CN116034033A - Food packaging paper - Google Patents
Food packaging paper Download PDFInfo
- Publication number
- CN116034033A CN116034033A CN202180055771.9A CN202180055771A CN116034033A CN 116034033 A CN116034033 A CN 116034033A CN 202180055771 A CN202180055771 A CN 202180055771A CN 116034033 A CN116034033 A CN 116034033A
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- CN
- China
- Prior art keywords
- coating layer
- resin
- styrene
- mass
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 235000013305 food Nutrition 0.000 title claims abstract description 161
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 84
- 239000011247 coating layer Substances 0.000 claims abstract description 232
- 239000000178 monomer Substances 0.000 claims abstract description 100
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 91
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 91
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 239000011347 resin Substances 0.000 claims abstract description 72
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 50
- 239000005033 polyvinylidene chloride Substances 0.000 claims abstract description 50
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 50
- 239000002952 polymeric resin Substances 0.000 claims abstract description 49
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 49
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 40
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 40
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 229920006026 co-polymeric resin Polymers 0.000 claims description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 54
- 239000012188 paraffin wax Substances 0.000 claims description 38
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 33
- 239000002174 Styrene-butadiene Substances 0.000 claims description 29
- 239000011115 styrene butadiene Substances 0.000 claims description 29
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- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 68
- 230000000903 blocking effect Effects 0.000 abstract description 37
- 239000000796 flavoring agent Substances 0.000 abstract description 23
- 235000019634 flavors Nutrition 0.000 abstract description 23
- 238000012545 processing Methods 0.000 abstract description 19
- 238000007789 sealing Methods 0.000 abstract description 11
- 239000000123 paper Substances 0.000 description 213
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- 239000007789 gas Substances 0.000 description 38
- 239000003795 chemical substances by application Substances 0.000 description 30
- 235000019271 petrolatum Nutrition 0.000 description 29
- -1 satin white Chemical compound 0.000 description 27
- 238000000034 method Methods 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 22
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- 238000000576 coating method Methods 0.000 description 21
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- 238000011156 evaluation Methods 0.000 description 17
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- 239000000049 pigment Substances 0.000 description 10
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 7
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- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
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- 235000019698 starch Nutrition 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 239000005003 food packaging material Substances 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
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- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
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- 238000004078 waterproofing Methods 0.000 description 3
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
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- 239000005977 Ethylene Substances 0.000 description 2
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 2
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The object is to provide a food packaging paper which has water resistance, oil resistance, gas barrier property, water vapor barrier property and flavor barrier property, heat sealing suitability and folding processing suitability, and blocking resistance. The problem is solved by a food wrap paper comprising a paper support, a first coating layer on one side of the paper support, a second coating layer on the outer side of the first coating layer with respect to the paper support, and a third coating layer on the outer side of the second coating layer with respect to the paper support, wherein the first coating layer contains kaolin and one or more selected from a styrene-butadiene copolymer resin and an acrylic resin as a binder, the second coating layer contains a polyvinylidene chloride polymer resin having a vinylidene chloride monomer as a structural unit of the resin as a main component, and the third coating layer contains an acrylic resin.
Description
Technical Field
The present invention relates to a food packaging paper, which is a food packaging material such as a food package, a food bag, or a food container, and the support of which is paper.
Background
Food packaging materials such as food packaging, food-containing bags, and food-containing containers are mostly laminated plastic films or films having metal vapor deposited films. On the other hand, there is a food packaging paper comprising a paper support having barrier properties against water vapor and oxygen from the outside in order to suppress deterioration of food due to environmental protection problems of plastic products. For example, as a paper barrier packaging material having a water vapor barrier layer and a gas barrier layer provided by application of a water-based paint and having both excellent gas barrier properties and water vapor barrier properties, a paper barrier packaging material is known in which a water vapor barrier layer containing a pigment and a water vapor barrier resin, a gas barrier layer containing a water-soluble polymer, and a water vapor barrier resin being an acrylic synthetic resin are provided in this order on a paper base material (for example, refer to patent document 1). It is also known that an adhesive layer formed by drying a dispersion of composite particles comprising an ethylene unsaturated carboxylic acid copolymer and an acrylic acid polymer and an adhesive layer formed by laminating a polyvinyl chloride and/or polyvinylidene chloride are provided on various plastic materials, various vapor deposition films, paper and other substrates that can be used for packaging foods and the like (for example, refer to patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2013-176950
Patent document 2: international publication 2016/076130 pamphlet
Disclosure of Invention
Problems to be solved by the invention
Food packaging paper such as packaging of food, food-containing bags, food-containing containers, and the like is required to have water resistance and oil resistance to moisture and oil derived from food. In addition, food packaging paper is required to prevent permeation of water vapor, moisture or oxygen, and protect food from deterioration in water vapor barrier property and gas barrier property. In addition, depending on the form of packaging, food packaging paper may be sealed after storing the food, and the food packaging paper needs to be heat-sealable. In addition, depending on the form of packaging, food packaging paper may be folded into a container shape so that food does not fall off, and folding suitability is required. When the folding processing adaptability of the food packaging paper is poor, the water resistance, oil resistance, gas barrier property, or water vapor barrier property is lowered in the folded portion of the paper. In recent years, there has been a demand for reducing the odor barrier property of the food packaging paper used for sealing, which is a result of social movement to claim the hazard related to the odor.
In addition, from the viewpoint of the effect on food, the food packaging paper preferably has heat seal suitability at a relatively low temperature. However, food packaging paper having heat seal suitability at relatively low temperatures is likely to cause blocking when stored in a wound state after production or in a laminated state after sheeting. Therefore, food packaging paper having heat seal suitability is required to have blocking resistance.
The present invention provides a food packaging paper which has water resistance, oil resistance, gas barrier property, water vapor barrier property and flavor barrier property, heat sealing suitability and folding processing suitability, and blocking resistance.
Means for solving the problems
The present inventors have conducted intensive studies and as a result, the object of the present invention is achieved in the following manner.
[1] A food wrap paper comprising a paper support, a first coating layer on one side of the paper support, a second coating layer on the outer side of the first coating layer with respect to the paper support, and a third coating layer on the outer side of the second coating layer with respect to the paper support,
the first coating layer contains kaolin and one or more selected from styrene-butadiene copolymer resin and acrylic resin as a binder,
The second coating layer contains a polyvinylidene chloride-based polymer resin having a vinylidene chloride monomer as a structural unit of the resin as a main component, and
the third coating layer contains an acrylic resin.
[2] The food wrap paper according to the above [1], wherein the first coating layer contains one or more selected from the group consisting of styrene-butadiene-based copolymer resins, or one or more selected from the group consisting of acrylic resins as a binder.
[3] The food packaging paper according to the above [2], wherein the first coating layer contains one or more selected from styrene-butadiene-based copolymer resins as a binder, and the total content of the styrene-butadiene-based copolymer resins in the first coating layer is 40 parts by mass or more and 400 parts by mass or less per 100 parts by mass of kaolin in the first coating layer per one side of the paper support.
[4] The food wrap paper according to the above [2], wherein the first coating layer contains one or more kinds selected from acrylic resins as a binder, and the total content of the acrylic resins in the first coating layer is 40 parts by mass or more and 400 parts by mass or less per 100 parts by mass of kaolin in the first coating layer per one side of the paper support.
[5] The food packaging paper according to any one of the above [1] to [4], wherein the polyvinylidene chloride-based polymer resin is a polyvinylidene chloride-based polymer resin in which a vinylidene chloride monomer in the resin is 85 mass% or more and 95 mass% or less.
[6] The food wrap paper according to any one of the above [1] to [5], wherein the acrylic resin contained in the third coating layer is a styrene-acrylic copolymer resin.
[7] The food wrap paper according to any one of the above [1] to [6], wherein the third coating layer further contains paraffin wax.
