Gas and water vapor barrier laminate

Abstract

A gas and water vapor barrier laminate characterized by having a halogenated ethylene polymer layer containing a halogenated ethylene polymer on a paper support, the halogenated ethylene polymer layer having a coating efficiency of 5.0 x 10 ‑9 m 3 / g or more.

Description

Technical Field

[0001] This invention relates to gas and water vapor barrier laminates. Background Technology

[0002] To maintain the quality of food and pharmaceuticals, these packaging materials need to be sealed to prevent the release of gases such as oxygen, nitrogen, carbon dioxide, and water vapor from the atmosphere. Among various resins, halogenated ethylene polymers such as polyvinylidene chloride have high barrier properties against gases and water vapor, and are therefore used in the form of aqueous dispersions coated onto supports such as plastic sheets and paper.

[0003] In recent years, due to increased awareness of environmental issues, the demand for paper packaging to replace existing plastic packaging has been growing. In the field of paper packaging materials, in addition to barrier properties, there are also requirements for yellowing resistance, heat sealing properties, and high recyclability.

[0004] In addition, thickening the barrier layer of the halogenated ethylene polymer is effective in improving barrier properties and processing characteristics. However, when using existing paper support latex, increasing the film thickness can lead to impaired pulp dissociation during recycling, and various studies have been conducted.

[0005] Patent document 1 discloses an aqueous dispersion of a halogenated ethylene polymer for coating plastic sheets used in existing plastic packaging.

[0006] Patent Document 2 discloses a moisture-proof paper with good dissociation properties, which is formed by coating a vinylidene chloride-based copolymer resin latex with a specific monomer composition and viscosity-enhancing properties onto a base paper. It further discloses that if the average particle size of the resin latex is below 120 nm, the tackiness during drying can be improved, enabling the formation of a sufficient coating.

[0007] In addition, Patent Document 3 discloses a moisture-proof paper, which is formed by laminating a base coating made of synthetic resin latex with a glass transition temperature of -5°C or less and a moisture-proof layer made of vinylidene chloride copolymer resin latex with a specific water vapor permeability onto a base paper.

[0008] In addition, Patent Document 4 discloses a method for manufacturing a barrier laminate, in which the paper substrate is sizing or coating to suppress the paper permeability of the barrier substance, and the barrier substance can be directly coated onto the paper substrate by performing a calendering process.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: International Publication No. 2013 / 125699

[0012] Patent Document 2: Japanese Patent Application Publication No. 11-12982

[0013] Patent Document 3: Japanese Patent Application Publication No. 2000-73294

[0014] Patent Document 4: Japanese Patent Publication No. 2020-530409 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] However, when attempting to transfer the aqueous dispersion of the halogenated ethylene polymer used for plastic sheet coating in Patent Document 1 to the coating of paper supports, problems arise such as low viscosity, pinholes caused by the pulp fibers of the paper support piercing the coating film, and inability to fully utilize the barrier properties.

[0017] In addition, while the moisture-proof paper of patent documents 2 and 3 does have excellent barrier and dissociation properties, the yellowing resistance and heat-sealing properties of the vinylidene chloride copolymer latex are insufficient. When the coating amount is increased to compensate for this, the dissociation property is impaired during recycling.

[0018] Furthermore, while the barrier properties of the barrier laminate in Patent Document 4 are indeed excellent, it suffers from insufficient heat-sealing properties.

[0019] Therefore, the object of the present invention is to provide a laminate that, in addition to having barrier properties against gases and water vapor, also has excellent heat-sealing properties, yellowing resistance, and recyclability.

[0020] Methods for solving problems

[0021] In order to solve the above-mentioned problems, the inventors have conducted in-depth research and found that by making a laminate having a layer of ethylene halide polymer containing a ethylene halide polymer with a coating efficiency within a specific range on a paper support, the above-mentioned problems can be solved, thus completing the present invention.

[0022] That is, the present invention is as follows.

[0023] (1) A gas and water vapor barrier laminate, characterized in that it has a ethylene halide polymer layer comprising an ethylene halide polymer on a paper support, the coating efficiency of the ethylene halide polymer layer being 5.0 × 10⁻⁶. -9 m 3 / g or more.

[0024] (2) The gas and water vapor barrier laminate as described in (1), wherein the above-mentioned halogenated ethylene polymer is a crystalline resin with a crystallization melting point of less than 180°C.

[0025] (3) The gas and water vapor barrier laminate as described in (1) or (2), wherein the weight-average molecular weight of the halogenated ethylene polymer is 100,000 or more.

[0026] (4) The gas and water vapor barrier laminate as described in any one of (1) to (3), wherein the halogenated ethylene polymer comprises more than 70% by mass of structural units derived from vinylidene chloride.

[0027] (5) A packaging material or packaging container, characterized in that it comprises a gas and water vapor barrier laminate as described in any one of (1) to (4).

[0028] (6)(5) The packaging materials or packaging containers described herein are used for packaging food.

[0029] A method for manufacturing a gas and water vapor barrier laminate according to any one of (7)(1) to (4), characterized in that the method comprises the following steps:

[0030] An aqueous dispersion of ethylene halide polymer particles with an average particle size greater than 120 nm is coated onto a paper support and then dried to form an ethylene halide polymer layer.

[0031] (8) The manufacturing method as described in (7), wherein the pH of the aqueous dispersion of the above-mentioned halogenated ethylene polymer particles is less than 4.0.

[0032] The effects of the invention

[0033] According to the present invention, a laminate can be provided that, in addition to barrier properties against gases and water vapor, also possesses excellent heat-sealing properties, yellowing resistance, and recyclability. Attached Figure Description

[0034] Figure 1 This is an example of a microscopic photograph obtained by taking a cross-section of the laminate (the interface between the paper support and the ethylene halide polymer layer) in order to determine the thickness of the ethylene halide polymer layer on the paper support in the laminate.

[0035] Figure 2 This diagram shows the selected location when manually measuring the pure water contact angle of a paper support using a contact angle meter. Detailed Implementation

[0036] The following provides a detailed description of specific embodiments of the present invention (hereinafter referred to as "this embodiment"). This embodiment is illustrative of the present invention and is not intended to limit the present invention to the following content. Furthermore, the present invention can be suitably implemented with modifications within the scope of its essential points.

[0037] [Gas and water vapor barrier laminates]

[0038] The gas and water vapor barrier laminate (hereinafter also simply referred to as "laminate") of this embodiment is characterized by having a ethylene halide polymer layer comprising an ethylene halide polymer on a paper support, the coating efficiency of which is 5.0 × 10⁻⁶. -9 m 3 / g or more.

[0039] [Paper Support]

[0040] The paper support in this embodiment is composed of pulp and fillers, and can contain various agents as needed. Furthermore, the paper support is preferably in sheet form.

[0041] As the paper support in this embodiment, various known paper supports can be cited, such as high-grade paper, mid-grade paper, coated paper, single-sided paper, kraft paper, single-sided kraft paper, bleached kraft paper, cellophane, card stock, white card stock, and lining paper.

[0042] From the perspective of flexibility for use in packaging materials, containers, cups, etc., for food, pharmaceuticals, etc., the basis weight of the paper support in this embodiment is preferably 200 g / m². 2 The following, or more preferably, is 100g / m 2 The following, and more preferably, is 80g / m 2 The following, the optimal value is 70g / m 2 The following is a preferred range, where the lower limit is not specifically defined. 2 above.

[0043] The pulp used as the paper support can be made of various types of pulp, including bleached sulfate pulp (LBKP), bleached sulfate pulp (NBKP), unbleached sulfate pulp (LUKP), unbleached sulfate pulp (NUKP), sulfite pulp, and other chemical pulps; mechanical pulps such as stone mill pulp and thermomechanical pulp; deinked pulp; waste paper pulp; and non-wood fibers such as flax, bamboo, and hemp. These can also be appropriately blended. Among these, wood fiber pulp, chemical pulp, and mechanical pulp are preferred, especially chemical pulp, because they are less likely to introduce foreign matter into the base paper, are less prone to discoloration over time when the laminated material (packaging container) is recycled from waste paper raw materials, have a high level of whiteness resulting in good surface finish during printing, and have increased value, particularly when used as packaging material.

[0044] Furthermore, the average fiber length of the pulp fibers constituting the paper support is preferably 5 mm or less, and the average fiber width is preferably 100 μm or less. The fiber length and width of these pulp fibers affect the size of the capillaries formed in the gaps between the pulp fibers in the paper support. The smaller the fiber length and width, the smaller the capillaries, which can suppress the absorption of the aqueous dispersion of the halogenated ethylene polymer particles (described later) by the paper support layer. In addition, since the mechanical strength of the paper support is increased, the coating speed of the aforementioned aqueous dispersion can be improved, and it is also easier to mold into packaging containers, etc.

[0045] The average fiber length is more preferably 4 mm or less, further preferably 3 mm or less, and particularly preferably 2 mm or less. No specific lower limit is set, but for the purpose of obtaining adequate mechanical strength, 1 mm or more is preferred.

[0046] Furthermore, the average fiber width is more preferably 50 μm or less, more preferably 40 μm or less, and particularly preferably 30 μm or less. The lower limit is not specifically set, but for the purpose of obtaining adequate mechanical strength, it is preferably 10 μm or more.

[0047] It should be noted that the average fiber length and average fiber width of the pulp fibers were determined using the following method. Ion-exchanged water and paper support were measured in a ratio of 0.1% by mass and a total weight of 300g. The pulp was prepared by opening the fibers using a high-shear homogenizer (e.g., Nippon Seiki Co., Ltd., product name "EXCEL AUTO HOMOGENIZER ED-7") at 15,000 rpm for 5 minutes. The resulting pulp was poured onto mica, air-dried, and then measured using a high-resolution scanning electron microscope (SEM). In the particle images obtained during this measurement, the major axis (L) and minor axis (D) of arbitrarily selected 100–150 particles were measured, and their average values ​​were taken as the average fiber length and average fiber width, respectively.

[0048] As fillers constituting the paper support, known fillers such as silica, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium dioxide, zeolite, and synthetic resin fillers can be used.

[0049] Furthermore, to improve the adhesion and yield characteristics of the ethylene halide polymer to the paper support, the paper support can contain various agents, and the surface can be treated with various agents. Examples of such agents include sizing agents, hydration-resistant agents, and paper strength enhancers.

[0050] Examples of sizing agents include styrene-based sizing agents, alkyl ketene dimers (AKD), alkenyl succinic anhydride (ASA), neutral rosin sizing agents, rosin sizing agents, and modified rosin emulsion sizing agents. Among these, rosin sizing agents and modified rosin emulsion sizing agents are preferred.

[0051] The aforementioned rosin sizing agents can be any substances already known in the papermaking industry, without particular limitation. Examples of rosin-based substances include reinforced rosin obtained by modifying rosins such as rosin resin, rosin wood, and tall oil rosin with α,β-unsaturated carboxylic acids or their anhydrides, such as fumaric acid, maleic acid, and acrylic acid; and rosin esters obtained by reacting the aforementioned rosins with polyols such as glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, and diglycerol. Furthermore, rosin sizing agents also include substances obtained by emulsifying these substances individually or in mixtures, and substances obtained by emulsifying them separately and then mixing them. In addition, to further improve sizing performance, the emulsified substances also include substances containing various polymers.

[0052] The content of sizing agent in the paper support, calculated based on solid content, is preferably 0.1 to 10 kg / t. When the content of sizing agent is within the above range, water absorption and missed coating on the paper support can be suppressed when coating an aqueous dispersion of ethylene halide polymer particles.

[0053] Examples of water-resistant agents include melamine-formaldehyde resins, glyoxal resins, polyamide-epoxy resins, and zirconium carbonate resins, which contain hydroxymethyl, aldehyde, and epoxy groups.

[0054] The content of the hydration-resistant agent in the paper support is preferably 0.02 to 3 parts by weight relative to 100 parts by weight of pulp. When the content of the hydration-resistant agent is within the above range, excellent initial bond strength can be obtained.

[0055] In addition, to give the paper support strength, a paper strength enhancer may be included. Various known substances such as polyacrylamide resins, polyamide resins, polyamine resins, acrylic resins, melamine resins, urea resins, and polyamide-epoxychloropropane resins can be used as paper strength enhancers. Among these, amphoteric paper strength enhancers are preferred, and amphoteric polyacrylamide is particularly preferred.

[0056] As amphoteric polyacrylamide, examples include acrylamide reacting with anionic monomers such as acrylic acid, methacrylic acid, 2-(meth)acrylamide-N-glycolic acid, N-acryloylglycine, and other unsaturated monocarboxylic acids; maleic acid, fumaric acid, itaconic acid, citraconic acid, and other unsaturated dicarboxylic acids; aconitic acid, 3-buten-1,2,3-tricarboxylic acid, and other unsaturated tricarboxylic acids; 1-penten-1,1,4,4-tetracarboxylic acid, 4-penten-1,2,3,4-tetracarboxylic acid, 3-hexen-1,1,6,6-tetracarboxylic acid, and other unsaturated tetracarboxylic acids; vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methylpropionic acid, etc. Unsaturated sulfonic acids such as alkyl sulfonic acids; unsaturated phosphonic acids such as vinylphosphonic acid and α-phenylvinylphosphonic acid; copolymers of the above-mentioned anionic vinyl monomers (such as sodium and potassium salts or ammonium salts) and cationic monomers (such as dimethylaminoethyl methacrylate, diallyl dimethyl ammonium chloride, diallyl diethyl ammonium chloride, methacryloyloxyethyl trimethylammonium methyl sulfate, methacryloyloxyethyl trimethylammonium methyl chloride, methacrylamidopropyl trimethylammonium chloride, etc.); Mannich modified products and Hoffmann decomposition products of copolymers of acrylamide and the above-mentioned anionic monomers.

[0057] Amphoteric polyacrylamide has a self-fixing function, so even if it is added to improve paper strength, it will not become excessively cationic, thus enabling the modified rosin emulsion sizing agent to be stably fixed.

