6 • 9 5 grams of IPA diluted 2 • 1 6 grams of the solution 1 1 1 This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 482818 A7 B7 V. Description of the invention). A final solution of 15% solids in IPA / water / methanol was prepared by adding 1.85 grams of I TA before the coating. The coating weight is approximately 2.5 grams. AM8 / Z-6076 / ITA (1 · · · · 75 · · 1 4): Mix 8 grams of Astramol AM8 (MW76 2) with 6 grams of Z-607 6 in 14 grams of I PA at 90 ° C Under reflux for 24 hours. Neutralize 17 grams of this solution with 3 · 31 grams of sodium methoxide (30% solution in methanol) to give a 4% solids content in I PA / Me〇H (1: 14 · 14 wt: wt) In solution. Dilute 2.11 grams of this solution with 6.25 grams of water and 5.18 grams of IPA. A final solution of 15% solids in IPA / water / methanol was prepared by adding 1.27 grams of ITA immediately before coating. The coating weight was approximately 2.5 grams. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs These solutions are formed into laminated structures with various configurations, as shown in Table 2 below. In Table 2, OPP is a 30 micron-thick Rayopp (R) oriented polypropylene film obtained from UCB Films after corona treatment; metOPP is a 30 micron-treated and oriented metal film also available from UCB Films. Stretched polypropylene, PE is a 50 micron low-density polyethylene film made by Dow Corning Corp. with a density of 0.92 and a melt index of 2. 0PET is a 12 micron oriented stretched polyethylene terephthalate, available from Lawson Martin under the name Ceramis CTXD, and OPPS iox is a 20 micron oriented stretch coated with S iox. Polypropylene is also available from Lawson Martin under the name Ceramis Co. -24- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

482818 Annex I (A) of the scope of patent application: (Please read the notes on the back before filling out this page) No. 87 1 0 1 247 Chinese Patent Application Amendment Amendment August 1990 A method for preparing a gas barrier-containing laminate including an amine salt, comprising: (I) coating at least one side of a substrate with a laminating adhesive; (Π) causing the coated side of the substrate to be coated Contacting the second substrate to form a multilayer film; and (II) treating the multilayer film with a radical initiator, wherein the laminating adhesive is reacted by decomposing itaconic acid or an ester thereof with Crosslinking agent made of polyethylenimine, where the polyethylenimine has four or more A, B or C units, where A is —R2 — N (R1) 2 Unit, B is —R1 — N (R2) 2 units, and C is (—R2) 3N —units, here: Jing Qiluo Zhicai Jiu Gou member !. Xiao Feiduo (屮) R R independently Is selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, aralkyl, and alkaryl, and R 2 is independently From the following combinations: linear or branched alkylene or substituted alkylene having 1 to 18 carbon atoms, and alkylene or substituted alkylene having 6 to 18 carbon atoms The paper size is applicable to China National Standards (CNS) A4 (210X: 297 mm) 482818 A8 B8 C8 _ D8 _ — ___ 6. Scope of patent application where the nitrogen atom in the polyethylenimine contains The molar ratio of the acid groups contained in itaconic acid or its ester is 10: 1 to 1: 100 ′, wherein the mixture is dissolved in a solvent and the solvent is selected from the group consisting of: water , Ether derivatives of alcohols, mono- and poly-diols, and mixtures thereof, and the solvent occupies 60 to 95 parts by weight of the total mixture, wherein the radical treatment in this step (in) uses an electron beam Radiation, r / radiation or ultraviolet radiation, which is initiated in the presence or absence of a photoinitiator, or the radical reaction is initiated thermally in the presence of a radical generator, and wherein in this step ( I) The mixture includes an organic crosslinking agent. 2. The method according to item 1 of the patent application range, wherein the electron beam processing is performed at 5 KeV to 2000 KeV and greater than 0.1 Mrads. 3. The method according to item 1 of the patent application range, wherein the electron beam processing is performed at 150 KeV and at least 5 Mrads. 4. The method according to item 1 of the scope of patent application, wherein the coated substrate of step (n) is a heated one. 5. The method according to item 4 of the scope of patent application, wherein the coated substrate of step (π) is heated in the presence of moisture. 6. The method of claim 1 in the patent scope, wherein the laminating adhesive includes an additive. 7 · The method according to item 6 of the patent application scope, wherein the additive is selected from the group consisting of: anti-blocking agent, anti-slip agent, polar additive, Zhongguanjia Standard (CNS) for paper use 〇χ297 > ^ Xian): ------- Binding (please read the precautions on the reverse side before filling out this page) 482818 A8 B8 C8 D8 The scope of patent application has been approved by '齐 郎 智% 财 4） L · Ψ t 'Silane, acrylate or methacrylate, polyethylenimine, glycidyl methacrylate, glycidyl alcohol, ethylene glycol diglycidyl acid, bisphenol A diglycidyl Ether and wetting agent. 