[8] The food wrap paper according to the above [7], wherein the paraffin wax of the third coating layer is a paraffin wax having a melting point of 50℃or more and 80℃or less.
[9] The food packaging paper according to the above [3], wherein the styrene-butadiene-based copolymer resin of the first coating layer is a styrene-butadiene-based copolymer resin having a styrene monomer content of 70 mass% or more and 90 mass% or less in the copolymer resin.
[10] The food wrap paper according to the above [4], wherein the acrylic resin of the first coating layer is a styrene-acrylic copolymer resin or a styrene- (meth) acrylonitrile-acrylic copolymer resin.
Effects of the invention
According to the present invention, a food packaging paper having water resistance, oil resistance, gas barrier property, water vapor barrier property, flavor barrier property, heat sealing suitability, folding suitability, and blocking resistance can be provided.
Detailed Description
The food wrapping paper includes a paper support, a first coating layer on one side of the paper support, a second coating layer on the outer side of the first coating layer with reference to the paper support, and a third coating layer on the outer side of the second coating layer with reference to the paper support. That is, the food wrap paper has a first coating layer, a second coating layer, and a third coating layer from the side near the paper support. The food packaging paper may have an intermediate coating layer between the paper support, the first coating layer, the second coating layer, and the third coating layer for the purpose of improving gas barrier properties, water vapor barrier properties, adhesion between coating layers, and the like. In some embodiments, the food wrap paper has no intermediate coating layer between each of the paper support, the first coating layer, the second coating layer, and the third coating layer. The reason for this is that the manufacturing cost of the food wrap paper becomes advantageous. In an embodiment of the food packaging paper, the surface of the food packaging paper facing the food is a surface of the food packaging paper on the side having the first coating layer, the second coating layer, and the third coating layer. In addition, the food packaging paper may have a coating layer or a back coating layer for printing on the side of the paper support opposite to the side having the first coating layer, the second coating layer, and the third coating layer for the purpose of improving printing suitability to a gravure printing machine and/or a digital printing machine or for the purpose of improving dimensional stability of the paper. A coating layer or a back coating layer for printing is conventionally known in the field of coated printing papers. Further, the food wrap paper may have a first coating layer, a second coating layer, and/or a third coating layer between the printing coating layer and the paper support.
The paper support is a base paper produced by a conventional well-known papermaking method from a stock comprising a pulp containing wood pulp and/or non-wood pulp, as required, added with various additives such as a filler, a sizing agent, a binder, a fixing agent, a yield-improving agent, and a paper strength-improving agent, a base paper produced by subjecting the base paper to a size-pressing treatment with a size-pressing liquid (japanese: upper part), a base paper produced by subjecting the base paper to a surface treatment with a surface-treating liquid, or a base paper produced by subjecting the base paper or the base paper to a rolling treatment.
In addition, as other additives, one or more selected from a pigment dispersant, a bulking agent, a thickener, a fluidity improver, a resin control agent (japanese patent application publication No. コ), a defoaming agent, a foam inhibitor, a release agent, a foaming agent, a penetrating agent, a humectant, a preservative, a mildew inhibitor, a water-resistant agent, a wet paper strength enhancer, a dry paper strength enhancer, and the like may be appropriately added to the stock within a range that does not impair the desired effects of the present invention.
The calendering process is a process of making paper pass between rolls to average the smoothness and thickness. Examples of the rolling treatment device include a mechanical rolling mill, a soft nip rolling mill, a super rolling mill, a multistage rolling mill, a multi-nip rolling mill, and the like.
Wood pulp is a pulp conventionally known in the paper making field. Examples of the wood Pulp include chemical Pulp such as LBKP (Leaf Bleached Kraft Pulp: broad leaf bleached sulfate process Pulp) and NBKP (Needle Bleached Kraft Pulp: needle bleached sulfate process Pulp), mechanical Pulp such as GP (group wood Pulp), PGW (Pressure GroundWood Pulp: pressure Pulp), RMP (Refiner Mechanical Pulp: disc refiner Pulp), TMP (ThermoMechanical Pulp: thermo refiner Pulp), CTMP (ChemiThermoMechanical Pulp: chemical thermo refiner Pulp), CMP (ChemiMechanical Pulp: chemical mechanical Pulp) and CGP (ChemiGroundwood Pulp: chemical Pulp), and waste paper Pulp such as DIP (DeInked Pulp: deInked Pulp).
The non-wood pulp is pulp containing non-wood fibers, which has been known in the art of paper making. Examples of the raw materials of the non-wood fibers include woody bast such as Broussonetia papyrifera (Japanese コ, square) and Coptis chinensis, herbal bast such as Louis and kenyaku, leaf fiber such as abaca and sisal, straw, wheat straw, sugarcane, bamboo and Spanish, and seed hair such as cotton (Japanese touch) and cotton linter. The wood pulp and/or the non-wood pulp is one or more selected from the above wood pulp and the above non-wood pulp.
The filler is a conventionally known pigment in the paper making field. Examples of the pigment include inorganic pigments such as light calcium carbonate, heavy calcium carbonate, various kaolin, talc, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, silica, aluminum silicate, diatomaceous earth, activated clay, alumina hydrate, aluminum hydroxide, lithopone, zeolite, magnesium carbonate, and magnesium hydroxide. Further, organic pigments such as styrene-based plastic pigments, acrylic-based plastic pigments, polyethylene-based plastic pigments, urea resins, melamine resins, and microcapsules can be mentioned. The filler is one or more selected from the above inorganic pigments and the above organic pigments.
In some embodiments, the ash content of the paper support of the food packaging paper is 8 mass% or less. The reason for this is that the paper support can obtain flexibility without reducing paper strength. Here, the ash amount refers to a ratio (mass%) of the mass of the incombustible after subjecting the paper support to the combustion treatment at 500 ℃ for 1 hour to the absolute dry mass of the paper support before the combustion treatment. The ash content can be controlled by a conventionally known method such as adjusting the filler content in the paper support.
The sizing agent is an internal sizing agent which has been conventionally known in the paper making field. The internal sizing agent may be, for example, a rosin sizing agent in the case of acidic paper, or an alkenyl succinic anhydride, an alkyl ketene dimer, a neutral rosin sizing agent, a cationic styrene-acrylic sizing agent, or the like in the case of neutral paper.
The surface sizing agent used in the size press liquid is a conventionally known surface sizing agent in the paper making field. Examples of the surface sizing agent include starch sizing agents, cellulose sizing agents, polyvinyl alcohol sizing agents, styrene-acrylic sizing agents, olefin sizing agents, styrene-maleic sizing agents, and acrylamide sizing agents.
The size press treatment is performed using a size press apparatus conventionally known in the paper making art. Examples of the size press device include an ink line size press, a horizontal size press, a rod size press as a film transfer machine, a roller size press and a doctor size press, a Simsizer as the rod size press, an optical size press and a speed size press, a gate roll coater as the roller size press, a beer doctor coater, a twin doctor blade coater, a Bei Erba pa coater, a pot size press, and a calendar size press.
The first coating layer contains kaolin and one or more selected from styrene-butadiene copolymer resin and acrylic resin as a binder. The first coating layer has a function as a coating layer for blocking the void provided in the paper support. The first coating layer has a function as a protective layer for protecting the second coating layer by blocking diffusion of moisture and oil from the back surface of the paper support (the side where the first, second, and third coating layers are not provided). The first coating layer functions as an adhesive layer for adhering the paper support to the second coating layer. The food packaging paper functions as a coating layer, a protective layer, and an adhesive layer by the first coating layer, and as a result, gas barrier properties, flavor barrier properties, and folding processing suitability can be obtained.