[0058] The content of the paper strength enhancer in the paper support is preferably 12 kg / t to 20 kg / t (based on solid content). By maintaining the content of the paper strength enhancer within this range, various paper strengths, such as interlayer strength, can be imparted. If the content of the paper strength enhancer is below this range, the interlayer strength may be insufficient. On the other hand, if the content of the paper strength enhancer is above this range, the interlayer strength hardly improves, and the yield of the added paper strength enhancer decreases, which may lead to fouling, foaming, etc., within the papermaking machine system, potentially reducing operability. Therefore, aluminum sulfate or various anionic, nonionic, or amphoteric yield enhancers, water permeability enhancers, and papermaking additives may be used as needed.

[0059] In addition, the paper support may contain additives such as dyes, optical brighteners, pH adjusters, defoamers, resin control agents, and pulp control agents, as needed. These agents can be those already known in the papermaking industry and are not particularly limited.

[0060] The preferred content of these additives in the paper support, calculated as solids, is 500 kg / t or less.

[0061] The paper support can be a single layer or composed of two or more layers.

[0062] There are no particular limitations on the manufacturing method of paper supports. Known long-wire forming machines, multi-wire forming machines, and sandwich forming machines can be used to manufacture paper supports by papermaking through acidic papermaking, neutral papermaking, and alkaline papermaking methods.

[0063] The upper limit of the pure water contact angle of the paper support is preferably 160° or less, more preferably 150° or less, even more preferably 140° or less, very preferably 130° or less, and particularly preferably 120° or less. The lower limit of the pure water contact angle of the paper support is preferably 20° or more, more preferably 25° or more, and even more preferably 30° or more. More preferably, it is 35° or more.

[0064] When the pure water contact angle of the paper support is within the above range, it tends to suppress excessive penetration of the aqueous dispersion of the ethylene halide polymer and suppress the occurrence of poor coating appearance such as missed coating or poor adhesion.

[0065] It should be noted that the contact angle can be measured using a contact angle meter via the static droplet method, specifically, it can be measured using the method described in the embodiments described later.

[0066] [coating]

[0067] The laminate of this embodiment has a coating layer laminated on a paper support.

[0068] The coating comprises a layer of ethylene halide polymers, but is not limited to being composed solely of a layer of ethylene halide polymers; it may further comprise a layer of (co)polymers of polymers other than ethylene halide polymers that are rich in polymerizable monomers.

[0069] When the coating includes layers other than the ethylene halide polymer layer, the lamination position of the ethylene halide polymer layer is not particularly limited, but from the perspective of anti-adhesion, the outermost layer is preferred.

[0070] From the perspective of exhibiting gas and water vapor barrier properties, the thickness of the coating constituting the laminate of this embodiment is 0.005 μm or more, more preferably 0.05 μm or more, further preferably 0.5 μm or more, particularly preferably 1 μm or more, and especially preferably 2 μm or more. If the coating thickness is less than 0.5 μm, it tends to weaken the heat-sealing strength and become a cause of breakage. The upper limit of the coating thickness is not specifically set, but from the perspective of film-forming properties and impact resistance, it is preferably 100 μm or less, more preferably 50 μm or less, and further preferably 30 μm or less.

[0071] Furthermore, the thickness of the ethylene halide polymer layer in the overall thickness of the coating is preferably 0.1% to 99%, more preferably 1% to 95%, and even more preferably 2% to 90%. When the thickness of the ethylene halide polymer layer is within the above range, excellent flexural strength and heat-sealing strength can be achieved.

[0072] [Halogenated ethylene polymer layer]

[0073] The ethylene halide polymer layer constituting the laminate of this embodiment comprises an ethylene halide polymer with a coating efficiency of 5.0 × 10⁻⁶. -9 m 3 / g or more.

[0074] The ethylene halide polymer layer can be laminated on at least a portion of the paper support; it can be a single layer or multiple layers.

[0075] From the perspectives of heat-sealing properties, film-forming properties, and impact resistance, the thickness of the ethylene halide polymer layer on the paper support is preferably 0.005–100 μm, more preferably 0.05–50 μm, and even more preferably 0.5–25 μm.

[0076] It should be noted that the thickness of the ethylene halide polymer layer on the paper support can be measured using a microscope, specifically using the method described in the examples below.

[0077] The coating efficiency of the ethylene halide polymer layer is 5.0 × 10⁻⁶. -9 m 3 / g or more, preferably 1.0×10 -8 m 3 / g or more, more preferably 1.5×10 -8 m 3 / g or more. The coating efficiency of the ethylene halide polymer layer is 5.0 × 10⁻⁶. -9 m 3 When the coating concentration is above a certain level (g), a uniform coating film is formed on the surface, exhibiting excellent barrier properties and heat-sealing properties. Furthermore, the upper limit of the coating efficiency of the ethylene halide polymer layer is not particularly limited, but is preferably 1.0 × 10⁻⁶. -6 m 3 / g or less, more preferably 0.95×10 -6 m 3 / g or less, more preferably 0.9×10 -6 m 3 / g or less. The coating efficiency of the ethylene halide polymer layer is 1.0 × 10⁻⁶. -6 m 3 When the coating is below / g, it tends to bond more firmly to the paper support through the anchoring effect.

[0078] It should be noted that the coating efficiency of the ethylene halide polymer layer can be calculated by the following formula, specifically by the method described in the examples below.

[0079] Coating efficiency of ethylene halide polymer layer (m 3 / g) = Thickness (μm) of the ethylene halide polymer layer on the paper support × 10 -6 / Content of halogenated polymers in the laminate (g / m 2 )

[0080] In addition to the ethylene halogenated polymer of this embodiment, the ethylene halogenated polymer layer may also contain other halogenated polymers with gas and water vapor barrier properties, waxes (described later), anchoring coatings, adhesive resins, etc.

[0081] -Halogenated vinyl polymer-

[0082] In this disclosure, the ethylene halide polymer can be a homopolymer comprising structural units derived from ethylene halide, or a copolymer further comprising structural units derived from monomers capable of copolymerizing with ethylene halide (hereinafter also referred to as "comonomers").

[0083] Examples of the aforementioned halogenated ethylene monomers include chlorinated monomers such as vinyl chloride, vinylidene chloride, 1,2-dichloroethylene, trichloroethylene, and tetrachloroethylene; fluorinated monomers such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, and vinyl fluoride; and bromine monomers such as vinylidene bromide, vinylidene bromine, tribromoethylene, and tetrabromoethylene. The aforementioned halogenated ethylene monomers can be used alone or in combination of two or more. Among these, chlorinated monomers are preferred from the perspective of ease of polymerization, and vinylidene chloride is particularly preferred from the perspective of barrier function.

[0084] Monomers capable of copolymerizing with ethylene halide include, for example, acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate; methacrylates such as methyl methacrylate and glycidyl methacrylate; nitriles such as acrylonitrile and methacrylonitrile; and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid. They can be used alone or in combination of two or more. Among these, acrylates, methacrylates, nitriles, and acrylic acid are preferred, and methyl acrylate, methyl methacrylate, methacrylonitrile, and acrylic acid are more preferred. Methyl acrylate and acrylic acid are also preferred, particularly from the perspective of the flexibility of the ethylene halide polymer layer.

[0085] The aforementioned ethylene halide polymer is preferably a copolymer containing 70% or more structural units derived from ethylene halide (e.g., halogenated ethylene) per 100% mass of the ethylene halide polymer. By maintaining the proportion of structural units derived from ethylene halide within this range, it tends to exhibit excellent barrier properties and film-forming properties. More preferably, it is 75% or more by mass, further preferably 80% or more by mass, particularly preferably 85% or more by mass, especially preferably 87% or more by mass, and most preferably 90% or more by mass. The upper limit is not specifically set; as a range exhibiting good film-forming properties, it is preferably 99% or less by mass, more preferably 96% or less by mass, and particularly preferably 94% or less by mass. By maintaining the structural units derived from ethylene halide within the above range, it is less likely to cause a decrease in barrier properties due to poor film formation or insufficient crystallinity, and it tends to produce an aqueous dispersion of the ethylene halide polymer that balances excellent barrier properties and film-forming properties.

[0086] The weight-average molecular weight (Mw) of the ethylene halide polymer in this embodiment is preferably 30,000 or more, more preferably 50,000 or more, further preferably 80,000 or more, and very preferably 100,000 or more. No upper limit is specifically set, but from the perspective of reducing film-forming properties by increasing the glass transition point due to the increased molecular weight, it is preferably 1,000,000 or less, more preferably 500,000 or less, further preferably 400,000 or less, and very preferably 300,000 or less. When the weight-average molecular weight of the ethylene halide polymer is within the above range, during the formation of the ethylene halide polymer layer, the polymer particles bond together in the drying process after coating, resulting in increased strength of the ethylene halide polymer layer and a tendency to improve barrier properties and heat-sealing properties. Furthermore, when the weight-average molecular weight is within the above range, the number of unstable polymer ends decreases, and the coloring (yellowing) of the polymer layer also tends to decrease.

[0087] It should be noted that the above weight-average molecular weight can be determined using GPC (gel permeation chromatography), specifically, it can be determined using the method described in the examples below.

[0088] The ethylene halide polymer is preferably a crystalline resin, and its crystallization melting point is preferably below 180°C, more preferably below 175°C, further preferably below 170°C, and very preferably below 165°C. The lower limit of the crystallization melting point is not specifically set, but for the purpose of exerting barrier properties through its crystalline structure, it is preferably above 50°C, more preferably above 60°C, further preferably above 70°C, and very preferably above 80°C.

[0089] When the crystallization melting point is within the above range, the crystallization of the resin in the aqueous dispersion is promoted and the elasticity is increased, which can prevent cracks caused by the inability to follow the unevenness on the paper support, and has the ability to prevent the coating surface from becoming sticky or sticking due to aging at high temperature after being wound on the paper support.

[0090] It should be noted that the above-mentioned crystallization melting point can be determined using a differential scanning calorimeter (DSC), specifically, it can be determined using the method described in the examples below.

[0091] In addition, the content of ethylene halide polymer in the laminate is preferably 1 to 150 g / m³. 2 More preferably, 2-100 g / m 2 A further preferred value is 3-50 g / m 2 When the content of the halogenated ethylene polymer is within the above range, a laminate with excellent flexural strength and barrier properties can be produced.

[0092] In this embodiment, the ethylene halide polymer layer may contain 0.001 to 20 parts by weight of wax relative to 100 parts by weight of the ethylene halide polymer. For the purpose of balancing crystallization rate and barrier properties, the wax content is more preferably 0.005 to 10 parts by weight, and even more preferably 0.01 to 5 parts by weight. The wax may be of only one type, or it may be a wax composition consisting of two or more types of wax.

[0093] Wax (or wax composition) may be added to the aqueous dispersion of the ethylene halide polymer in the formation of the ethylene halide polymer layer described later. By adding wax, the effects of improved slip properties and prevention of adhesion can be obtained.

[0094] The types of wax that can be used in this embodiment are not particularly limited. Natural or synthetic waxes can be used, such as polyolefin wax, paraffin wax, carnauba wax, beeswax, Chinese insect wax, paraffin wax and lignite wax, as well as their esters, either alone or in the form of a composition containing them as main components (more than 50% by mass of the whole). Polyolefin wax and carnauba wax are preferred.

[0095] It should be noted that when wax is added to ethylene halide polymers, crystallization can easily occur, causing changes in the initial physical properties. Therefore, it is preferable to adjust the amount of wax according to the morphology of the ethylene halide polymer layer.

[0096] It should be noted that in the laminate of this embodiment, when the ethylene halide polymer layer is not the outermost layer, it is preferable that the ethylene halide polymer layer does not contain wax. By not containing wax, the coating of the ethylene halide polymer cures slowly, tending to have good impact resistance of the barrier paper.

[0097] [Method for forming the ethylene halide polymer layer]

[0098] The method for forming the ethylene halide polymer layer in this embodiment includes the steps of coating an aqueous dispersion of ethylene halide polymer particles (hereinafter also referred to as "aqueous dispersion") onto a paper support and drying it.

[0099] The method for coating an aqueous dispersion of ethylene halide polymer particles onto a paper support in this embodiment is not particularly limited, and coating can be performed using known coating apparatus and coating systems. For example, gravure coating methods such as direct gravure coating, two-roll oscillating coating, bottom-feed three-roll reverse coating, doctor blade coating, air knife coating, die coating, bar coating, dip coating, spray coating, scraper coating, curtain coating, sizing press coating, and guillotine coating can be used.

[0100] The amount of aqueous dispersion applied during coating can be adjusted appropriately according to the desired thickness of the ethylene halide polymer layer, without any particular limitation. By repeatedly applying and drying once or multiple times, the desired ethylene halide polymer layer can be formed. As long as the coating amount is set to avoid insufficient drying or solvent residue, a laminate that effectively exhibits properties such as gas and water vapor barrier properties, heat sealing properties, yellowing resistance, and recyclability can be obtained.

[0101] Furthermore, there are no particular limitations on the drying method. Examples include natural drying, drying in an oven set to a specific temperature, using a dryer attached to the coating machine, such as a steam heater, gas heater, infrared heater, electric heater, hot air heater, microwave, or drum dryer. The drying conditions can be appropriately selected depending on the drying method. For example, in the oven drying method, drying at a temperature of 60–200°C for approximately 1 second to 5 minutes is preferred.

[0102] -Aqueous dispersion of ethylene halide polymer particles-

[0103] The aqueous dispersion of ethylene halide polymer particles in this embodiment comprises ethylene halide polymer particles and water, for example, obtained by emulsion polymerization of a monomer containing ethylene halide.

[0104] There are no particular limitations on the emulsion polymerization method for halogenated ethylene polymers; well-known methods can be used.

[0105] From the perspective of preventing penetration into the paper support or reduction in barrier properties due to puncture of pulp fibers, the content of ethylene halide polymer particles in the aqueous dispersion of this embodiment is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, calculated in terms of solid content. Furthermore, the upper limit is not specifically set, but is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less. By setting the content of ethylene halide polymer particles within this range, an aqueous dispersion of a poly(ethylene halide) polymer with appropriate viscosity can be obtained.