8. The method according to item 1 of the scope of patent application, wherein the substrate in this step (π) is treated with a primer. 9. The method according to item 8 of the scope of patent application, wherein the primer is selected from the group consisting of silane, polyethylenimine, and carbodiimide. 1 0. The method of claim 1 in which the polyethylenimine has a molecular weight in the range of 600 to 25,000. 1 1 · The method according to item 1 of the patent application range, wherein the substrate is selected from the group consisting of: polyolefins, including oriented stretch polypropylene (0PP), cast polypropylene, polyethylene, and polymer Ethylene copolymers, polystyrene, polyesters, including polyethylene terephthalate (PET), or polyethylene naphthalate (PEN); polyolefin copolymers, including ethylene / vinyl acetate, Ethylene / acrylic acid and ethylene / vinyl alcohol (EV 0Ο); polyvinyl alcohol and copolymers thereof; polyamines, including nylon, and MXD6; polyimide, polyacrylonitrile, polyvinyl chloride, polyvinyl chloride, Polyvinylidene chloride, polyacrylates, ions, polysaccharides, including regenerated cellulose; silicones, such as rubber or sealants' natural or synthetic rubber, cellophane or clay coated paper, cardboard; kraft paper; and metal treated The polymer film and the polymer film coated with the vapor-deposited metal oxide include eighty ten ten thousand, thirty ten thousand, or ten ten thousand. 1 2. If the method of the scope of application for the first item of the patent, which forms this layer (please read the notes on the back before filling out this page)-installation ·, · · This paper size applies Chinese National Standard (CNS) Α4 specifications (210X297 Mm) -3-482818 A8 B8 C8 D8 6. Scope of patent application (please first read the notes on the back and then fill out this page) The second substrate used for the press is selected from the following combinations: Polyolefins, including oriented polypropylene (0pp), cast polypropylene, polyethylene and polyethylene copolymers, polystyrene, polyester, including polyethylene terephthalate (PET), or polynaphthalene Polyethylene glycol diformate (PEN); polyolefin copolymers including ethylene / vinyl acetate, ethylene / acrylic acid and ethylene / vinyl alcohol (EV〇Η); polyvinyl alcohol and its copolymers; polyamides, including nylon , And MXD 6; polyimide, polyacrylonitrile, polyvinyl chloride, polyvinyl chloride, polyvinylidene chloride, polyacrylate, ionomer, polysaccharide, including regenerated cellulose; silicone, including rubber Or sealant, natural or synthetic rubber, cellophane or white Coated paper, cardboard; kraft paper; and metal-treated polymer films and vapor-deposited metal oxide-coated polymer films, including A 1OX, S IOX, or DIOX. 1 3 The method of claim 1 in which the organic cross-linking agent is selected from the group consisting of: polyfunctional acrylate, methacrylate, epoxide, isocyanate, thiocyanate, ' Acid halides, anhydrides, esters, alkyl halides and aldehydes, and mixtures thereof. 1 4. The method according to item 1 of the scope of patent application, wherein the cross-linking agent has the general formula QS 1 R m (〇R ) 3-m reactive silane, where Q contains a group selected from the group consisting of acrylate, aldehyde, methacrylate, acrylamide, methacrylamide, isocyanate, isothiocyanate Esters, anhydrides, epoxy groups, acid chlorides, linear or branched halogenated alkyl groups, and halogenated aryl groups, and 1 is 1, 2, or 3, and R is a group having 1 to 4 carbon atoms, And the mixture in step I can be neutralized. 1 5 · If the method of claim 14 in the scope of patent application, In this reaction, the paper size is applicable to Chinese National Standard (CNS) A4 specification (210 ×: 297 mm) 7Γ1 ^ 482818 A8 B8 C8 D8 6. The scope of patent application Silane is selected from the following combinations: r-propylene Methoxypropyltrimethoxysilane, r monomethacrylic oxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxy Silane, r-isocyanatopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri- (2-epoxycyclohexyl) silane, ethyltrimethylsilane Oxysilane, chloropropyltriethoxysilane, chloropropylethyldimethoxysilane, methyldimethoxysilane and glycidoxypropylmethyldimethoxysilane, and step I The mixture can be neutralized. 16. The method according to item 1 of the scope of patent application, wherein the obtained multilayer film is used for manufacturing packaging containers. 17. The method according to item 16 of the scope of patent application, wherein the packaging is selected from the group consisting of pouches, tubes, bottles, vials, bottles, bags in boxes, upright pouches, herringbone tops Carton boxes, thermoformed trays, brick-packs, boxes, and cigarette packages. -------- φά ------ Order ----- (Please read the notes on the back before filling out this page) Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Consumption Printed paper Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) _ 5-