The kaolin is produced by industrially refining and processing natural kaolin raw ores such as kaolinite, nacrite, dickite, halloysite, and hydrated halloysite, and is produced by pulverizing, washing, removing iron, and classifying. The kaolin may also include layered kaolin in a thin plate form by applying a shearing force to increase the aspect ratio, engineered kaolin in which the particle size distribution is adjusted to be sharp, and kaolin with high processability such as calcined kaolin with improved aggregation.
Kaolin is typically charged differently at the planar and edge portions. Kaolin is charged and therefore readily adsorbs the binder compared to other pigments. The styrene-butadiene copolymer resin has high pigment binding property. Since the acrylic resin has a polarity in the molecule, the acrylic resin is excellent in adsorption to kaolin. Therefore, the first coating layer containing kaolin and one or a combination of two or more selected from the group consisting of a styrene-butadiene-based copolymer resin and an acrylic resin is excellent in forming a film. As a result, the function as a coating layer, a protective layer, and an adhesive layer is well exhibited.
In some embodiments, the first coating layer contains one or two or more selected from styrene-butadiene-based copolymer resins, or one or two or more selected from acrylic resins as a binder. This is because the film formation is good if one or more selected from styrene-butadiene copolymer resins or one or more selected from acrylic resins. The reason for this is considered to be that phase separation is likely to occur when a resin containing a styrene monomer in the molecule and a resin containing an acrylic monomer in the molecule coexist.
In at least one embodiment, the first coating layer contains one or more selected from styrene-butadiene-based copolymer resins as a binder, and the total content of the styrene-butadiene-based copolymer resins in the first coating layer is 40 parts by mass or more and 400 parts by mass or less per 100 parts by mass of kaolin in the first coating layer for each side of the paper support. The reason for this is that the gas barrier property, flavor barrier property and/or folding processing suitability of the food packaging paper become good.
The styrene-butadiene copolymer resin is a copolymer resin of a styrene monomer and butadiene. Examples of the styrene monomer include styrene derivatives having a substituent on a vinyl group such as styrene and α -methylstyrene, and derivatives having a substituent on a benzene ring such as vinyltoluene and p-chlorostyrene. In some embodiments, the styrene-butadiene-based copolymer resin has a styrene-based monomer content of 67 mass% or more and less than 100 mass%. In at least one embodiment, the styrene-butadiene-based copolymer resin has a styrene-based monomer content of 70 mass% or more and 90 mass% or less. This is because the gas barrier property, flavor barrier property and folding processing suitability of the food packaging paper become good.
The styrene-butadiene copolymer resin may have a monomer copolymerizable with the styrene monomer and butadiene in addition to the styrene monomer and butadiene. Examples of copolymerizable monomers include (meth) acrylonitrile, (meth) acrylic acid salts, (meth) acrylic acid esters, maleic acid, vinyl acetate, vinyl chloride, vinylidene chloride, and ethylene.
The styrene-butadiene copolymer resin can be synthesized by a known emulsion polymerization method. For example, the synthesis is a method of mixing the monomers, an emulsifier and water in a predetermined reaction vessel, adding a radical polymerization initiator, stirring and heating. The mass ratio of each monomer contained in the copolymer resin can be adjusted by the amount of each monomer blended in the reaction vessel. The styrene-butadiene copolymer resin is commercially available from Denka, asahi chemical Co., ltd., BASF, JSR, etc.
In at least one embodiment, the first coating layer contains one or more selected from acrylic resins as a binder, and the total content of the acrylic resins in the first coating layer is 40 parts by mass or more and 400 parts by mass or less per 100 parts by mass of kaolin in the first coating layer for each side of the paper support. The reason for this is that the gas barrier property, flavor barrier property and/or folding processing suitability of the food packaging paper become good.
In some embodiments, the acrylic resin of the first coating layer is a resin containing more than 50 mass% acrylic monomer in the resin. The reason for this is that the gas barrier property, flavor barrier property and/or folding processing suitability of the food packaging paper become good.
Examples of the acrylic monomer include (meth) acrylic acid, (meth) acrylic acid salts and alkyl (meth) acrylates. Examples of the (meth) acrylic acid salt include lithium (meth) acrylate, sodium (meth) acrylate, potassium methacrylate, and sodium 2-sulfoethyl (meth) acrylate. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, decyl (meth) acrylate, and undecyl (meth) acrylate. In addition, as an example of the acrylic monomer, examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1, 2-propanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate, diacetone alcohol, acetol (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, polycaprolactone-modified hydroxyalkyl (meth) acrylate, acetol (meth) acrylate, 2- (acetoacetoxyethyl (meth) acrylate, and (3, 4-epoxycyclohexyl) methyl (meth) acrylate.
The acrylic resin may contain other monomers copolymerizable with the acrylic monomer in addition to the acrylic monomer. Examples of the other monomers include styrene, vinyl acetate, vinyl chloride, (meth) acrylonitrile, ethylene, propylene, divinylbenzene, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N' -methylenebis (meth) acrylamide, sodium vinylsulfonate, sodium p-styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, sodium 3-allyloxy-2-hydroxypropanesulfonate, sodium polyoxyethylene styrenated phenylsulfate, sodium glycerol monoallyl ether Shan Huangji succinate, (meth) acrylamide sodium stearate, diallyl phthalate, triallyl cyanurate, acrolein, diacetone (meth) acrylamide, formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, (meth) acryloxyalkyl acrolein, and diacetone (meth) acrylamide.
In some embodiments, the acrylic resin is a resin obtained by polymerizing one or more monomers selected from the acrylic monomers. In some embodiments, the acrylic resin is a resin obtained by copolymerizing one or more monomers selected from the acrylic monomers and one or more monomers selected from the monomers other than the acrylic monomers.
In some embodiments, the acrylic resin is a styrene-acrylic copolymer resin obtained by copolymerizing an acrylic monomer and styrene, or a styrene- (meth) acrylonitrile-acrylic copolymer resin obtained by copolymerizing an acrylic monomer, styrene, and (meth) acrylonitrile. In at least one embodiment, the acrylic resin is a styrene-acrylic copolymer resin obtained by copolymerizing styrene with one or more acrylic monomers selected from the group consisting of (meth) acrylic acid, a (meth) acrylate salt, and an alkyl (meth) acrylate. In at least one embodiment, the acrylic resin is a styrene- (meth) acrylonitrile-acrylic copolymer resin obtained by copolymerizing styrene and (meth) acrylonitrile with one or more acrylic monomers selected from the group consisting of (meth) acrylic acid, a (meth) acrylate salt, and an alkyl (meth) acrylate. This is because the gas barrier property and flavor barrier property of the food packaging paper become good. The acrylic resin is commercially available from, for example, sanjing chemical Co., east Asia Synthesis Co., ltd., first dope production Co., DIC Co., PS Japan Co., japan Polyethylene, xudi chemical Co., toli Co., DOW-MITSUI POLYCHEMICALS, BASF, etc.
The acrylic resin can be synthesized by a known emulsion polymerization method. For example, the synthesis is a method of mixing the monomers, an emulsifier and water in a predetermined reaction vessel, adding a radical polymerization initiator, stirring and heating. The mass ratio of each monomer contained in the copolymer resin can be adjusted by the amount of each monomer blended in the reaction vessel.
The first coating layer may contain various conventionally known additives as required, in addition to kaolin and a styrene-butadiene copolymer resin and an acrylic resin as binders. Examples of the additives include inorganic pigments other than kaolin, organic pigments, various binders other than styrene-butadiene copolymer resins and acrylic resins, polysaccharides such as starches and celluloses, surfactants, dispersants, thickeners, water-retaining agents, antifoaming agents, water-proofing agents, and the like.