[0106] It should be noted that the content of ethylene halide polymer particles in the aqueous dispersion refers to the value obtained by the drying loss method, which is determined by the following method. Using a SMART SYSTEM 5 manufactured by CEM, 2-4 g of aqueous dispersion (e.g., latex) is added to a glass fiber pad using a dropper, and the mass of the solid component after drying at a temperature of 40% output is measured. The content of the solid component (mass%) is calculated using the formula "(mass after drying / mass of aqueous dispersion) × 100", and this is taken as the content of the ethylene halide polymer particles.

[0107] It should be noted that if the aqueous dispersion also includes resins other than ethylene halogenated polymers, the content of ethylene halogenated polymers alone shall be determined as follows: After defatting the weighing dish with acetone or the like, measure 1 ± 0.1 g to 0.1 mg of the aqueous dispersion and spread it evenly on the bottom of the weighing dish. (A) Dry the mixture at 80°C for 120 minutes using a hot air dryer or the like. After drying, transfer the weighing dish to a desiccator and cool it to room temperature. Measure the mass. Repeat step (A) until the difference in mass fraction between repeated measurements is less than 0.5%. Calculate the dried mass of the aqueous dispersion in this way. Next, collect the obtained dried components and dissolve them in a solvent that can dissolve resins other than ethylene halogenated polymers. Acetone is preferred as the solvent. Take out all the solvent-insoluble components and spread them evenly on the bottom of the weighing dish. (B) Dry the mixture at 105°C for 60 minutes. After drying, transfer the weighing dish to a desiccator and return it to room temperature. Measure the mass to the order of 0.1 mg. Repeat step (B) until the difference in repeated measurements is less than 2% by mass. The mass of the solvent-insoluble component obtained in this way is the mass of the ethylene halide polymer only, and the content of the ethylene halide polymer particles is defined as "mass of solvent-insoluble component (g) / dry mass of aqueous dispersion (g)".

[0108] From the perspective of suppressing the reduction in barrier properties caused by pulp fiber puncture, the viscosity of the aqueous dispersion of the halogenated ethylene polymer is preferably 2 mPa·s or more, more preferably 3 mPa·s or more, further preferably 4 mPa·s or more, particularly preferably 5 mPa·s or more, and especially preferably 6 mPa·s or more. Furthermore, from the perspective of leveling, the viscosity is preferably 1 MPa·s or less, more preferably 1 × 10⁻⁶ MPa·s or less. -2 Below MPa·s, more preferably 1×10 -4 Below MPa·s, especially preferably 1×10 -5 Below MPa·s, preferably 1×10 -6 Below MPa·s.

[0109] It should be noted that viscosity can be measured as follows: Using a BLII type viscometer manufactured by Toki Sangyo Co., Ltd., while adjusting the temperature of the aqueous dispersion of the ethylene halide polymer to 20°C in a constant temperature bath, rotate the viscometer for 20-30 seconds. Then, stop rotation with the clamping lever pressed and read the pointer value. Select an appropriate rotor model and rotation speed based on the viscosity of the aqueous dispersion of the ethylene halide polymer, and multiply by the conversion factor corresponding to the rotation speed and rotor model to calculate the viscosity.

[0110] In this embodiment, the ethylene halide polymer in the aqueous dispersion is particulate, with an average particle size preferably greater than 120 nm. The average particle size of this ethylene halide polymer is closely related to the film-forming properties, barrier properties, heat-sealing properties, and dissociation properties of the ethylene halide polymer layer. When the average particle size is within the aforementioned range, water evaporation is promoted during the coating and drying process of the aqueous dispersion onto the paper support, allowing the polymer particles to combine and merge before being attracted into the capillaries formed in the gaps between the pulp fibers of the paper. As a result, a more uniform layer can be formed with a small amount of polymer, thus improving barrier properties and heat-sealing properties. Furthermore, in the process of recycling the laminate, when the paper support and the ethylene halide polymer layer are dissociated in water, the dissociation property is improved because the interface between the polymer layer and the paper support does not undergo the necessary bonding (the polymer does not enter the paper in the necessary amount).

[0111] The average particle size of the halogenated ethylene polymer is preferably 130 nm or more, more preferably 140 nm or more, further preferably 150 nm or more, particularly preferably 160 nm or more, and most preferably 170 nm or more. The larger the average particle size, the better the above-mentioned effect. Therefore, the upper limit is not specifically set, but considering the coatability and the preservation stability (emulsification stability) of the aqueous dispersion, it is preferably 400 nm or less, more preferably 300 nm or less, further preferably 250 nm or less, and particularly preferably 200 nm or less.

[0112] It should be noted that the above average particle size refers to the value measured by dynamic light scattering method. Specifically, it can be measured by the method described in the following examples.

[0113] The emulsifier used in the manufacture of the aqueous dispersion of the halogenated polymer particles in this embodiment is not particularly limited. Examples include anionic amphiphilic compounds such as carboxylates, sulfates, sulfonates, and phosphates, as well as geminate amphiphilic compounds and nonionic amphiphilic compounds.

[0114] Examples of carboxylate salts include, for instance, soaps, sodium octanoate, sodium decanoate, sodium laurylate, sodium tetradecanoate, sodium palmitate, sodium stearate, sodium oleate, sodium perfluorooctanoate, sodium N-lauroyl sarcosinate, sodium cocoyl glutamate, and α-sulfo fatty acid methyl ester salts.

[0115] As sulfate esters, such as higher alcohol sulfate esters, higher alkyl ether sulfate esters, sulfated oils, sulfated fatty acid esters, and sulfated fatty acids, they are a general term for anionic amphiphilic compounds produced by sulfated higher alcohols containing alkyl groups.

[0116] As higher alcohol sulfate salts, there are sodium lauryl sulfate, sodium myristyl sulfate, sodium hexadecyl sulfate, sodium stearyl sulfate, sodium oleyl sulfate, etc.

[0117] Higher alkyl ether sulfates are a general term for amphiphilic compounds formed by the addition of ethylene oxide to higher alcohols to produce sulfates. Examples of higher alkyl ether sulfates include sodium lauryl ether sulfate, sodium myristole sulfate, sodium hexadecyl ether sulfate, sodium stearyl ether sulfate, sodium oleyl ether sulfate, and secondary alcohol ethylene oxide adduct sulfates.

[0118] Sulfated oils are a general term for substances obtained by sulfatating and neutralizing waxes formed by esterification of higher fatty acids and higher aliphatic alcohols. Examples include sulfonated castor oil (formed by sulfatating castor oil), sulfated olive oil, sulfated tallow, sulfated peanut oil, sulfated cetyl oil, and their esters.

[0119] Sulfated fatty acid esters and sulfated fatty acids are a general term for anionic amphiphilic compounds formed by sulfation of fatty acid esters or fatty acids containing hydroxyl groups or double bonds into sulfate salts. Examples include α-sulfonated fatty acids, and substances formed by sulfation of unsaturated fatty acids or epoxides of unsaturated fatty acid esters.

[0120] Examples of sulfonates represented by R-SO3Na include sodium 1-hexanesulfonate, sodium 1-octanesulfonate, sodium 1-decanesulfonate, sodium 1-dodecanesulfonate, sodium perfluorobutanesulfonate, sodium linear alkylbenzenesulfonate, sodium naphthalenesulfonate, sodium naphthalenedisulfonate, sodium naphthalenetrisulfonate, sodium butylnaphthalenesulfonate, and sodium perfluorooctanesulfonate. It should be noted that sodium linear alkylbenzenesulfonate includes sodium toluenesulfonate, sodium cumenesulfonate, sodium octylbenzenesulfonate, and sodium dodecylbenzenesulfonate.

[0121] Examples of phosphate salts include lauryl phosphate, sodium lauryl phosphate, and potassium lauryl phosphate. It should be noted that substances formed by adding ethylene oxide to these salts are also included.

[0122] Geminid amphiphilic compounds have two fatty acid chains in one molecule, such as dialkyl sulfonated succinate salts.

[0123] Among the above-mentioned anionic amphiphilic compounds and geminal amphiphilic compounds, soaps, sulfonates, and geminal amphiphilic compounds are preferred; more preferably, sodium dodecylbenzenesulfonate, sodium alkyl sulfonate, sodium palmitate, and dialkyl sulfonated succinate salts are included; even more preferably, sodium dodecylbenzenesulfonate and dialkyl sulfonated succinate salts are included; and particularly preferably, sodium dodecylbenzenesulfonate is preferred.

[0124] In addition, nonionic emulsifiers are amphiphilic compounds that do not undergo ionic dissociation in water and have hydrophilic groups such as hydroxyl groups and ether bonds (polyoxyethylene chains, etc.).

[0125] As nonionic amphiphilic compounds, they include ester, ether, ester-ether, alkanolamide, alkyl glycoside, and higher alcohols.

[0126] Examples of ester types include glyceryl lauryl acid ester, glyceryl monostearate ester, sorbitan fatty acid ester, and sucrose fatty acid ester.

[0127] Examples of ether-type ethers include polyoxyethylene alkyl ethers, pentaethylene glycol monododecyl ether, and octaethylene glycol monododecyl ether.

[0128] Examples of ester-ether types include polyoxyethylene glycerol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, sorbitan fatty acid esters, polyvinylhexyl alcohol fatty acid esters, and sorbitan fatty acid esters in polyethylene glycol.

[0129] Examples of alkanolamides include lauric acid diethanolamide, oleic acid diethanolamide, stearic acid diethanolamide, and coconut oil fatty acid diethanolamide.

[0130] Examples of alkyl glycosides include octyl glucoside, decyl glucoside, and lauryl glucoside.

[0131] Examples of higher alcohols include cetyl alcohol, stearyl alcohol, and oleyl alcohol.

[0132] These anionic and nonionic emulsifiers can be used alone or in combination.

[0133] In this embodiment, the pH of the aqueous dispersion is preferably less than 4.0. The pH of the aqueous dispersion has a significant impact on the yellowing resistance of the coated ethylene halide polymer layer. In ethylene halide polymers, dehydrohalogenation occurs from the ends of unstable polymer chains, resulting in conjugated chains in the main chain, which causes discoloration (yellowing). This yellowing is prone to occur at high temperatures, and in the manufacturing of the laminate of this embodiment, it is prone to occur during the drying process. If the pH is low, i.e., the hydrogen ion concentration in the water is high, dehydrohalogenation in the aqueous dispersion is less likely to occur. The pH of the aqueous dispersion is more preferably 3.5 or less, further preferably 3.0 or less, and particularly preferably 2.5 or less. The lower limit is not specifically set, but considering the corrosion of the coating apparatus, it is preferably 1.0 or more.

[0134] It should be noted that the pH of the aqueous dispersion can be measured using a pH meter, specifically using the method described in the examples below.

[0135] The surface tension of the aqueous dispersion in this embodiment is suitably selected based on the physical properties of the paper support, such as the surface contact angle and permeability. Preferably, it is 10 mN / m or more, more preferably 20 mN / m or more, and even more preferably 30 mN / m or more. An upper limit is not specifically set, but preferably 60 mN / m or less, more preferably 55 mN / m or less, and even more preferably 45 mN / m or less. When the surface tension of the aqueous dispersion is within this range, the aqueous dispersion is uniformly coated on the paper support, and the ethylene halide polymer layer forms a tight film. Therefore, defects are less likely to occur at the interface, thus providing gas and water vapor barrier properties.

[0136] It should be noted that the surface tension of the aqueous dispersion can be measured using the plate method with an automatic surface tension meter CBVP-Z (Kyowa Interface Chemicals) in a constant temperature room of 20℃ and 55%RH.

[0137] [Anchoring Coating]

[0138] Furthermore, the laminate of this embodiment can have an anchoring coating containing an anchoring agent between the paper support and the coating, as needed. The anchoring coating improves the adhesion between the paper support and the coating.

[0139] Examples of anchoring coating agents include polyethylene resins (low-density, medium-density, high-density), polypropylene resins, polyacrylate resins (polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, etc.), polymethacrylate resins (polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly-2-ethylhexyl methacrylate, etc.), polystyrene resins, polyacrylate / styrene-butadiene resins, acrylic resins, styrene-acrylic resins, styrene-butadiene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl butyral, polyvinyl alcohol formaldehyde, ethylene / vinyl acetate resins, and alkane-based resins. Resins, including urethane resins, isocyanate resins, polyester resins, oxazoline resins, carbodiimide resins, vinyl acetate / butyl acrylate copolymers, maleic anhydride copolymers, acrylic acid / methyl acrylate copolymers, etc.; polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymer polyvinyl alcohol; proteins such as casein, soy protein, and synthetic protein; starches such as oxidized starch, cationic starch, urea phosphate starch, hydroxyethyl etherified starch, and oxidized modified starch; cellulose derivatives such as carboxymethyl cellulose, hydroxymethyl cellulose, and hydroxymethyl cellulose; sodium alginate; polyvinylpyrrolidone; and sodium alginate.

[0140] Among the above-mentioned anchoring coating agents, the preferred ones are polyethylene resins (low density, medium density, high density), polypropylene resins, polyacrylate resins (polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, etc.), polymethacrylate resins (polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, poly-2-ethylhexyl methacrylate, etc.), polystyrene resins, polyacrylate / styrene-butadiene resins, acrylic resins, styrene-acrylic resins, styrene-butadiene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl butyral, polyvinyl alcohol formaldehyde, ethylene / vinyl acetate resins, alkane resins, urethane resins, isocyanate resins, polyester resins, oxazoline resins, carbodiimide resins, vinyl acetate / butyl acrylate copolymers, maleic anhydride copolymers, and acrylic / methyl acrylate copolymers. From the perspective of adhesion, further preferred resins include polyacrylic styrene / butadiene resins, acrylic resins, styrene-acrylic resins, styrene-butadiene resins, polyvinyl chloride resins, polyvinylidene chloride resins, urethane resins, isocyanate resins, polyester resins, vinyl acetate / butyl acrylate copolymers, and acrylic / methyl acrylate copolymers. Most preferred are polyacrylic styrene / butadiene resins, acrylic resins, styrene-acrylic resins, and styrene-butadiene resins. By using these anchoring coating agents for surface treatment, the surface of the paper support composed of hydrophilic cellulose can be hydrophobicized, improving the smoothness of the paper support, inhibiting the permeation of the aqueous dispersion of halogenated polymer particles, reducing the coating amount, and imparting superior adhesion.