The second coating layer contains a polyvinylidene chloride-based polymer resin having a vinylidene chloride monomer as a structural unit of the resin as a main component. In some embodiments, the content of the polyvinylidene chloride-based polymer resin in the second coating layer is 85 mass% or more per one side of the paper support with respect to the dry solid content of the second coating layer. The reason for this is that the polyvinylidene chloride-based polymer resin serves as a barrier agent, and the gas barrier property, the water vapor barrier property, and the flavor barrier property of the food packaging paper become good.
The second coating layer may contain various conventionally known additives, as required, in addition to the polyvinylidene chloride-based polymer resin. Examples of the additives include inorganic pigments, organic pigments, various resins other than polyvinylidene chloride-based polymer resins, polysaccharides such as starches and celluloses, surfactants, dispersants, thickeners, water retention agents, antifoaming agents, water-proofing agents, and the like.
In a polyvinylidene chloride-based polymer resin having a vinylidene chloride monomer as a structural unit of the resin as a main component, the vinylidene chloride monomer in the resin exceeds 80 mass%. In some embodiments, the polyvinylidene chloride-based polymer resin having a vinylidene chloride monomer as a main component as a structural unit of the resin is a resin obtained by copolymerizing one or more of a vinylidene chloride monomer and another monomer copolymerizable with the vinylidene chloride monomer.
In some embodiments, in the polyvinylidene chloride-based polymer resin having a vinylidene chloride monomer as a structural unit of the resin as a main component, the vinylidene chloride monomer in the resin is 85 mass% or more. This is because if the vinylidene chloride monomer content in the resin is 85 mass% or more, the gas barrier property and the water vapor barrier property of the food packaging paper become good. In some embodiments, in the polyvinylidene chloride-based polymer resin having a vinylidene chloride monomer as a structural unit of the resin as a main component, the vinylidene chloride monomer in the resin is 95 mass% or less. This is because if the vinylidene chloride monomer is 95 mass% or less, rapid crystallization can be suppressed at the time of forming the coating film of the second coating layer, and thus a time for the second coating layer to become flat can be obtained. As a result, defects in the second coating layer are reduced, and the gas barrier property and the water vapor barrier property of the food packaging paper become good. In at least one embodiment, the polyvinylidene chloride-based polymer resin having a vinylidene chloride monomer as a main component as a structural unit of the resin is a resin in which the vinylidene chloride monomer is 85 mass% or more and 95 mass% or less in the resin.
The other monomer copolymerizable with the vinylidene chloride monomer is not particularly limited as long as it is a monomer copolymerizable with the vinylidene chloride monomer. Examples of the other monomer include acrylonitrile (meth) and methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, N-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, N-octyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, N-dimethylacrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone, vinyl propionate, vinyl stearate, vinyl acetate, and the like.
In some embodiments, the second coating layer of the polyvinylidene chloride-based polymer resin, the other monomer is one or more selected from the group consisting of (meth) acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. In the polyvinylidene chloride-based polymer resin, the vinylidene chloride monomer in the resin is 85 mass% or more and 95 mass% or less, the monomer selected from (meth) acrylonitrile is 2 mass% or more and 10 mass% or less, and the monomer selected from methyl (meth) acrylate, ethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate is 0.5 mass% or more and 5 mass% or less. In at least one embodiment, in the polyvinylidene chloride-based polymer resin, the vinylidene chloride monomer in the resin is 85 mass% or more and 95 mass% or less, the monomer selected from (meth) acrylonitrile is 2 mass% or more and 10 mass% or less, and the monomer selected from methyl (meth) acrylate and ethyl (meth) acrylate is 0.5 mass% or more and 5 mass% or less. This is because the gas barrier property and the water vapor barrier property of the food packaging paper become good.
When the total content of the vinylidene chloride monomer and the other monomer is less than 100% by mass, the polyvinylidene chloride-based polymer resin may contain one or more monomers copolymerizable with these monomers.
The molecular weight of the polyvinylidene chloride-based polymer resin is not particularly limited. In some embodiments, the molecular weight of the polyvinylidene chloride-based polymer resin is 8 ten thousand or more in terms of weight average molecular weight measured by gel permeation chromatography using polystyrene having a known molecular weight as a standard substance. The reason for this is that if the molecular weight is in the above range, the polyvinylidene chloride-based polymer resin has good heat and light stability.
The polyvinylidene chloride-based polymer resin can be synthesized by a known emulsion polymerization method. For example, the synthesis is a method of mixing various monomers, an emulsifier and water in a predetermined reaction vessel, adding a radical polymerization initiator, stirring and heating. The polyvinylidene chloride-based polymer resin is commercially available from, for example, asahi chemical industry Co.
The third coating layer contains an acrylic resin. In the third coating layer, the acrylic resin serves as a water-resistant oil-resistant agent and functions as a water-resistant oil-resistant layer. The acrylic resin contained in the third coating layer may be any resin that exhibits water and oil resistance, and the monomer constituting the acrylic resin contained in the third coating layer is the same as the monomer constituting the acrylic resin of the first coating layer, and the description thereof is omitted. When the first coating layer contains an acrylic resin, the acrylic resin of the first coating layer and the acrylic resin of the third coating layer may be the same type of resin or different types of resins.
In some embodiments, the acrylic resin of the third coating layer is a styrene-acrylic copolymer resin formed by copolymerizing an acrylic monomer with styrene. This is because if the acrylic resin of the third coating layer is a styrene-acrylic copolymer resin, the adhesion and film forming properties of the second coating layer containing a polyvinylidene chloride polymer resin are good, and as a result, the folding workability of the food packaging paper becomes good. The reason for this is that the acrylic resin contains styrene having high crystallinity, and thus the blocking resistance of the food packaging paper is improved. In addition, in some embodiments, the acrylic resin of the third coating layer contains more than 50 mass% of the alkyl (meth) acrylate in the resin as the acrylic monomer. The reason for this is that water resistance and oil resistance become good. In at least one embodiment, the acrylic resin of the third coating layer is a styrene-acrylic copolymer resin containing more than 50 mass% of an alkyl (meth) acrylate as an acrylic monomer and copolymerized with styrene.
In some embodiments, the third coating layer further comprises paraffin wax. The reason for this is that the food packaging paper is excellent in water vapor barrier property and/or blocking resistance. In at least one embodiment, the content of paraffin wax in the third coating layer is 3 parts by mass or more and 15 parts by mass or less per one side of the paper support with respect to 100 parts by mass of the acrylic resin in the third coating layer. The reason for this is that if the content of paraffin wax is within this range, the water vapor barrier property and blocking resistance can be optimized without impeding the heat sealing suitability of the food packaging paper. In addition, in some embodiments, the paraffin wax in the third coating layer has a melting point of 50 ℃ or higher. In addition, in some embodiments, the paraffin wax in the third coating layer has a melting point of 80 ℃ or less. In at least one embodiment, the paraffin wax in the third coating layer has a melting point of 50 ℃ or more and 80 ℃ or less. The reason for this is that the water vapor barrier property and the blocking resistance can be optimized without impeding the heat sealing suitability of the food packaging paper, and that paraffin wax having a melting point exceeding 80 ℃ is difficult to obtain.
Paraffin wax is a so-called petroleum wax, and is produced by separating and purifying from vacuum distillation distillate oil in petroleum refining. Petroleum wax according to JIS K2235:1991 is roughly classified into 3 types of paraffin wax, microcrystalline wax, and petrolatum. Similarly, the main component of the separated and purified microcrystalline wax is branched hydrocarbon (isoparaffin) or cyclic hydrocarbon (naphthene) having a molecular weight of 500 to 800 and a carbon number of about 30 to 60 and having a side chain in a large main chain, whereas the molecular weight of paraffin is as small as 300 to 550, and the linear hydrocarbon is a main component and has a carbon number of about 20 to 40. Paraffin wax is commercially available from, for example, zhongjing oil and fat company, japanese refined wax company, BYK-Chemie Japan company, etc.
The third coating layer may contain various conventionally known additives, as required, in addition to the acrylic resin and the paraffin wax. Examples of the additives include inorganic pigments, organic pigments, various resins other than acrylic resins, polysaccharides such as starches and celluloses, surfactants, dispersants, thickeners, water-retaining agents, antifoaming agents, water-proofing agents, colorants, ultraviolet absorbers, and the like.
In some embodiments, the first coating layer of the food wrap paper contains kaolin and one or more selected from a styrene-butadiene-based copolymer resin and an acrylic resin, the second coating layer contains a polyvinylidene chloride-based polymer resin, and the third coating layer contains a styrene-acrylic copolymer resin as an acrylic resin. In at least one embodiment, the first coating layer of the food wrap paper contains kaolin and one or more selected from a styrene-butadiene-based copolymer resin and an acrylic resin, the second coating layer contains a polyvinylidene chloride-based polymer resin, and the third coating layer contains a styrene-acrylic copolymer resin as an acrylic resin and paraffin wax having a melting point of 50 ℃ to 80 ℃.
In some embodiments, the first coating layer of the food wrap paper contains kaolin and one or more selected from styrene-butadiene-based copolymer resins, or one or more selected from acrylic resins, the second coating layer contains polyvinylidene chloride-based polymer resins, and the third coating layer contains styrene-acrylic copolymer resins as acrylic resins. In at least one embodiment, the first coating layer of the food wrap paper contains kaolin and one or more selected from styrene-butadiene-based copolymer resins or one or more selected from acrylic resins, the second coating layer contains polyvinylidene chloride-based polymer resins, and the third coating layer contains styrene-acrylic copolymer resins as acrylic resins and paraffin wax having a melting point of 50 ℃ to 80 ℃.
In some embodiments, the first coating layer of the food wrap paper contains kaolin and one or more selected from styrene-butadiene-based copolymer resins, the second coating layer contains polyvinylidene chloride-based polymer resins, and the third coating layer contains styrene-acrylic copolymer resins as acrylic resins. In at least one embodiment, the first coating layer of the food wrap paper contains kaolin and one or more selected from styrene-butadiene-based copolymer resins, the second coating layer contains polyvinylidene chloride-based polymer resins, and the third coating layer contains styrene-acrylic copolymer resins as acrylic resins and paraffin wax having a melting point of 50 ℃ to 80 ℃.
In some embodiments, the first coating layer of the food wrap paper contains kaolin and one or more selected from acrylic resins, the second coating layer contains a polyvinylidene chloride-based polymer resin, and the third coating layer contains a styrene-acrylic copolymer resin as an acrylic resin. In at least one embodiment, the first coating layer of the food wrap paper contains kaolin and one or more selected from acrylic resins, the second coating layer contains a polyvinylidene chloride-based polymer resin, and the third coating layer contains a styrene-acrylic copolymer resin as an acrylic resin and paraffin wax having a melting point of 50 ℃ to 80 ℃.
The food wrap paper may be manufactured by sequentially providing a first coating layer, a second coating layer, and a third coating layer to the paper support. The method of sequentially disposing the first coating layer, the second coating layer, and the third coating layer on the paper support is not particularly limited. As an example, a method of applying and drying a coating liquid for forming each coating layer using a coating apparatus and a drying apparatus which have been conventionally known in the paper making field is given. Examples of the coating apparatus include a film press coater, a bar coater, an air knife coater, a bar blade coater, a bar coater, a blade coater, a gravure coater, a curtain coater, an E-bar coater, and a film transfer coater. Examples of the drying device include various drying devices such as a hot air dryer such as a linear tunnel dryer, an arch dryer, an air-loop dryer, a sinusoidal air-float dryer (japanese drive), an infrared heating dryer, and a dryer using microwaves.
The coating liquid of the first coating layer contains kaolin and one or more selected from styrene-butadiene copolymer resin and acrylic resin as a binder, the coating liquid of the second coating layer contains polyvinylidene chloride polymer resin, and the coating liquid of the third coating layer contains acrylic resin or acrylic resin and paraffin wax, whereby each of the obtained coating layers may contain kaolin and one or more selected from styrene-butadiene copolymer resin and acrylic resin, polyvinylidene chloride polymer resin, and acrylic resin or acrylic resin and paraffin wax, respectively.
In some embodiments, the first coating layer is applied in an amount of 3g/m dry solids content per side of the paper support 2 Above and 15g/m 2 The following is given.
In some embodiments, the second coating layer is applied in an amount of 4g/m dry solids content per side of the paper support 2 Above and 15g/m 2 The following is given.
In some embodiments, the third coating layer is applied in an amount of 4g/m dry solids content per side of the paper support 2 Above and 25g/m 2 The following is given.
In at least one embodiment, the first coating layer is applied in an amount of 3g/m as dry solids content per side of the paper support in the food wrap paper 2 Above and 15g/m 2 The second coating layer was applied in an amount of 4g/m in terms of dry solid content 2 Above and 15g/m 2 The third coating layer was applied in an amount of 4g/m in terms of dry solid content 2 Above and 25g/m 2 The following is given.
The reason for this is that the effects of the present invention can be stably obtained and the material cost can be suppressed.
The food packaging paper can be used as food packaging materials such as food packaging bags, food-containing bags, and food-containing containers.
Examples
The present invention will be described in further detail with reference to examples. The present invention is not limited to these examples. Here, "parts by mass" and "mass%" refer to "parts by mass" and "mass%" of the dry solid component amount or the substantial component amount, respectively. The coating amount of the coating layer represents the dry solid component amount.
< paper support >
The following papers were prepared.
The paper stock matched with the above is manufactured by a fourdrinier paper machine, and the weight per unit area is 55g/m 2 Is used as a base paper of (a) a paper sheet. The paper support was obtained by subjecting it to a calendering treatment using a mechanical calender at a temperature of 60℃and a treatment speed of 500 m/min. The ash content of the paper support was 5 mass%.
< coating liquid of first coating layer >
The following coating solutions were prepared using water as a medium.
Pigment types and parts by mass are described in tables 1 and 2
The types and parts by mass of the resins are shown in tables 1 and 2
< coating liquid for second coating layer >
The following coating solutions were prepared using water as a medium.
The resin types are shown in tables 1 and 2 per 100 parts by mass
< coating liquid of third coating layer >
The following coating solutions were prepared using water as a medium.
The resin types are shown in tables 1 and 2 per 100 parts by mass
The paraffin wax types and mass parts are shown in tables 1 and 2
[ Table 1 ]
[ Table 2 ]
The materials shown in tables 1 and 2 are as follows.