[0141] There are no particular restrictions on the form of the anchoring coating agent; it can be a solution type containing organic solvents, an aqueous solution type, an aqueous emulsion type, etc.

[0142] Examples of solvents that can be used to dissolve or disperse the above-mentioned anchoring coating agents include alcohols, esters, glycol ethers, glycol ether acetates, ketones, ethers, chlorides, hydrocarbons, 2-nitropropane, and water.

[0143] Alcohols are a general term for substances formed by replacing a portion of a hydrocarbon with a hydroxyl group. Examples include methanol, ethanol, isopropanol, n-propanol, sec-butanol, isobutanol, and n-butanol.

[0144] Esters are organic solvents that have ester bonds within their molecules. Examples include methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, sec-butyl acetate, isobutyl acetate, n-butyl acetate, methyl ethyl acetate, and ethyl lactate.

[0145] Glycol ethers are a general term for substances that have both an ether group and a hydroxyl group in their molecules. Examples include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether.

[0146] Diol ether acetates are a general term for substances that contain ether, hydroxyl, and acetyl groups within their molecules. Examples include ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, and diethylene glycol butyl ether acetate.

[0147] Ketones are a general term for substances that contain a ketone group in their molecules. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, methyl cyclohexane, ethyl pentyl ketone, diisobutyl ketone, diacetone alcohol, and isophorone.

[0148] Ethers are a general term for substances that contain an ether group in their molecules. Examples include diethyl ether, isopropyl ether, tetrahydrofuran, and 1,4-dioxane.

[0149] Chlorides are a general term for substances that contain chlorine groups in their molecules, such as dichloromethane, trichloroethane, perchloroethylene, and dichloropropane.

[0150] Hydrocarbons are molecules composed of carbon and hydrogen, and are classified into aliphatic and aromatic systems. Examples of aliphatic hydrocarbons include cyclohexane, heptane, hexane, paint solvent oil, octane, SBP, Shellsol, and isoparaffins. Examples of aromatic hydrocarbons include benzene, toluene, and xylene.

[0151] Regarding the solvent for dissolving or dispersing the anchoring coating agent, alcohols, esters, ketones, and hydrocarbons are preferred in terms of the solubility of the anchoring coating agent. In terms of evaporation rate, surface tension, and viscosity, methanol, isopropanol, n-propanol, ethyl acetate, methyl acetate, sec-butyl acetate, isobutyl acetate, n-butyl acetate, acetone, tetrahydrofuran, methyl ethyl ketone, benzene, toluene, and xylene are more preferred.

[0152] The solvents mentioned above can be used alone, or two or more can be mixed to adjust the solubility of the anchoring coating agent and the volatility of the solvent.

[0153] Furthermore, from an environmental perspective, the anchoring coating agent is preferably used in the form of an aqueous emulsion in which polymer particles are dispersed in water.

[0154] In a paper support that has undergone surface treatment with an anchoring coating agent (with an anchoring coating deposited), the arithmetic mean roughness Ra of the surface coated with the aqueous dispersion of ethylene halide polymer particles is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. When the arithmetic mean roughness is 20 μm or less, it can prevent puncture of the coating due to the fibers of the paper support and peeling due to unevenness, and can reduce the coating amount (content) of the ethylene halide polymer. The lower limit of the above-mentioned arithmetic mean roughness Ra is not specifically set, but is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.5 μm or more.

[0155] It should be noted that the arithmetic mean roughness Ra mentioned above was determined by the following method.

[0156] Using the SJ-500 (manufactured by Mitutoyo Co., Ltd.), calibration is performed using the standard film provided with the device through the following settings.

[0157] <Calibration Settings (Roughness Correction)>

[0158] Standard: JIS 1994

[0159] Filter: GAUSS

[0160] Number of intervals: 5

[0161] Sampling length value: 2.5mm

[0162] Measured velocity: 0.5 mm / s

[0163] Standard film nominal value: 2.970

[0164] Correction was performed after confirming that the measured Ra was within ±3% of the nominal value of the standard.

[0165] <Sample Evaluation Conditions>

[0166] Standard: ISO 1997

[0167] Curve: R

[0168] Filter: GAUSS

[0169] lc: 0.8mm

[0170] ls: 2.5mm

[0171] Number of intervals: 5

[0172] Walk forward / walk behind: lc

[0173] Waveform Removal: OFF

[0174] Curve Correction: OFF

[0175] Parameters: Ra, Rz, Rq

[0176] <Measurement Conditions>

[0177] Measurement speed: 0.5 mm / s

[0178] Return speed: 10mm / s

[0179] Measuring range: 800mm

[0180] Overrange: ESC

[0181] Automatic ranging: OFF

[0182] X-axis drive: ON

[0183] Arm correction: OFF

[0184] Post-interruption calculation: OFF

[0185] Polarity switching: +

[0186] Set the sample on the paper support with the anchoring coating horizontally. Make the stylus contact the sample, lower the detector until the height of the main panel is 0 mm, and press the START / STOP switch to begin measurement. The arithmetic mean roughness Ra refers to the value expressed in micrometers (μm) obtained by taking only a reference length (l) along the direction of the mean line of the roughness curve, taking the X-axis along the direction of the mean line of this section, and the Y-axis along the direction of the longitudinal magnification factor, and representing the roughness curve as y = f(χ).

[0187] [Number 1]

[0188]

[0189] The thickness of the anchoring coating is preferably 200 μm or less, more preferably 100 μm or less, further preferably 50 μm or less, and most preferably 25 μm or less. The lower limit is not specifically set, but is preferably 0.001 μm or more, more preferably 0.01 μm or more, further preferably 0.1 μm or more, and most preferably 1 μm or more. By making the thickness of the anchoring coating within this range, in terms of the flexibility of the laminate, the coating is less likely to crack when the laminate is bent, the penetration of the aqueous dispersion of ethylene halide polymer particles into the paper support can be prevented, and high adhesion can be obtained through surface modification of the cellulose fibers of the paper support.

[0190] There are no particular restrictions on the application method of anchoring coating agent on paper support. Metering rod sizing press, tank sizing press, doctor blade coater, doctor blade coater, roller coater, air knife coater, reverse roller coater, curtain coater, spray coater, sizing press coater, dip coater, gate roller coater, etc.

[0191] Furthermore, there are no particular restrictions on the drying method for the anchoring coating agent; curing methods such as ultraviolet / electron ray curing can also be used, but drying by applying heat is preferred. There are no particular restrictions on the heat-based drying method; conventional methods using steam heaters, gas heaters, infrared heaters, hot air heaters, microwave heaters, drum dryers, etc., can be used.

[0192] In addition, the aforementioned anchoring coating may contain pigments. As pigments, one or more of the following can be used: kaolin, clay, engineered kaolin, layered clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicates, colloidal silica, satin white, and other inorganic pigments, as well as solid, hollow, or core-shell organic pigments. Among these, colloidal silica is the most preferred for improving adhesion.

[0193] The pigment content, based on dry weight, is preferably 300 parts by weight or less, more preferably 250 parts by weight or less, further preferably 150 parts by weight or less, and most preferably 100 parts by weight or less relative to 100 parts by weight of the anchoring coating agent.

[0194] Furthermore, the aforementioned anchoring coating agent can be included in the ethylene halide polymer layer. By appropriately mixing the aforementioned anchoring coating agent with an aqueous dispersion of ethylene halide polymer particles for coating, the number of coating passes can be reduced, the adhesion to the paper support becomes stronger, and yellowing of the ethylene halide polymer can be suppressed. However, if the content of the anchoring coating agent is too high, the barrier properties unique to the ethylene halide polymer are impaired. Therefore, it is preferable that the anchoring coating agent, based on the resin solids content of the ethylene halide polymer, is 50% by mass or less, more preferably 40% by mass or less, further preferably 20% or less, and most preferably 10% or less. The lower limit is not specifically set, but is preferably 0.001% by mass or more, more preferably 0.01% or more, further preferably 0.1% or more, and most preferably 1% or more. When more than 50% by mass of anchoring coating agent is added, the barrier properties of the ethylene halide polymer are impaired, and if it is less than 0.001% by mass, excellent adhesion cannot be obtained.

[0195] To improve the adhesion between the paper support and the coating, the surface of the paper support or the surface of the anchoring coating can be activated before the coating is formed. Methods for activating the surface of the paper support or the anchoring coating include corona discharge treatment, plasma discharge treatment, strong acid treatment, electron beam treatment, ultraviolet treatment, and flame treatment, which introduce hydrophilic components such as hydroxyl, carboxyl, ester, carboxylic acid, ether, amino, imino, amide, and sulfate groups onto the surface of the paper support or the anchoring coating.

[0196] In the laminate of this embodiment, in order to maintain the molded shape, a universal resin film can be present between any of the layers of the paper support, the anchoring coating, the coating, and the adhesive resin layer described later.

[0197] There are no particular limitations on resin membranes. Examples include membranes made from fossil resources such as polyester, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polypropylene, polyethylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polymethylpentene, polyvinyl chloride, polyacrylonitrile, acrylonitrile / butadiene / styrene, acrylonitrile / styrene / poly(meth)acrylic acid, polyvinylidene chloride, polyamide (nylon), polyacetal, and polycarbonate; polylactic acid (PLA); cellulose acetate; polybutylene succinate (PBS); polybutylene succinate / adipate-butylene glycol ester (PBSA); bio-polyethylene; bio-polyethylene terephthalate; and bio-polyurethane.

[0198] It should be noted that biological resins refer to polymeric materials with a number average molecular weight (Mn) of 1,000 or higher, which are synthesized through chemical or biological processes using substances derived from renewable organic resources as raw materials.

[0199] In addition, as resins derived from fossil resources and resins derived from organisms, any one of the following can be used: polylactic acid (PLA), cellulose acetate, polybutylene succinate (PBSA), and other biodegradable resins (biodegradable resins); polyethylene, polypropylene, polyester, polyethylene terephthalate, polyamide (nylon), biodegradable polyethylene, and other non-biodegradable resins.

[0200] It should be noted that biodegradable resins are resins that can be decomposed to the molecular level through the action of microorganisms, ultimately becoming carbon dioxide and water and cycling in nature.

[0201] As a method for laminating the film, examples include laminating the various resins described above using an extrusion lamination method to create a resin laminate. When the resin laminate is a film bonding layer, examples include bonding films made of the various resins described above using dry lamination, sand lamination, or similar methods to create a resin laminate. Preferably, the resin laminate is located on the surface of the paper support containing the halogenated polymer layer.

[0202] In this embodiment, when the resin laminate is a film lamination layer, the preferred barrier films are those made of resins including polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, and polyacrylonitrile; those made of various metals such as aluminum laminated onto films made of the aforementioned resins; and those made of various metals such as aluminum or inorganic oxides such as silicon oxide or aluminum oxide vapor-deposited onto films made of the aforementioned resins. Vapor-deposited films are more preferred. These films can be laminated in one or more layers for use, depending on the purpose.

[0203] The moisture barrier properties (water vapor transmission rate) of the gas and water vapor barrier laminate in this embodiment are preferably 200 g / m³. 2 • Less than 24 hours, more preferably 100g / m 2 • Less than 24 hours, preferably 50g / m 2 • Less than 24 hours, more preferably 10g / m 2 • Less than 24 hours, optimally 5g / m 2 • Less than 24 hours

[0204] It should be noted that the above-mentioned moisture resistance (water vapor transmission rate) can be determined by using a moisture permeation cup for a moisture permeation test. Specifically, it can be determined by the method described in the following examples.

[0205] The laminate of this embodiment can be used directly in laminate form, laminated with various resins, or laminated with various general-purpose films, barrier films, aluminum foils, etc., and can be used in packaging materials for food packaging, containers, cups, etc., or in various industrial materials. Among these, it can be suitably used as a packaging material for food packaging, containers, cups, etc.

[0206] There are no particular limitations on the packaging materials or containers that comprise the laminated body of this embodiment, and examples include liquid cartons (brick-shaped, mountain-shaped, paper cans, etc.), paper pallets (box pallets, deep-drawn pallets, molded pulp pallets, etc.), cosmetic cases, wrapping paper, labels, corrugated paper, four-side sealable bags, three-side sealable bags, pillow-type packaging bags, adhesive bags, corner-supported bags, square-bottom bags, stand-up pouches, deep-drawn containers, vacuum packaging bags, skin packaging bags, snap-on bags, spouted bags, twist-up packaging, outer packaging, trays, cups, bottles, caps, inner caps, etc. Pillow-type packaging bags are particularly preferred for food packaging applications.

[0207] When the laminate of this embodiment is used as packaging material or container for food, especially flexible packaging material, a heat-sealing adhesive resin other than a halogenated ethylene polymer can be further laminated. This improves heat-sealing strength and low-temperature sealing performance, prevents deterioration of contents due to oxygen, moisture, etc., and extends shelf life.

[0208] The aforementioned heat-sealing adhesive resin preferably comprises at least one selected from the group consisting of polyurethane resins, polyester resins, acrylic resins, and vinyl acetate copolymers. Polyurethane resins are particularly preferred. The content of these resins is not particularly limited as long as it does not impair the properties of the adhesive resin, and can be 50% by mass or more of the adhesive resin.

[0209] It should be noted that flexible packaging refers to packaging materials made of flexible materials.

[0210] In addition, adhesive resins may include, within a range that does not impair the properties of the adhesive resin, preferably less than 50% by mass (more preferably less than 40% by mass, particularly preferably less than 30% by mass), such as polyvinyl butyral resins, vinyl phenyl resins, polyamide resins, vinyl chloride / vinyl acetate copolymers, vinyl chloride / polyester resins, chlorinated polyolefins (chlorinated polypropylene, chlorinated polyethylene, etc.), styrene block copolymers and their derivatives (styrene-isoprene block copolymers, styrene-butadiene block copolymers, and their hydrogenates and maleic anhydride modifiers, etc.).

[0211] The polyurethane resins mentioned here are the reaction products of polyisocyanates and polyols.

[0212] The polyisocyanate compounds used in the synthesis of polyurethane resins are not particularly limited as long as they are organic polyisocyanate compounds containing two or more isocyanate groups per molecule. Examples include toluene diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexane diisocyanate, 1,5-naphthalene diisocyanate, phenylenediamine diisocyanate, 2,6-diisocyanate methylhexanoate, isophorone diisocyanate (IPDI), methylcyclohexane-2,4-(or 2,6-)diisocyanate, and 4,4'-methylenebis(cyclohexyl isocyanate), as well as aromatic, aliphatic, and alicyclic organic diisocyanates. A single type or a mixture of two or more types can be used. From the perspective of preventing coloration, aliphatic isocyanates are preferred, while from the perspective of resin strength, aromatic isocyanates are preferred.

[0213] Polyols used in the synthesis of polyurethane resins include, for example, polyester glycol, polyether glycol, polyester polyol, polyacrylate glycol, polyesteramide glycol, polycarbonate glycol, or mixtures thereof or copolymers thereof.

[0214] Examples of polyether glycols include polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyoxypentane glycol, copolyether glycol composed of 1,4-butylene and 2,2-dimethylpropylene, copolyether glycol composed of 1,4-butylene and 3-methyl-1,4-butylene, or mixtures thereof.

[0215] Examples of polyester diols include, for instance, polycarboxylic acids and their anhydrides esterified with alkyl polyols, as well as esterified products obtained by polymerizing hydroxycarboxylic acids and / or lactones as internal esters using alkyl polyols as initiators.

[0216] Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3,3-diethylglutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,1-cyclobutanedicarboxylic acid.

[0217] Specific examples of alkyl polyols constituting polyester polyols include ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,9-decanediol, 1,4-cyclohexanediol, 1, 4-Dimethylolcyclohexane, 2,2-diethylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 3-methylpentane-1,4-diol, 2,2-diethylbutane-1,3-diol, 4,5-nonanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, glycerol, pentaerythritol, erythritol, sorbitol, mannitol, trimethylolpropane, trimethylolethane, etc.

[0218] Among these, polyester glycol is preferred in terms of resin strength.

[0219] Polyester resins are polymers synthesized through the polycondensation reaction of polycarboxylic acids and polyols, and various raw materials can be used. Types of polyester resins include saturated homopolymer polyester resins (without unsaturated bonds in the polyester backbone), saturated copolymer polyester resins, alkyd resins, and unsaturated polyester resins (with unsaturated bonds in the polyester backbone). Saturated copolymer polyester resins are preferred due to their superior low-temperature heat-sealing properties and resistance to tack.

[0220] Examples of polycarboxylic acids that undergo condensation polymerization include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, and citric acid.

[0221] Examples of polyols that can undergo polycondensation include ethylene glycol, propylene glycol, butanediol, and glycerol.

[0222] These substances can be used alone or in combination of two or more. Examples of polyester resins include resins composed of one polycarboxylic acid (e.g., phthalic acid) and two polyols (e.g., ethylene glycol and butanediol).

[0223] Acrylic resins are polymers containing an olefinically unsaturated monomer having at least one carboxyl or carboxylic ester group as a monomer component. They can be homopolymers of olefinically unsaturated monomers having at least one carboxyl or carboxylic ester group, or copolymers of the monomer with other monomers capable of copolymerization therewith. Furthermore, acrylic resins can be alkali metal salts, amine salts, or ammonium salts of the carboxyl (carboxylic acid) groups of the aforementioned homopolymers or copolymers.

[0224] Examples of olefinic unsaturated monomers having carboxyl or carboxylic acid ester groups include methacrylic acid, acrylic acid, methacrylates, and acrylates.

[0225] When acrylic resins are copolymers, the "other monomers" mentioned above can include: ethylene; aromatic vinyl monomers such as styrene, α-methylstyrene (vinyltoluene), and chlorostyrene; cyano-containing olefinic unsaturated monomers such as acrylonitrile and methacrylonitrile; acrylamide monomers such as acrylamide, N-hydroxymethylmethacrylamide, and N-butoxymethylacrylamide.

[0226] Specific examples of copolymers in which acrylic resins are used include methacrylate-acrylate copolymers, acrylate-acrylate copolymers, ethylene-acrylic acid copolymers (EAA), ethylene-methacrylate copolymers (EMAA), ethylene-acrylate copolymers, styrene-acrylic acid copolymers, and styrene-acrylate copolymers.

[0227] The glass transition temperature of acrylic resins can be adjusted by appropriately changing the types and proportions of monomers used in copolymerization.

[0228] When the acrylic resin is a copolymer, the proportion of structural units with an acrylic structure is preferably more than 20% of the total copolymer.

[0229] Vinyl acetate copolymers are copolymers of vinyl acetate and at least one monomer capable of copolymerizing with vinyl acetate.

[0230] Monomers that can copolymerize with vinyl acetate include, for example, ethylene, n-butyl methacrylate, alkyl methacrylates such as 2-ethylhexyl methacrylate, hydroxyl-containing methacrylates such as 2-hydroxyethyl methacrylate, and acrylic acid.

[0231] As a specific example of vinyl acetate copolymers, ethylene vinyl acetate copolymers can be cited.

[0232] In vinyl acetate copolymers, the proportion of structural units having a vinyl acetate structure is preferably more than 20% of the total copolymer.

[0233] Alternatively, fillers can be added to the aforementioned adhesive resins. Suitable fillers include inorganic fillers such as calcium carbonate, fluororesins, silicones, silica, glass beads, titanium dioxide, alumina, magnesium oxide, and other metal oxides; various granular polymers such as nylon, polyethylene (PE), polystyrene (PS), cross-linked polystyrene polymers, polypropylene (PP), polyesters, acrylic resins (polymethyl methacrylate, cross-linked copolymers of polymethyl methacrylate, etc.); and urethane plastics.

[0234] These fillers can be used individually or in combination of two or more.

[0235] As a filler, from the aspects of not easily causing sedimentation and separation in the coating liquid of adhesive resin, stability as an emulsion, heat resistance during heat sealing, and gloss after coating, an organic filler comprising at least one selected from the group consisting of polymethyl methacrylate, its crosslinked polymer, and polystyrene crosslinked polymer is preferred.

[0236] The filler content is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, relative to 100 parts by mass of the adhesive resin. If the filler content is less than 0.5 parts by mass, adhesion may occur during sea transport in summer or in high temperature (40°C) and high humidity (90% RH) atmospheres equivalent to subtropical regions, and low-temperature heat-sealing properties may deteriorate. No specific upper limit is set, but it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 15 parts by mass or less. If it exceeds 50 parts by mass, when a printed portion is provided between the adhesive resin layer and the laminate, there is a tendency for the outline of the printed characters to become blurred, and the visibility and transparency to deteriorate.

[0237] Furthermore, as a lamination method for adhesive resins, a method of coating onto the laminate and then drying is preferred. Moreover, from an environmental perspective, the adhesive resin is preferably coated in the form of an aqueous emulsion consisting of polymer particles dispersed in water.

[0238] In this embodiment, the preparation can be carried out simultaneously with the polymerization of the adhesive resin. There is no particular limitation on the preparation method of the aqueous emulsion in this case. Examples of polymerization methods include emulsion polymerization, suspension polymerization, bulk polymerization, and microemulsion polymerization. In particular, from the perspective of stably producing an emulsion with good dispersion stability and an average particle size of about 10 nm to 1 μm, emulsion polymerization is preferred.

[0239] From the perspectives of heat-sealing properties, elongation, and the ability of the packaged contents to puncture the laminate, the thickness of the adhesive resin layer is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 6 μm or more. An upper limit is not specifically set, but is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 15 μm or less. If it is 1 μm or more, it provides sufficient heat-sealing properties and good elongation. However, if it is higher than 50 μm, there is a tendency for the packaged contents to easily puncture the laminate.

[0240] Furthermore, the aforementioned adhesive resin can be included in the ethylene halide polymer layer of the laminate. By appropriately mixing the adhesive resin and the aqueous dispersion of the ethylene halide polymer particles, the adhesive resin acts as a plasticizer, lowering the crystallization melting point of the ethylene halide polymer and imparting low-temperature heat-sealing properties. However, if the mixing amount is too large, the barrier properties characteristic of the ethylene halide polymer are impaired. Therefore, relative to 100% by mass of the resin solids content of the ethylene halide polymer, the content of the resin solids content of the adhesive resin is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 20% by mass or less, and most preferably 10% by mass or less. The lower limit is not specifically set, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, and most preferably 1% by mass or more. If the adhesive resin content is higher than 50% by mass, there is a tendency for the barrier properties of the ethylene halide polymer to be impaired; if it is lower than 0.001% by mass, there is a tendency for excellent low-temperature heat-sealing properties not to be obtained.

[0241] Furthermore, when the laminate of this embodiment is used in industrial materials, it can prevent corrosion and deterioration by inhibiting the intrusion of oxygen and moisture. In addition, it can also be expected to have effects such as VOC leakage and odor barrier properties.

[0242] Example

[0243] The present invention will be described in more detail below through examples, but the present invention is not limited to the examples. In addition, where the examples and comparative examples are simply referred to as "parts" or "%", unless otherwise explicitly stated, they mean "parts by mass" or "% by mass".

[0244] It should be noted that the physical property determination / evaluation of the examples and comparative examples were carried out by the following methods.

[0245] <Determination-Evaluation Methods>

[0246] (1) Weight-average molecular weight (Mw) of halogenated ethylene polymers

[0247] The weight-average molecular weight (Mw) of the halogenated ethylene polymers obtained in the Examples / Comparative Examples was determined using GPC (gel permeation chromatography).

[0248] 0.03 g of dried ethylene halide polymer was dissolved in 10 mL of tetrahydrofuran and used as a sample for determination under the following conditions.

[0249] <GPC Determination Conditions>

[0250] (Data Processing): EcoSEC-WS manufactured by Tosoh Corporation

[0251] (Device): HLC-8320GPC EcoSEC manufactured by Tosoh Corporation

[0252] (Column): 1 Tosoh TSKgel SuperHZ M-M (4.6mm I.D. × 15cm) + 1 Tosoh TSKgel SuperHZ2000 (4.6mm I.D. × 15cm)

[0253] (Oven temperature): 40℃

[0254] (Eluent): Tetrahydrofuran 0.35 mL / min

[0255] (Sample volume): 20 μL (1.0 mg / mL)

[0256] (Detector): RI

[0257] (Correction Curve): Polystyrene (Pst) Conversion

[0258] (2) Average particle size of ethylene halide polymer particles in aqueous dispersion

[0259] An aqueous dispersion of the ethylene halide polymer obtained in the Examples / Comparative Examples, containing 0.1 to 1% by mass of the dried solids content, was prepared by dilution with pure water. 5 to 9 cc of the aqueous dispersion was dispensed into a glass measuring cell (Maruemu Cent Tube STS-2), and the average particle size (nm) of the ethylene halide polymer particles in the aqueous dispersion was determined using a particle size analyzer (Otsuka Electronics FPAR-1000).

[0260] (3) pH of aqueous dispersions of halogenated ethylene polymers

[0261] The pH of the aqueous dispersion of the ethylene halide polymer particles prepared in (2) above was determined using a pH METER HM-50G (manufactured by Toa DKK Corporation). Before measurement, the pH of the aqueous dispersion of the ethylene halide polymer particles at a constant temperature of 20±1℃ was calibrated using 0.05 mol / L oxalate standard solution (pH 1.68), 0.05 mol / L phthalate standard solution (pH 4.01), and 0.025 mol / L neutral phosphate standard solution (pH 6.86).

[0262] (4) The thickness of the ethylene halide polymer layer in the laminate on the paper support

[0263] Sections were prepared by cutting the laminates obtained in the examples / comparative examples using a large rotary Microtome OSK 97LF506 (manufactured by OGAWA SEIKI). The cross-sections of the sections were observed using a KH-7700 microscope (manufactured by HIROX). For the paper support coated with ethylene halide polymer, the thickness was measured at 30 locations at 100 μm intervals from the center to the left and right, and the average value was taken as the thickness (μm) of the ethylene halide polymer layer.

[0264] It should be noted that, regarding the interface between the paper support and the ethylene halide polymer layer, such as Figure 1 The microscopic images shown depict the paper support, with the aggregated portion containing porous pulp fibers serving as the paper matrix and the portion forming a continuous, non-porous layer serving as the ethylene halide polymer layer. The thickness of each layer was measured. Furthermore, to address situations where the interface between the paper support and the ethylene halide polymer layer is blurred due to cross-sectional crushing, thickness sampling was not performed; instead, the thickness at a position 100 μm ahead was measured.

[0265] (5) Content of halogenated ethylene polymers

[0266] The laminates obtained in the examples / comparative examples were cut into 5 cm square pieces using a cutting knife and heat-treated at 115°C for 30 minutes using a hot air dryer. Afterwards, they were allowed to stand at 20°C and 55% RH for 30 minutes, and the mass of the laminate sample was measured using a precision balance capable of measuring to four decimal places (Measurement 1). 100 mL of tetrahydrofuran was added to a 140 mL glass bottle, and the 5 cm square laminate sample was immersed in it. An ultrasonic cleaner (US CLEANER, model USK-1R) manufactured by AS-1 Corporation was filled with pure water, and the glass bottle containing 100 mL of tetrahydrofuran and the laminate sample was immersed in the pure water and ultrasonically cleaned for 5 minutes at a set temperature of 25°C. Next, prepare two clean 140mL glass bottles, each containing 100mL of tetrahydrofuran. Using a Yamato Scientific SA300 shaker, stir at 100rpm for 5 minutes. Transfer the laminated sample to one of the glass bottles containing the clean tetrahydrofuran, and further stir at 100rpm for 5 minutes using the Yamato Scientific SA300 shaker. Remove the laminated sample and wipe both surfaces several times with clean gauze soaked in tetrahydrofuran. Then, heat-treat the sample in a hot air dryer at 115°C for 30 minutes. Remove the heat-treated laminated sample and allow it to stand at 20°C and 55%RH for 30 minutes. The mass is then measured using a precision balance capable of measuring to four decimal places (Measurement 2), and the content of the ethylene halide polymer is calculated using the following formula.