Kaolin: kaolin having a cumulative frequency of 88% by volume of less than 2 μm
Calcium carbonate: calcium carbonate having a cumulative frequency of 87 vol% or less of 2 μm
Styrene-butadiene series 1: styrene-butadiene copolymer resin (styrene-based monomer content: 63 mass%)
Styrene-butadiene series 2: styrene-butadiene copolymer resin (styrene-based monomer content: 70 mass%)
Styrene-butadiene series 3: styrene-butadiene copolymer resin (styrene-based monomer content: 88 mass%)
Styrene-butadiene series 4: styrene-butadiene copolymer resin (styrene-based monomer content: 96% by mass)
Acrylic resin 1: poly (n-butyl acrylate) resin
Acrylic resin 2: methyl methacrylate-2-ethylhexyl acrylate copolymer resin
Acrylic resin 3: styrene-acrylonitrile-ethyl acrylate copolymer resin
Acrylic resin 4: styrene-ethyl acrylate copolymer resin
Acrylic resin 5: styrene, n-butyl acrylate copolymer resin
PVDC1: polyvinylidene chloride polymer resin
(compounding ratio of monomers in mass%)
Vinylidene chloride: 80
Methacrylonitrile: 15
Ethyl acrylate: 5
PVDC2: polyvinylidene chloride polymer resin
(compounding ratio of monomers in mass%)
Vinylidene chloride: 85
Methacrylonitrile: 10
Ethyl acrylate: 5
PVDC3: polyvinylidene chloride polymer resin
(compounding ratio of monomers in mass%)
Vinylidene chloride: 90
Acrylonitrile: 9
Ethyl acrylate: 1
PVDC4: polyvinylidene chloride polymer resin
(compounding ratio of monomers in mass%)
Vinylidene chloride: 95
Acrylonitrile: 3
Ethyl acrylate: 2
PVDC5: polyvinylidene chloride polymer resin
(compounding ratio of monomers in mass%)
Vinylidene chloride: 98
Methacrylonitrile: 1.5
Ethyl acrylate: 0.5
PVDC6: polyvinylidene chloride polymer resin
(compounding ratio of monomers in mass%)
Vinylidene chloride: 95
Methacrylonitrile: 2
Ethyl acrylate: 3
PVDC7: polyvinylidene chloride polymer resin
(compounding ratio of monomers in mass%)
Vinylidene chloride: 94
Methacrylonitrile: 5.5
Ethyl acrylate: 0.5
PVA: polyvinyl alcohol
(unmodified, completely saponified, average degree of polymerization 1700)
Ethylene-vinyl acetate system: ethylene-vinyl acetate copolymer resin
Paraffin 1: paraffin wax with melting point of 43 DEG C
Paraffin 2: paraffin with melting point of 51 DEG C
Paraffin 3: paraffin with melting point of 70 DEG C
Paraffin 4: paraffin wax with melting point of 77 DEG C
< coating >
Paper holder using rod coaterThe support is coated with the coating liquid of the first coating layer on one side and dried. At a coating amount of 10g/m 2 The coater conditions are adjusted in the manner of (a).
Next, the first coating layer was coated with a coating liquid for the second coating layer by an air knife coater and dried. At a coating amount of 10g/m 2 The coater conditions are adjusted in the manner of (a). Next, the second coating layer was coated with a coating liquid for the third coating layer by an air knife coater and dried. At a coating amount of 15g/m 2 The coater conditions are adjusted in the manner of (a).
< Water resistance >
The evaluation of water resistance was performed as follows: about 2ml of red-colored water droplets were dropped on the surface of the food packaging paper (the side having the first, second, and third coating layers), and the degree of penetration of the dropped water on the surface of the food packaging paper and the degree of bleeding on the back surface of the food packaging paper (the side not having the first, second, and third coating layers) were visually observed. From the observation results, the water resistance was evaluated according to the following criteria. In the present invention, if the evaluation of the food wrap paper is a or B, it is considered to have water resistance.
A: no penetration and no exudation was confirmed.
B: penetration was slightly confirmed. However, no exudation was confirmed.
C: infiltration was confirmed. In addition, exudation was confirmed.
< oil resistance >
The oil resistance was evaluated as follows: about 1ml of oil droplets were dropped on the surface of the food packaging paper (the side having the first, second and third coating layers), and the degree of penetration of the dropped water on the surface of the food packaging paper and the degree of bleeding on the back surface of the food packaging paper (the side not having the first, second and third coating layers) were visually observed. Salad oil was used as the oil. From the observation results, oil resistance was evaluated according to the following criteria. In the present invention, if the evaluation of the food wrap paper is a or B, it is considered to have oil resistance.
A: no penetration and no exudation was confirmed.
B: penetration was slightly confirmed. However, no exudation was confirmed.
C: infiltration was confirmed. In addition, exudation was confirmed.
< gas Barrier Property >
The gas barrier properties were evaluated according to ISO15105-2:2003"plastics-Film and sheeting-Determination of gas-transmission rate-Part2: the measurement results were carried out by the method of Equat-pressure (JIS K7126-2:2006 "Plastic-film and sheet-gas permeation test method-2 nd: isobaric method"). The measurement was performed with the side having the first, second, and third coating layers as the outside. The gas permeation rate test was carried out using oxygen as the oxygen permeation rate, and the temperature and humidity conditions were set to 23.+ -. 0.5 ℃ and a relative humidity of 85.+ -. 2%. In the present invention, the food packaging paper is considered to have gas barrier properties if it is evaluated as A, B or C.
A: oxygen transmission rate of 50cc/m 2 24 h.atm or less.
B: although inferior to A above, the oxygen permeability was 100cc/m 2 24 h.atm or less, is generally good.
C: although inferior to the above B, the oxygen permeability was 150cc/m 2 24 h.atm or less, and is practical.
D: worse than C above, oxygen transmission exceeding 150cc/m 2 24 h.atm, which is impractical.
< Water vapor Barrier Property >
The water vapor barrier property was evaluated according to JIS Z0208:1976 "moisture permeability test method (cup method)" of moisture-proof packaging materials. The measurement was performed with the side having the first coating layer, the second coating layer, and the third coating layer as the inner side. The water vapor permeability was set, and the temperature and humidity conditions were set at 40.+ -. 0.5 ℃ and 90.+ -. 2%. In the present invention, the food packaging paper is considered to have water vapor barrier properties if it is evaluated as A, B or C.
A: the water vapor transmission rate was 30g/m 2 24 hours or less, is preferable.
B: although worse than A above, waterVapor transmission rate of 50g/m 2 24 hours or less, generally good.
C: although inferior to the above B, the water vapor permeability was 100g/m 2 24h or less, and is practical.
D: the water vapor transmission rate exceeds 100g/m, which is inferior to the above C 2 24h, which is impractical.
< fragrance Barrier Property >
As the aroma-generating substance, a commercially available standard coffee powder was used. Standard coffee powder was placed in the glass, the opening of the glass was covered with the food wrapping paper with the surface of the food wrapping paper (the side having the first, second, and third coating layers) as the inner side, and the periphery of the opening was tightly sealed with an adhesive tape. The 5 subjects smell the openings of the cups sealed with the food packaging paper, and evaluated in sensory evaluation according to the following criteria.
3, the method comprises the following steps: no smell was perceived.
2, the method comprises the following steps: the smell was slightly felt.
1, the method comprises the following steps: an odor was perceived.
The evaluation of the flavor barrier property was based on the results of 5-person sensory evaluation, and was performed according to the following criteria. In the present invention, if the food packaging paper is evaluated as a or B, it is considered to have flavor blocking property.
A: 3 or more and 0 in evaluation 1.
B: evaluation 2 was 3 or more and evaluation 1 was 0.
C: the number of evaluation 1 was 1 or more.
< Heat seal suitability >
The evaluation sample was prepared by using 2 sheets of food-packaging paper, and heat-sealing the surfaces of the food-packaging paper on the sides having the first, second, and third coating layers with each other under a pressure of 0.5MPa and 140 ℃ for 1 second by a heat sealer.
The evaluation of heat seal suitability was performed as follows: the heat-sealed food packaging paper was cut out at a width of 15mm, left standing at 23℃and 50% RH for 24 hours, and then the peel strength of the heat-sealed portion was measured at a tensile speed of 300 mm/min and a tensile angle of 180 degrees using a tensile tester. The measurement was performed in 5 parts of the sample, and an average value of 5 parts was taken. Based on the measured values, heat seal suitability was evaluated according to the following criteria. In the present invention, if the evaluation of the food wrap paper is A, B or C, it is considered to have heat seal suitability.
A: the value is more than 10N/15mm.
B: the value is more than 6N/15mm and less than 10N/15mm.
C: the value is more than 3N/15mm and less than 6N/15mm.
D: the value is less than 3N/15mm.
< blocking resistance >
The food wrap paper was wound into a roll (length 500 m) around a paper tube having a diameter of 150mm with the third coating layer on the outside. The roll was allowed to stand at 30℃and 80% RH for 24 hours by the 2 methods of direct standing and suspending. The blocking resistance was evaluated by performing an operation (unwinding) of releasing the food packaging paper from the wound product after standing. During unwinding, the state of blocking of the food packaging paper was visually observed. From the observation results, blocking resistance was evaluated according to the following criteria. In the present invention, if the evaluation of the food wrap paper is A, B or C, it is regarded as having blocking resistance.
A: no blocking was confirmed in the 2 methods of direct placement and suspension.
B: very little blocking was confirmed in the direct placement method. No blocking was confirmed in the floating method.
C: blocking was slightly confirmed in the direct placement method. No blocking was confirmed in the floating method.
D: worse than C above, blocking was confirmed in the direct placement method. Alternatively, blocking was confirmed in the floating method.
< folding processing adaptability >
The food wrap paper is folded once in the MD direction with the third coating layer as the inner side, and then opened, and then folded once in the CD direction with the rubber roller. This was performed with 10 pieces of food wrap paper. The evaluation of the folding suitability was performed by blowing a red test liquid (japanese) from the third coating layer side to the folded portion, and visually observing the leakage of the test liquid from the opposite side. The test liquid was a perfect seal test liquid from Fuji image company. Based on the observation results, folding suitability was evaluated according to the following criteria. In the present invention, if the evaluation of the food wrap paper is A, B or C, it is regarded as having folding processing suitability.
A: the number of sheets in which leakage was observed was 0.
B: the number of sheets in which leakage was observed was 1 to 2.
C: the number of sheets in which leakage was observed was 3 to 4 sheets.
D: the number of sheets in which leakage was observed was 5 or more.
The evaluation results are shown in tables 3 and 4.
[ Table 3 ]
[ Table 4 ]
As is clear from tables 3 and 4, examples 1 to 48 according to the present invention are food wrapping papers having water resistance, oil resistance, gas barrier property, water vapor barrier property, flavor barrier property, heat sealing suitability, folding suitability, and blocking resistance. On the other hand, it was found that comparative examples 1 to 12 which did not satisfy the constitution of the present invention were food wrapping papers which did not satisfy at least one of these effects.
As is apparent from the comparison between examples 1, 3 and 6 to 9, if the first coating layer contains one or more selected from styrene-butadiene based copolymer resins as a binder, the total content of the styrene-butadiene based copolymer resins in the first coating layer is 40 parts by mass or more and 400 parts by mass or less per 100 parts by mass of kaolin in the first coating layer per one side of the paper support, and the gas barrier property, flavor barrier property and/or folding processing suitability of the food packaging paper become good.
As is apparent from the comparison between examples 25 to 30, the gas barrier property, the flavor barrier property and/or the folding workability of the food packaging paper were improved if the first coating layer contained one or more kinds selected from the acrylic resins as the binder, and the total content of the acrylic resins in the first coating layer was 40 parts by mass or more and 400 parts by mass or less per 100 parts by mass of the kaolin in the first coating layer per one side of the paper support.
From the comparison between examples 7 and examples 10 to 15 and the comparison between examples 17 to 23, it is evident that, in the second coating layer, if the vinylidene chloride monomer in the resin is a polyvinylidene chloride-based polymer resin of 85 mass% or more and 95 mass% or less, the gas barrier property and the water vapor barrier property of the food wrap paper become good.
As is clear from comparison of mainly examples 7 and 16, examples 18 and 31, examples 24 and 32, examples 28 and 33, examples 39 and 45, examples 42 and 46, examples 43 and 47, and examples 44 and 48, in the third coating layer, if the acrylic resin is a styrene-acrylic copolymer resin, folding processing suitability and blocking resistance of the food wrap paper become good.
As is evident mainly from the comparison of examples 7 and 39, examples 18 and 42, examples 24 and 43, examples 28 and 44, examples 16 and 45, examples 31 and 46, examples 32 and 47, and examples 33 and 48, if the third coating layer contains paraffin wax, the water vapor barrier property and/or blocking resistance of the food wrap paper becomes good.
As is apparent from the comparison between examples 35 to 38, if the paraffin wax of the third coating layer is a paraffin wax having a melting point of 50 ℃ or more and 80 ℃ or less, the water vapor barrier property and blocking resistance of the food wrap paper become good without impairing the heat seal suitability.
As is apparent from the comparison between examples 2 to 5, when the styrene-butadiene-based copolymer resin of the first coating layer contains the styrene-based monomer in a mass ratio of 70 mass% or more and 90 mass% or less, the gas barrier property, flavor barrier property and folding workability of the food packaging paper become good.
Mainly from the comparison between examples 18, 24 and 28, examples 31 to 33, examples 42 to 44 and examples 46 to 48, if the acrylic resin of the first coating layer is a styrene-acrylic copolymer resin obtained by copolymerizing an acrylic monomer with styrene or a styrene- (meth) acrylonitrile-acrylic copolymer resin obtained by copolymerizing an acrylic monomer, styrene and (meth) acrylonitrile, the gas barrier property and the flavor barrier property of the food wrap paper become good.
The following supplementary notes are also disclosed with respect to the embodiments of the present invention described above.
<1>
A food wrap paper comprising a paper support, a first coating layer on one side of the paper support, a second coating layer on the outer side of the first coating layer with respect to the paper support, and a third coating layer on the outer side of the second coating layer with respect to the paper support, wherein the first coating layer contains kaolin and one or more selected from a styrene-butadiene copolymer resin and an acrylic resin as a binder, the second coating layer contains a polyvinylidene chloride polymer resin having a vinylidene chloride monomer as a structural unit of the resin as a main component, and the third coating layer contains an acrylic resin.
The food packaging paper has water resistance, oil resistance, gas barrier property, water vapor barrier property, and flavor barrier property, heat sealing suitability, folding processing suitability, and blocking resistance.
<2>
The food wrap paper according to the above <1>, wherein the first coating layer contains one or more selected from the group consisting of styrene-butadiene-based copolymer resins, or one or more selected from the group consisting of acrylic resins as a binder.
<3>
The food packaging paper according to the above <2>, wherein the first coating layer contains one or more selected from styrene-butadiene-based copolymer resins as a binder, and the total content of the styrene-butadiene-based copolymer resins in the first coating layer is 40 parts by mass or more and 400 parts by mass or less per 100 parts by mass of kaolin in the first coating layer per one side of the paper support.
Thus, the gas barrier property, flavor barrier property and/or folding processing adaptability of the food packaging paper become good.
<4>
The food wrap paper according to the above <2>, wherein the first coating layer contains one or more kinds selected from acrylic resins as a binder, and the total content of the acrylic resins in the first coating layer is 40 parts by mass or more and 400 parts by mass or less per 100 parts by mass of kaolin in the first coating layer per one side of the paper support.
Thus, the gas barrier property, flavor barrier property and/or folding processing adaptability of the food packaging paper become good.
<5>
The food packaging paper according to any one of the above <1> to <4>, wherein the polyvinylidene chloride-based polymer resin has a vinylidene chloride monomer content of 85 mass% or more and 95 mass% or less.
Thus, the gas barrier property and the water vapor barrier property of the food packaging paper become good.
<6>
The food wrap paper according to any one of the above <1> to <5>, wherein the acrylic resin contained in the third coating layer is a styrene-acrylic copolymer resin.
Thus, the folding processing adaptability and blocking resistance of the food packaging paper become good.
<7>
The food wrap paper according to any one of the above <1> to <6>, wherein the third coating layer further contains paraffin wax.
Thus, the food packaging paper is excellent in water vapor barrier property and/or blocking resistance.
<8>
The food wrap paper according to the above <7>, wherein the wax of the third coating layer has a melting point of 50 ℃ or more and 80 ℃ or less.
Thus, the food packaging paper is excellent in water vapor barrier property and blocking resistance without deteriorating heat sealing suitability.