[0267] The mass (g / 5cm) measured by determination 1 2 ) - Mass determined by determination 2 (g / 5cm) 2 )×400(m 2 / 25×10 - 4 m 2 )

[0268] (6) Coating efficiency of ethylene halide polymer layer

[0269] For the halogenated ethylene polymer layer of the laminate obtained in the examples / comparative examples, the coating efficiency was calculated using the following formula.

[0270] Coverage efficiency (m 3 The thickness (μm) of the ethylene halide polymer layer obtained in (4) on the paper support is 10. -6 The content of halogenated polymers obtained in (5) (g / m 2 )

[0271] (7)Moisture resistance

[0272] The laminates obtained in the examples / comparative examples were cut into circles with a diameter of 7 cm using a circular cutter. A permeable cup (circular base with a diameter of 6 cm and a permeable area of ​​28.6 cm²) was then used. 2The aluminum (treated with anodized vapor) is wiped with a cloth soaked in tetrahydrofuran, dried, and placed on a level cup stand (made of cast brass). Approximately 10g of calcium chloride (made by Fujifilm and Koujun Pharmaceutical Co., Ltd.), suitable for JIS K8125, is measured as a desiccant and placed in the permeation cup. A test piece cut to a diameter of 7cm is placed on the upper edge of the permeation cup, with the center of the test piece overlapping the center of the circular bottom surface of the cup. A guide (made of cast brass) is placed on the permeation cup, corresponding to the groove in the cup stand. A ring (treated with anodized vapor on aluminum) is pressed in corresponding to the guide until it is tightly sealed against the upper edge of the permeation cup containing the test piece. A weight (made of cast brass) is then placed on top. After vertically lifting and removing the guide, heat the cup to approximately 100°C while rotating it using a heating plate. This allows molten sealing wax (a mixture of beeswax, white granules (Fujifilm and Koichi Pharmaceutical) / alkanes mp64-66°C = 6 / 4) to flow around the cup, sealing the edges of the test piece. After the sealing wax has cured, remove the weight and the cup platform. Wipe away any remaining sealing wax outside the sealed area with gauze soaked in tetrahydrofuran to create the test piece. Place the test piece in a constant temperature and humidity chamber at 20°C and 55% RH for at least 1 hour, then weigh it using an electronic balance capable of weighing to the nearest 0.001 mg. After weighing, place the test piece in a constant temperature and humidity chamber at 40°C and 90% RH for 24 hours, then remove it and place it in a constant temperature and humidity chamber at 20°C and 55% RH for at least 1 hour. Finally, weigh the test piece using an electronic balance capable of weighing to the nearest 0.001 mg. The moisture resistance of the test piece was calculated using the following formula.

[0273] Moisture resistance (g / m 2 •24hr)=240×increased mass of test subject (mg / 24hr)×28.6 (cm) 2 )

[0274] (8) Dissociation

[0275] For the laminates obtained in the examples / comparative examples, a mixture of laminate / water in a mass ratio of 3 / 100 was added to a 2L test pulper (manufactured by Kumagai Riki Kogyo Co., Ltd.), and the paper support (pulp) was dissociated at 122 rpm for 10 minutes.

[0276] The evaluation of the dissociation properties of the paper support (pulp) was conducted by adding a small amount of pulp treated by a beater to a 2L glass test tube filled with water, shaking thoroughly, and then visually observing the degree of dissociation. Three laminates were tested in each example / comparative example.

[0277] [Evaluation Criteria]

[0278] ◎: No residue larger than a few millimeters and smaller than 1 cm was identified, nor was any residue larger than 1 cm identified.

[0279] 〇: Residues of 1-6 mm or larger and less than 1 cm were identified; residues larger than 1 cm were not identified.

[0280] △: More than 7 pieces of residue larger than 1 mm and smaller than 1 cm were identified; no residue larger than 1 cm was identified.

[0281] ×: Both residues larger than a few millimeters and smaller than 1 cm were identified, as well as residues larger than 1 cm.

[0282] (9) Heat seal strength

[0283] After the laminates obtained in the examples / comparative examples were cut into lengths of 150 mm and widths of 15 mm using a cutter, heat sealing and tensile tests were performed on the coated surfaces of the halogenated ethylene polymers using a thermal tilt testing machine HG-100 (Toyo Seiki Co., Ltd.) with the following settings.

[0284] Cases where no seal is observed even after heat sealing are recorded as "cannot be determined," and cases where the paper support fails in the tensile test due to a strong seal are recorded as "failure."

[0285] <Heat-sealing conditions>

[0286] Temperature: 120℃, 130℃, 140℃, 150℃, 160℃

[0287] Pressure: 1 kg / f / cm 2

[0288] Time: 2 seconds

[0289] <Tension Test Conditions>

[0290] Securely fasten both ends of the sample with clamps, and perform a 90° T-shaped peel test using an Autograph AGS-50NX (manufactured by Shimadzu Corporation) under the following conditions in a constant temperature chamber of 20°C and 55%RH. Calculate the maximum point test force (N) as the heat seal strength.

[0291] Tensioning speed: 100mm / min

[0292] Distance between chucks: 100mm

[0293] (10) Yellowing

[0294] The laminate obtained in the examples / comparative examples and high-grade paper (70 g / m²) without halogenated ethylene polymer coating were dried in a hot air circulating dryer at 60°C. 2The samples were allowed to stand for 3 days. A CM-5 spectrophotometer (manufactured by Konica Minolta) was prepared, and after zero and white calibration, the samples taken from the hot air circulating dryer were placed on a target mask. The YI value was measured using a reflectance meter. Uncoated high-grade paper was used as a control to evaluate yellowing, with the evaluation criteria set at the following three levels. Three laminates were tested for each example / comparative example.

[0295] [Evaluation Criteria]

[0296] ◎: The YI value is less than 1, and the whiteness is roughly the same as that of uncoated high-grade paper, so there is no problem.

[0297] 〇: The YI value is above 1 and less than 2. Compared with uncoated high-grade paper, it is slightly yellowish, but there is no problem.

[0298] △: The YI value is above 2 and less than 3. It appears more yellow than uncoated high-grade paper, but it is not a problem in practical use.

[0299] ×: If the YI value is above 3, the yellowing is significantly increased compared with uncoated high-grade paper, making it an undesirable choice for practical use.

[0300] (11) Determination of the melting point of crystallization

[0301] After drying the paper support (coated paper) coated with ethylene halide polymer at 60°C for 24 hours in a hot air dryer to allow it to crystallize fully, 5 mg of the coated ethylene halide polymer was weighed from the coating surface using tweezers and other means in a Tzero Hermetic Pan. The crystallization melting point was determined using a DSC (Q2000, manufactured by TA) and an RCS cooling system (manufactured by TA).

[0302] (Standby temperature): 40℃

[0303] (Heating rate): 10℃ / min

[0304] (Heating temperature): 200℃

[0305] Use Universal Analysis to analyze the obtained data. In a graph where the Y-axis represents heat flow and the X-axis represents temperature (°C), select Analyza, then Integrate Peak, and choose the baseline type. Use the crosshair cursor to select from 45°C to 180°C, and take the obtained endothermic peak temperature as the crystallization melting point (°C).

[0306] It should be noted that when multiple endothermic peaks are observed on the graph using Universal Analysis, the temperatures of all endothermic peaks are measured and used as the crystallization melting point.

[0307] (12) Pure water contact angle of paper support

[0308] The measurements were performed using a portable pure water contact angle meter PG-X plus (manufactured by MATSUBO Corporation). The main body of the device was placed on a paper support before the ethylene halide polymer was coated, and its horizontal position was confirmed using video monitoring. Pure water was used as the standard solution, and the static contact angle was measured in static mode. Measurements were taken for 10 water drops, and the average value was taken as the pure water contact angle (degrees).

[0309] Droplet volume: 4 μL

[0310] Hold time after addition: 2 seconds

[0311] If the droplet cannot be maintained due to osmosis within 2 seconds after addition, it is judged that the contact angle is less than 20°.

[0312] In image processing, adjusting image contrast and brightness can be done manually, such as... Figure 2 As shown, the contact angle is measured at three points: the droplet lines at both ends of the droplet and the sample surface, and the apex of the droplet.

[0313] [Example 1]

[0314] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0315] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) are added, along with 80 parts of pure water, 0.007 parts of sodium hydroxymethanesulfinate dihydrate (sodium dichloroisocyanurate), and 0.18 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents is maintained at 45°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methyl acrylate (MA), and acrylic acid (AA) are prepared according to a composition ratio (VDC / MA / AA) of 90.5 / 9.2 / 0.3. 20 parts of the 100 parts of the raw material monomer mixture are added all at once to the pressure-resistant reactor, and polymerization is carried out until the internal pressure decreases. Next, the remaining 80 parts of the monomer mixture were added all at once, and in parallel, 0.6 parts of sodium alkyl sulfonate emulsifier were added all at once. A solution of initiator (0.0023 parts of tert-butyl hydroperoxide dissolved in 1.9 parts of pure water) and a solution of reducing agent (0.0014 parts of sodium hypochlorite dissolved in 1.6 parts of pure water) were continuously and quantitatively injected under pressure. The contents were kept at 45°C with stirring until the internal pressure was sufficiently reduced, yielding a vinylidene chloride-based copolymer resin latex. The polymerization yield was 99.8%. Since the polymerization yield was approximately 100%, it can be said that the composition of the copolymer was approximately equal to the feed ratio.

[0316] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex was 176 nm, and the weight-average molecular weight (Mw) was 280,000.

[0317] After removing unreacted monomers from the obtained latex by steam stripping, the pH was adjusted to 3.0 using a 5% ammonia solution. Subsequently, the vinylidene chloride copolymer resin was adjusted to 40-50% (solids content) with pure water, and 1.1 parts of a 30% sodium lauryl sulfonate aqueous solution were added relative to 100 parts of the vinylidene chloride copolymer resin in the latex, adjusting the surface tension of the latex at 20°C to 42 (mN / m).

[0318] (Fabrication of laminates)

[0319] The aqueous dispersion of the ethylene halide polymer (vinylidene chloride-based copolymer latex) obtained above was wound with a wire rod to achieve a content of 20 g / m of the dried ethylene halide polymer (vinylidene chloride-based copolymer latex). 2 Coated to a pure water contact angle of 92° and a weight of 70 g / m². 2 Commercially available high-grade paper was dried in a hot air circulating dryer at 100°C for 2 minutes, and then aged in a hot air dryer at 40°C for 24 hours to obtain a laminate.

[0320] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0321] [Example 2]

[0322] Except for adjusting the pH of the vinylidene chloride-based copolymer latex to 4.0 using 5% ammonia, the laminate was prepared using the same method as in Example 1.

[0323] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0324] [Example 3]

[0325] Except for adjusting the pH of the vinylidene chloride copolymer latex to 2.0 using 5% ammonia, the laminate was prepared using the same method as in Example 1.

[0326] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0327] [Example 4]

[0328] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0329] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) were added, along with 100 parts of pure water, 0.09 parts of sodium persulfate, and 0.15 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents was maintained at 55°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methacrylonitrile (MAN), methyl methacrylate (MMA), and acrylic acid (AA) were prepared in a composition ratio (VDC / MAN / MMA / AA) of 91.0 / 4.0 / 4.0 / 1.0. Ten parts of the 100 parts of the raw material monomer mixture were added all at once to the pressure-resistant reactor, and polymerization was carried out until the internal pressure decreased. Then, the remaining 90 parts of the monomer mixture were continuously and quantitatively injected over 12 hours, and in parallel, 1.0 part of the emulsifier sodium alkyl sulfonate was continuously and quantitatively injected over 10 hours. During this process, the contents were maintained at 55°C, and the reaction was carried out until the internal pressure was sufficiently reduced. The polymerization yield was 99.9%. Since the polymerization yield is approximately 100%, it can be said that the composition of the copolymer is roughly equal to the feed ratio.

[0330] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex is 142 nm, and the weight-average molecular weight (Mw) is 100,000.

[0331] Adding a 15% aqueous solution of sodium alkyl sulfonate adjusts the surface tension of the latex at 20°C to 42 mN / m.

[0332] After removing unreacted monomers from the obtained latex via steam stripping, a dialysis membrane with a molecular weight cutoff of 10,000 made of cellulose was used for 12 hours of dialysis to achieve a resistivity of 3000 Ω·m at 25°C. Subsequently, the pH was adjusted to 4.0 using a 5% ammonia solution, and the vinylidene chloride copolymer resin was adjusted with pure water to a solids content of 40–50%.

[0333] (Fabrication of laminates)

[0334] Using the aqueous dispersion of the obtained halogenated ethylene polymer (vinylidene chloride copolymer latex), a laminate was prepared using the same method as in Example 1.

[0335] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0336] [Example 5]

[0337] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0338] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) were added, along with 100 parts of pure water, 0.05 parts of sodium persulfate, and 0.18 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents was maintained at 55°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methacrylonitrile (MAN), methyl methacrylate (MMA), and acrylic acid (AA) were prepared in a composition ratio (VDC / MAN / MMA / AA) of 91.0 / 4.0 / 4.0 / 1.0. Ten parts of the 100 parts of the raw material monomer mixture were added all at once to the pressure-resistant reactor, and polymerization was carried out until the internal pressure decreased. Then, the remaining 90 parts of the monomer mixture were continuously and quantitatively injected over 12 hours, and in parallel, 1.0 part of the emulsifier sodium alkyl sulfonate was continuously and quantitatively injected over 10 hours. During this process, the contents were maintained at 55°C, and the reaction was carried out until the internal pressure was sufficiently reduced. The polymerization yield was 99.9%. Since the polymerization yield is approximately 100%, it can be said that the composition of the copolymer is roughly equal to the feed ratio.

[0339] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex is 125 nm, and the weight-average molecular weight (Mw) is 200,000.

[0340] Adding a 15% aqueous solution of sodium alkyl sulfonate adjusts the surface tension of the latex at 20°C to 42 mN / m.

[0341] After removing unreacted monomers from the obtained latex via steam stripping, a dialysis membrane with a molecular weight cutoff of 10,000 made of cellulose was used for 12 hours of dialysis to achieve a resistivity of 3000 Ω·m at 25°C. Subsequently, the pH was adjusted to 4.0 using a 5% ammonia solution, and the vinylidene chloride copolymer resin was adjusted with pure water to a solids content of 40–50%.

[0342] (Fabrication of laminates)

[0343] Using the aqueous dispersion of the obtained halogenated ethylene polymer (vinylidene chloride copolymer latex), a laminate was prepared using the same method as in Example 1.

[0344] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0345] [Example 6]

[0346] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0347] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) were added, along with 100 parts of pure water, 0.09 parts of sodium persulfate, and 0.18 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents was maintained at 55°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methacrylonitrile (MAN), methyl methacrylate (MMA), and acrylic acid (AA) were prepared in a composition ratio (VDC / MAN / MMA / AA) of 91.0 / 4.0 / 4.0 / 1.0. Ten parts of the 100 parts of the raw material monomer mixture were added all at once to the pressure-resistant reactor, and polymerization was carried out until the internal pressure decreased. Then, the remaining 90 parts of the monomer mixture were continuously and quantitatively injected over 12 hours, and in parallel, 1.0 part of the emulsifier sodium alkyl sulfonate was continuously and quantitatively injected over 10 hours. During this process, the contents were maintained at 55°C, and the reaction was carried out until the internal pressure was sufficiently reduced. The polymerization yield was 99.9%. Since the polymerization yield is approximately 100%, it can be said that the composition of the copolymer is roughly equal to the feed ratio.

[0348] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex is 123 nm, and the weight-average molecular weight (Mw) is 100,000.

[0349] Adding a 15% aqueous solution of sodium alkyl sulfonate adjusts the surface tension of the latex at 20°C to 42 mN / m.

[0350] After removing unreacted monomers from the obtained latex via steam stripping, a dialysis membrane with a molecular weight cutoff of 10,000 made of cellulose was used for 12 hours of dialysis to achieve a resistivity of 3000 Ω·m at 25°C. Subsequently, the pH was adjusted to 4.0 using a 5% ammonia solution, and the vinylidene chloride copolymer resin was adjusted with pure water to a solids content of 40–50%.

[0351] (Fabrication of laminates)

[0352] Using the aqueous dispersion of the obtained halogenated ethylene polymer (vinylidene chloride copolymer latex), a laminate was prepared using the same method as in Example 1.

[0353] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0354] [Example 7]

[0355] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0356] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) are added, along with 66.0 parts of pure water, 0.0009 parts of sodium silicate, and 0.21 parts of sodium alkylbenzene sulfonate. After degassing under stirring, the temperature of the contents is maintained at 45°C. In another container, (1) 90 parts of a raw material monomer mixture of vinylidene chloride (VDC), methyl methacrylate (MMA), acrylonitrile (AN), and 2-hydroxyethyl acrylate (HEA) are prepared according to a composition ratio (VDC / MMA / AN / HEA) of 81.27 / 6.12 / 0.99 / 1.62, and (2) 10 parts of a raw material monomer mixture of vinylidene chloride (VDC), acrylonitrile (AN), methyl methacrylate (MA), and 2-hydroxyethyl acrylate (HEA) are prepared according to a composition ratio (VDC / AN / MA / HEA) of 8.6 / 0.8 / 0.4 / 0.2. Nine parts of monomer mixture (1) from 100 parts of the raw material monomer mixture were added at once to the pressure-resistant reactor described above, and polymerization was carried out until the internal pressure decreased. Then, 81 parts of monomer mixture (1) were continuously and quantitatively injected, along with a solution of an initiator prepared by dissolving 0.012 parts of tert-butyl hydroperoxide in 4.92 parts of pure water, a solution of a reducing agent prepared by dissolving 0.023 parts of sodium hydroxide in 4.97 parts of pure water, and a solution of an emulsifier prepared by dissolving 0.36 parts of sodium alkylbenzene sulfonate in 8.36 parts of pure water. The contents were kept at 45°C with stirring, and the reaction was carried out until the internal pressure decreased sufficiently. Then, 10 parts of monomer mixture (2) were continuously and quantitatively injected, along with the same initiator solution, reducing agent solution, and emulsifier solution as in (1). The contents were kept at 45°C with stirring, and the reaction was carried out until the internal pressure decreased sufficiently. The polymerization yield was 99.7%. Since the polymerization yield is approximately 100%, it can be said that the composition of the copolymer is roughly equal to the feed ratio.

[0357] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex is 150 nm, and the weight-average molecular weight (Mw) is 140,000.

[0358] After removing unreacted monomers from the obtained latex by steam stripping, the pH was adjusted to 3.0 using a 5% ammonia solution. Subsequently, the vinylidene chloride copolymer resin was adjusted to 40-50% (based on solids content) with pure water, and a 15% aqueous solution of sodium alkyl sulfonate was added to adjust the surface tension of the latex at 20°C to 42 mN / m.

[0359] (Fabrication of laminates)

[0360] Using the aqueous dispersion of the obtained halogenated ethylene polymer (vinylidene chloride copolymer latex), a laminate was prepared using the same method as in Example 1.

[0361] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0362] [Example 8]

[0363] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0364] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) are added, along with 67.0 parts of pure water, 0.0066 parts of sodium D-arabinose ascorbate, and 0.29 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents is maintained at 45°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methacrylonitrile (MAN), methyl methacrylate (MMA), and acrylic acid (AA) are prepared according to a composition ratio (VDC / MAN / MMA / AA) of 91.5 / 5.2 / 2.4 / 0.9. Nine parts of the 100 parts of the raw material monomer mixture are added all at once to the pressure-resistant reactor described above, and polymerization is carried out until the internal pressure decreases. Next, the remaining 91 parts of the monomer mixture were continuously and quantitatively injected, along with an initiator solution prepared by dissolving 0.033 parts of the initiator tert-butyl hydroperoxide in 6.00 parts of pure water, a reducing agent solution prepared by dissolving 0.127 parts of the reducing agent sodium D-arabinose ascorbate in 6.0 parts of pure water, and an emulsifier solution prepared by dissolving 1.0 part of the emulsifier sodium alkyl diphenyl ether disulfonate in 10.0 parts of pure water. The contents were maintained at 45°C with stirring during the reaction until the internal pressure was sufficiently reduced. The polymerization yield was 99.9%. Since the polymerization yield was approximately 100%, it can be said that the composition of the copolymer was approximately equal to the feed ratio.

[0365] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex was 121 nm, and the weight-average molecular weight (Mw) was 120,000.

[0366] After removing unreacted monomers from the obtained latex by steam stripping, the pH was adjusted to 3.0 using a 5% ammonia solution. Subsequently, the vinylidene chloride copolymer resin was adjusted to 40-50% (based on solids content) with pure water, and a 15% aqueous solution of sodium alkyl sulfonate was added to adjust the surface tension of the latex at 20°C to 42 mN / m.

[0367] (Fabrication of laminates)

[0368] Using the aqueous dispersion of the obtained halogenated ethylene polymer (vinylidene chloride copolymer latex), a laminate was prepared using the same method as in Example 1.

[0369] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0370] [Example 9]

[0371] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0372] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) were added, along with 100 parts of pure water, 0.09 parts of sodium persulfate, and 0.19 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents was maintained at 55°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methacrylonitrile (MAN), methyl methacrylate (MMA), and acrylic acid (AA) were prepared in a composition ratio (VDC / MAN / MMA / AA) of 91.0 / 4.0 / 4.0 / 1.0. Ten parts of the 100 parts of the raw material monomer mixture were added all at once to the pressure-resistant reactor, and polymerization was carried out until the internal pressure decreased. Then, the remaining 90 parts of the monomer mixture were continuously and quantitatively injected over 12 hours, and in parallel, 1.0 part of the emulsifier sodium alkyl sulfonate was continuously and quantitatively injected over 10 hours. During this process, the contents were maintained at 55°C, and the reaction was carried out until the internal pressure was sufficiently reduced. The polymerization yield was 99.9%. Since the polymerization yield is approximately 100%, it can be said that the composition of the copolymer is roughly equal to the feed ratio.

[0373] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex is 122 nm, and the weight-average molecular weight (Mw) is 100,000.

[0374] Adding a 15% aqueous solution of sodium alkyl sulfonate adjusts the surface tension of the latex at 20°C to 42 mN / m.

[0375] After removing unreacted monomers from the obtained latex via steam stripping, a dialysis membrane with a molecular weight cutoff of 10,000 made of cellulose was used for 12 hours of dialysis to achieve a resistivity of 3000 Ω·m at 25°C. Subsequently, the pH was adjusted to 4.0 using a 5% ammonia solution, and the vinylidene chloride copolymer resin was adjusted with pure water to a solids content of 40–50%.

[0376] (Fabrication of laminates)

[0377] Using the aqueous dispersion of the obtained halogenated ethylene polymer (vinylidene chloride copolymer latex), a laminate was prepared using the same method as in Example 1.

[0378] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0379] [Example 10]

[0380] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0381] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) were added, along with 100 parts of pure water, 0.09 parts of sodium persulfate, and 0.20 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents was maintained at 55°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methacrylonitrile (MAN), methyl methacrylate (MMA), and acrylic acid (AA) were prepared in a composition ratio (VDC / MAN / MMA / AA) of 91.0 / 4.0 / 4.0 / 1.0. Ten parts of the 100 parts of the raw material monomer mixture were added all at once to the pressure-resistant reactor, and polymerization was carried out until the internal pressure decreased. Then, the remaining 90 parts of the monomer mixture were continuously and quantitatively injected over 12 hours, and in parallel, 1.0 part of the emulsifier sodium alkyl sulfonate was continuously and quantitatively injected over 10 hours. During this process, the contents were maintained at 55°C, and the reaction was carried out until the internal pressure was sufficiently reduced. The polymerization yield was 99.9%. Since the polymerization yield is approximately 100%, it can be said that the composition of the copolymer is roughly equal to the feed ratio.

[0382] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex is 121 nm, and the weight-average molecular weight (Mw) is 100,000.

[0383] Adding a 15% aqueous solution of sodium alkyl sulfonate adjusts the surface tension of the latex at 20°C to 42 mN / m.

[0384] After removing unreacted monomers from the obtained latex via steam stripping, a dialysis membrane with a molecular weight cutoff of 10,000 made of cellulose was used for 12 hours of dialysis to achieve a resistivity of 3000 Ω·m at 25°C. Subsequently, the pH was adjusted to 4.0 using a 5% ammonia solution, and the vinylidene chloride copolymer resin was adjusted with pure water to a solids content of 40–50%.

[0385] (Fabrication of laminates)

[0386] Using the aqueous dispersion of the obtained halogenated ethylene polymer (vinylidene chloride copolymer latex), a laminate was prepared using the same method as in Example 1.

[0387] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0388] [Example 11]

[0389] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0390] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) are added, along with 80 parts of pure water, 0.007 parts of sodium hydroxymethanesulfinate dihydrate (sodium dichloroisocyanurate), and 0.18 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents is maintained at 45°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methyl acrylate (MA), and acrylic acid (AA) are prepared according to a composition ratio (VDC / MA / AA) of 80.5 / 19.2 / 0.3. 20 parts of the 100 parts of the raw material monomer mixture are added all at once to the pressure-resistant reactor, and polymerization is carried out until the internal pressure decreases. Next, the remaining 80 parts of the monomer mixture were added all at once, and in parallel, 0.6 parts of sodium alkyl sulfonate emulsifier were added all at once. A solution of initiator prepared by dissolving 0.0023 parts of tert-butyl hydroperoxide in 1.9 parts of pure water and a solution of reducing agent prepared by dissolving 0.0014 parts of sodium hypochlorite in 1.6 parts of pure water were continuously and quantitatively added. During this process, the contents were maintained at 45°C with stirring, and the reaction continued until the internal pressure was sufficiently reduced, yielding a vinylidene chloride-based copolymer resin latex. The polymerization yield was 99.8%. Since the polymerization yield was approximately 100%, it can be said that the composition of the copolymer was approximately equal to the feed ratio.

[0391] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex is 175 nm, and the weight-average molecular weight (Mw) is 280,000.

[0392] After removing unreacted monomers from the obtained latex by steam stripping, the pH was adjusted to 3.0 using a 5% ammonia solution. Subsequently, the vinylidene chloride copolymer resin was adjusted to 40-50% (solids content) with pure water. For every 100 parts of the vinylidene chloride copolymer resin in the latex, 1.1 parts of a 30% sodium lauryl sulfonate aqueous solution were added, adjusting the surface tension of the latex at 20°C to 42 (mN / m).

[0393] (Fabrication of laminates)

[0394] The aqueous dispersion of the ethylene halide polymer (vinylidene chloride-based copolymer latex) obtained above was wound with a wire rod to achieve a content of 20 g / m of the dried ethylene halide polymer (vinylidene chloride-based copolymer latex). 2 Coated to a pure water contact angle of 92° and a weight of 70 g / m². 2 Commercially available high-grade paper was dried in a hot air circulating dryer at 100°C for 2 minutes, and then aged in a hot air dryer at 40°C for 24 hours to obtain a laminate.

[0395] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0396] [Example 12]

[0397] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0398] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) are added, along with 80 parts of pure water, 0.007 parts of sodium hydroxymethanesulfinate dihydrate (sodium dichloroisocyanurate), and 0.18 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents is maintained at 45°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methyl acrylate (MA), and acrylic acid (AA) are prepared according to a composition ratio (VDC / MA / AA) of 70.5 / 29.2 / 0.3. 20 parts of the 100 parts of the raw material monomer mixture are added all at once to the pressure-resistant reactor, and polymerization is carried out until the internal pressure decreases. Next, the remaining 80 parts of the monomer mixture were added all at once, and in parallel, 0.6 parts of sodium alkyl sulfonate emulsifier were added all at once. A solution of initiator prepared by dissolving 0.0023 parts of tert-butyl hydroperoxide in 1.9 parts of pure water and a solution of reducing agent prepared by dissolving 0.0014 parts of sodium hypochlorite in 1.6 parts of pure water were continuously and quantitatively added. During this process, the contents were maintained at 45°C with stirring, and the reaction continued until the internal pressure was sufficiently reduced, yielding a vinylidene chloride-based copolymer resin latex. The polymerization yield was 99.8%. Since the polymerization yield was approximately 100%, it can be said that the composition of the copolymer was approximately equal to the feed ratio.

[0399] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex was 176 nm, and the weight-average molecular weight (Mw) was 280,000.

[0400] After removing unreacted monomers from the obtained latex by steam stripping, the pH was adjusted to 3.0 using a 5% ammonia solution. Subsequently, the vinylidene chloride copolymer resin was adjusted to 40-50% (solids content) using pure water. 1.1 parts of a 30% sodium lauryl sulfonate aqueous solution were added per 100 parts of the vinylidene chloride copolymer resin in the latex, and the surface tension of the latex at 20°C was adjusted to 42 (mN / m).

[0401] (Fabrication of laminates)

[0402] The aqueous dispersion of the ethylene halide polymer (vinylidene chloride-based copolymer latex) obtained above was wound with a wire rod to achieve a content of 20 g / m of the dried ethylene halide polymer (vinylidene chloride-based copolymer latex). 2 Coated to a pure water contact angle of 92° and a weight of 70 g / m². 2 Commercially available high-grade paper was dried in a hot air circulating dryer at 100°C for 2 minutes, and then aged in a hot air dryer at 40°C for 24 hours to obtain a laminate.

[0403] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0404] [Example 13]

[0405] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0406] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) are added, along with 80 parts of pure water, 0.007 parts of sodium hydroxymethanesulfinate dihydrate (sodium dichloroisocyanurate), and 0.18 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents is maintained at 45°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methyl acrylate (MA), and acrylic acid (AA) are prepared according to a composition ratio (VDC / MA / AA) of 69.0 / 30.7 / 0.3. 20 parts of the 100 parts of the raw material monomer mixture are added all at once to the pressure-resistant reactor, and polymerization is carried out until the internal pressure decreases. Next, the remaining 80 parts of the monomer mixture were added all at once, and in parallel, 0.6 parts of sodium alkyl sulfonate emulsifier were added all at once. A solution of initiator prepared by dissolving 0.0023 parts of tert-butyl hydroperoxide in 1.9 parts of pure water and a solution of reducing agent prepared by dissolving 0.0014 parts of sodium hypochlorite in 1.6 parts of pure water were continuously and quantitatively added. During this process, the contents were maintained at 45°C with stirring, and the reaction continued until the internal pressure was sufficiently reduced, yielding a vinylidene chloride-based copolymer resin latex. The polymerization yield was 99.8%. Since the polymerization yield was approximately 100%, it can be said that the composition of the copolymer was approximately equal to the feed ratio.

[0407] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex was 176 nm, and the weight-average molecular weight (Mw) was 280,000.

[0408] After removing unreacted monomers from the obtained latex by steam stripping, the pH was adjusted to 3.0 using a 5% ammonia solution. Subsequently, the vinylidene chloride copolymer resin was adjusted to 40-50% (solids content) with pure water. For every 100 parts of the vinylidene chloride copolymer resin in the latex, 1.1 parts of a 30% sodium lauryl sulfonate aqueous solution were added, adjusting the surface tension of the latex at 20°C to 42 (mN / m).

[0409] (Fabrication of laminates)

[0410] The aqueous dispersion of the ethylene halide polymer (vinylidene chloride-based copolymer latex) obtained above was wound with a wire rod to achieve a content of 20 g / m of the dried ethylene halide polymer (vinylidene chloride-based copolymer latex). 2 Coated to a pure water contact angle of 92° and a weight of 70 g / m². 2Commercially available high-grade paper was dried in a hot air circulating dryer at 100°C for 2 minutes, and then aged in a hot air dryer at 40°C for 24 hours to obtain a laminate.

[0411] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0412] [Example 14]

[0413] Except for using high-grade paper with a pure water contact angle of 158° in the paper support, the laminate was made using the same method as in Example 1.

[0414] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0415] [Example 15]

[0416] Except for using high-grade paper with a pure water contact angle of 130° in the paper support, the laminate was made using the same method as in Example 1.

[0417] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0418] [Example 16]

[0419] Except for using high-grade paper with a pure water contact angle of 111° in the paper support, the laminate was made using the same method as in Example 1.

[0420] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0421] [Example 17]

[0422] Except for using high-grade paper with a pure water contact angle of 70° in the paper support, the laminate was made using the same method as in Example 1.

[0423] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0424] [Example 18]

[0425] Except for using high-grade paper with a pure water contact angle of 38° in the paper support, the laminate was made using the same method as in Example 1.

[0426] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0427] [Example 19]

[0428] Except for using high-grade paper with a pure water contact angle of less than 35° in the paper support, the laminate was made using the same method as in Example 1.

[0429] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0430] [Comparative Example 1]

[0431] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0432] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) were added, along with 100 parts of pure water, 0.075 parts of sodium persulfate, and 0.18 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents was maintained at 55°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methacrylonitrile (MAN), methyl methacrylate (MMA), and acrylic acid (AA) were prepared in a composition ratio of VDC / MAN / MMA / AA = 91.0 / 4.0 / 4.0 / 1.00. Ten parts of the 100 parts of the raw material monomer mixture were added all at once to the pressure-resistant reactor, and polymerization was carried out until the internal pressure decreased. Then, the remaining 90 parts of the monomer mixture were continuously and quantitatively injected over 12 hours, and in parallel, 1.0 part of the emulsifier sodium alkyl sulfonate was continuously and quantitatively injected over 10 hours. During this process, the contents were maintained at 55°C, and the reaction was carried out until the internal pressure was sufficiently reduced. The polymerization yield was 99.9%. Since the polymerization yield is approximately 100%, it can be said that the composition of the copolymer is roughly equal to the feed ratio.

[0433] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex is 115 nm, and the weight-average molecular weight (Mw) is 90,000.

[0434] Adding a 15% aqueous solution of sodium alkyl sulfonate adjusts the surface tension of the latex at 20°C to 42 mN / m.

[0435] After removing unreacted monomers from the obtained latex via steam stripping, a dialysis membrane with a molecular weight cutoff of 10,000 made of cellulose was used for 12 hours of dialysis to achieve a resistivity of 3000 Ω·m at 25°C. Subsequently, the pH was adjusted to 4.0 using a 5% ammonia solution, and the vinylidene chloride copolymer resin was adjusted with pure water to a solids content of 40–50%.

[0436] (Fabrication of laminates)

[0437] Using the aqueous dispersion of the obtained halogenated ethylene polymer (vinylidene chloride copolymer latex), a laminate was prepared using the same method as in Example 1.

[0438] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0439] [Comparative Example 2]

[0440] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0441] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) were added, along with 100 parts of pure water, 0.09 parts of sodium persulfate, and 0.2 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents was maintained at 55°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methacrylonitrile (MAN), methyl methacrylate (MMA), and acrylic acid (AA) were prepared in a composition ratio (VDC / MAN / MMA / AA) of 91.0 / 4.0 / 4.0 / 1.0. Ten parts of the 100 parts of the raw material monomer mixture were added all at once to the pressure-resistant reactor, and polymerization was carried out until the internal pressure decreased. Then, the remaining 90 parts of the monomer mixture were continuously and quantitatively injected over 12 hours, and in parallel, 1.0 part of the emulsifier sodium alkyl sulfonate was continuously and quantitatively injected over 10 hours. During this process, the contents were maintained at 55°C, and the reaction was carried out until the internal pressure was sufficiently reduced. The polymerization yield was 99.9%. Since the polymerization yield is approximately 100%, it can be said that the composition of the copolymer is roughly equal to the feed ratio.

[0442] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex is 115 nm, and the weight-average molecular weight (Mw) is 100,000.

[0443] Adding a 15% aqueous solution of sodium alkyl sulfonate adjusts the surface tension of the latex at 20°C to 42 mN / m.

[0444] After removing unreacted monomers from the obtained latex via steam stripping, a dialysis membrane with a molecular weight cutoff of 10,000 made of cellulose was used for 12 hours of dialysis to achieve a resistivity of 3000 Ω·m at 25°C. Subsequently, the pH was adjusted to 4.0 using a 5% ammonia solution, and the vinylidene chloride copolymer resin was adjusted with pure water to a solids content of 40–50%.

[0445] (Fabrication of laminates)

[0446] Using the aqueous dispersion of the obtained halogenated ethylene polymer (vinylidene chloride copolymer latex), a laminate was prepared using the same method as in Example 1.

[0447] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0448] [Comparative Example 3]

[0449] (Preparation of aqueous dispersions of halogenated ethylene polymers)

[0450] In a pressure-resistant reactor with a glass liner, 100 parts of the raw material monomer mixture (described later) were added, along with 100 parts of pure water, 0.1 parts of sodium persulfate, and 0.15 parts of sodium alkyl sulfonate. After degassing with stirring, the temperature of the contents was maintained at 55°C. In another container, 100 parts of a raw material monomer mixture of vinylidene chloride (VDC), methacrylonitrile (MAN), methyl methacrylate (MMA), and acrylic acid (AA) were prepared in a composition ratio (VDC / MAN / MMA / AA) of 91.0 / 4.0 / 4.0 / 1.00. Ten parts of the 100 parts of the raw material monomer mixture were added all at once to the pressure-resistant reactor, and polymerization was carried out until the internal pressure decreased. Then, the remaining 90 parts of the monomer mixture were continuously and quantitatively injected over 12 hours, and in parallel, 1.0 part of the emulsifier sodium alkyl sulfonate was continuously and quantitatively injected over 10 hours. During this process, the contents were maintained at 55°C, and the reaction was carried out until the internal pressure was sufficiently reduced. The polymerization yield was 99.9%. Since the polymerization yield is approximately 100%, it can be said that the composition of the copolymer is roughly equal to the feed ratio.

[0451] The average particle size of the vinylidene chloride copolymer resin particles in the obtained vinylidene chloride copolymer resin latex is 140 nm, and the weight-average molecular weight (Mw) is 90,000.

[0452] Adding a 15% aqueous solution of sodium alkyl sulfonate adjusts the surface tension of the latex at 20°C to 42 mN / m.

[0453] After removing unreacted monomers from the obtained latex via steam stripping, a dialysis membrane with a molecular weight cutoff of 10,000 made of cellulose was used for 12 hours of dialysis to achieve a resistivity of 3000 Ω·m at 25°C. Subsequently, the pH was adjusted to 4.0 using a 5% ammonia solution, and the vinylidene chloride copolymer resin was adjusted with pure water to a solids content of 40–50%.

[0454] (Fabrication of laminates)

[0455] Using the aqueous dispersion of the obtained halogenated ethylene polymer (vinylidene chloride copolymer latex), a laminate was prepared using the same method as in Example 1.

[0456] The results of the measurement / evaluation of each physical property are shown in Table 1.

[0457]

[0458] Industrial applicability

[0459] The laminate of the present invention has excellent gas and water vapor barrier properties, heat sealing properties, yellowing resistance and recyclability, and is therefore suitable for use as various packaging materials and containers such as food packaging, pharmaceutical packaging containers, and cups.

Claims

1. A gas and water vapor barrier laminate, characterized in that, A ethylene halide polymer layer comprising an ethylene halide polymer is present on a paper support, the coating efficiency of which is 5.0 × 10⁻⁶. -9 m 3 The weight-average molecular weight of the ethylene halide polymer is above 100,000, and the ethylene halide polymer is in particulate form with an average particle size greater than 120 nm.

2. The gas and water vapor barrier laminate as described in claim 1, wherein, The halogenated ethylene polymer is a crystalline resin with a crystallization melting point of less than 180°C.

3. The gas and water vapor barrier laminate as described in claim 1 or 2, wherein, The ethylene halide polymer contains more than 70% by mass of structural units derived from vinylidene chloride.

4. The gas and water vapor barrier laminate as described in claim 1 or 2, wherein, The thickness of the ethylene halide polymer layer is 0.1 μm to 100 μm.

5. The gas and water vapor barrier laminate as described in claim 1 or 2, wherein, The coating efficiency of the ethylene halide polymer layer is 1.0 × 10⁻⁶. -8 m 3 / g or more 1.0×10 -6 m 3 / g or less.

6. The gas and water vapor barrier laminate as described in claim 1 or 2, wherein, The weight-average molecular weight of the halogenated ethylene polymer is between 100,000 and 500,000.

7. The gas and water vapor barrier laminate as described in claim 1 or 2, wherein, In the laminate, the content of the halogenated ethylene polymer is 3 g / m³. 2 ~50g / m 2 .

8. The gas and water vapor barrier laminate as described in claim 1 or 2, wherein, Water vapor transmission rate is 10 g / m 2 • Less than 24 hours 9. A packaging material or packaging container, characterized in that, It comprises a gas and water vapor barrier laminate as described in any one of claims 1 to 8.

10. Use of the packaging material or packaging container according to claim 9 for packaging food.

11. A manufacturing method, comprising the manufacturing method of the gas and water vapor barrier laminate according to any one of claims 1 to 8, characterized in that, The method includes the following steps: An aqueous dispersion of ethylene halide polymer particles with an average particle size greater than 120 nm is coated onto a paper support and then dried to form an ethylene halide polymer layer.

12. The manufacturing method as described in claim 11, wherein, The pH of the aqueous dispersion of the halogenated ethylene polymer particles is less than 4.0.

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