<9>
The food packaging paper according to the above <3>, wherein the styrene-butadiene-based copolymer resin of the first coating layer has a styrene-based monomer content of 70 mass% or more and 90 mass% or less.
Thus, the gas barrier property, flavor barrier property and folding processing adaptability of the food packaging paper become good.
<10>
The food wrap paper according to the above <4>, wherein the acrylic resin of the first coating layer is a styrene-acrylic copolymer resin or a styrene- (meth) acrylonitrile-acrylic copolymer resin.
Thus, the gas barrier property and flavor barrier property of the food packaging paper become good.
<11>
The food wrap paper according to the above <3>, wherein in the polyvinylidene chloride-based polymer resin of the second coating layer, a vinylidene chloride monomer in the resin is 85 mass% or more and 95 mass% or less, a monomer selected from (meth) acrylonitrile is 2 mass% or more and 10 mass% or less, and a monomer selected from methyl (meth) acrylate and ethyl (meth) acrylate is 0.5 mass% or more and 5 mass% or less.
Thus, the gas barrier property and the water vapor barrier property of the food packaging paper become good.
<12>
The food wrap paper according to the above <4>, wherein, in the polyvinylidene chloride-based polymer resin of the second coating layer, a vinylidene chloride monomer in the resin is 85 mass% or more and 95 mass% or less, a monomer selected from (meth) acrylonitrile is 2 mass% or more and 10 mass% or less, and a monomer selected from methyl (meth) acrylate and ethyl (meth) acrylate is 0.5 mass% or more and 5 mass% or less.
Thus, the gas barrier property and the water vapor barrier property of the food packaging paper become good.
<13>
The food wrap paper according to the above <3>, wherein the acrylic resin of the third coating layer is a styrene-acrylic copolymer resin comprising more than 50 mass% of a (meth) acrylic acid alkyl ester as an acrylic monomer and a copolymer of a (meth) acrylic acid alkyl ester and styrene.
Thus, the food wrap paper is excellent in water resistance, oil resistance, folding work adaptability and blocking resistance.
<14>
The food wrap paper according to the above <4>, wherein the acrylic resin of the third coating layer is a styrene-acrylic copolymer resin comprising more than 50 mass% of a (meth) acrylic acid alkyl ester as an acrylic monomer and a copolymer of a (meth) acrylic acid alkyl ester and styrene.
Thus, the food wrap paper is excellent in water resistance, oil resistance, folding work adaptability and blocking resistance.
<15>
The food wrap paper according to the above <1>, wherein the styrene monomer content of the styrene-butadiene copolymer resin of the first coating layer is 70 mass% or more and 90 mass% or less, the acrylic resin of the first coating layer is a styrene-acrylic copolymer resin or a styrene- (meth) acrylonitrile-acrylic copolymer resin, the vinylidene chloride monomer of the resin is 85 mass% or more and 95 mass% or less, the monomer selected from (meth) acrylonitrile is 2 mass% or more and 10 mass% or less, the monomer selected from (meth) methyl acrylate and ethyl (meth) acrylate is 0.5 mass% or more and 5 mass% or less, and the acrylic resin of the third coating layer is a styrene-acrylic copolymer resin.
Thus, the gas barrier property, the water vapor barrier property, the flavor barrier property, the folding processing adaptability and the blocking resistance of the food packaging paper become good.
<16>
The food wrap paper according to the above <15>, wherein the third coating layer further comprises paraffin wax.
Thus, the food packaging paper is excellent in water vapor barrier property and/or blocking resistance.
<17>
The food wrap paper according to the above <16>, wherein the wax of the third coating layer has a melting point of 50 ℃ or more and 80 ℃ or less.
Thus, the food packaging paper is excellent in water vapor barrier property and blocking resistance without deteriorating heat sealing suitability.
Claims (10)
1. A food wrap paper comprising a paper support, a first coating layer on one side of the paper support, a second coating layer on the outer side of the first coating layer with respect to the paper support, and a third coating layer on the outer side of the second coating layer with respect to the paper support,
the first coating layer contains kaolin and one or more than two selected from styrene-butadiene copolymer resin and acrylic resin as a binder,
the second coating layer contains a polyvinylidene chloride-based polymer resin having a vinylidene chloride monomer as a structural unit of the resin as a main component, and
The third coating layer contains an acrylic resin.
2. The food wrap paper according to claim 1, wherein the first coating layer contains one or two or more selected from styrene-butadiene-based copolymer resins or one or two or more selected from acrylic resins as a binder.
3. The food wrap paper according to claim 2, wherein the first coating layer contains one or more selected from styrene-butadiene-based copolymer resins as a binder, and a total content of the styrene-butadiene-based copolymer resins in the first coating layer is 40 parts by mass or more and 400 parts by mass or less per 100 parts by mass of kaolin in the first coating layer per one side of the paper support.
4. The food wrap paper according to claim 2, wherein the first coating layer contains one or more selected from acrylic resins as a binder, and a total content of the acrylic resins in the first coating layer is 40 parts by mass or more and 400 parts by mass or less per 100 parts by mass of kaolin in the first coating layer per one side of the paper support.
5. The food packaging paper according to any one of claims 1 to 4, wherein the polyvinylidene chloride-based polymer resin is a polyvinylidene chloride-based polymer resin in which a vinylidene chloride monomer in the resin is 85 mass% or more and 95 mass% or less.
6. The food wrap paper according to any one of claims 1 to 5, wherein the acrylic resin contained in the third coating layer is a styrene-acrylic copolymer resin.
7. The food wrap paper according to any one of claims 1 to 6, wherein the third coating layer further comprises paraffin wax.
8. The food wrap paper according to claim 7, wherein the paraffin wax of the third coating layer is a paraffin wax having a melting point of 50 ℃ or more and 80 ℃ or less.
9. The food wrap paper according to claim 3, wherein the styrene-butadiene-based copolymer resin of the first coating layer is a styrene-butadiene-based copolymer resin having a styrene monomer content of 70 mass% or more and 90 mass% or less in the copolymer resin.
10. The food wrap paper according to claim 4, wherein the acrylic resin of the first coating layer is a styrene-acrylic copolymer resin or a styrene- (meth) acrylonitrile-acrylic copolymer resin.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020-154407 | 2020-09-15 | ||
| JP2020154407 | 2020-09-15 | ||
| JP2021086241A JP2022048970A (en) | 2020-09-15 | 2021-05-21 | Food packaging paper |
| JP2021-086241 | 2021-05-21 | ||
| PCT/JP2021/026552 WO2022059324A1 (en) | 2020-09-15 | 2021-07-15 | Food packaging paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116034033A true CN116034033A (en) | 2023-04-28 |
Family
ID=80776025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180055771.9A Pending CN116034033A (en) | 2020-09-15 | 2021-07-15 | Food packaging paper |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20230069087A (en) |
| CN (1) | CN116034033A (en) |
| DE (1) | DE112021004880T5 (en) |
| WO (1) | WO2022059324A1 (en) |
Families Citing this family (2)
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|---|---|---|---|---|
| JP2023537263A (en) | 2020-07-30 | 2023-08-31 | ザ プロクター アンド ギャンブル カンパニー | Absorbent article packaging material containing natural fibers |
| WO2024090483A1 (en) * | 2022-10-27 | 2024-05-02 | 株式会社クラレ | Structure, method for producing structure, oil-resistant paper, gas barrier paper, flavor barrier paper and packaging material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013176950A (en) | 2012-02-29 | 2013-09-09 | Nippon Paper Industries Co Ltd | Paper-made barrier packaging material |
| JP5848477B1 (en) * | 2015-04-08 | 2016-01-27 | 大王製紙株式会社 | Fibrous casing and manufacturing method thereof |
| WO2016076130A1 (en) | 2014-11-12 | 2016-05-19 | 三井化学株式会社 | Aqueous dispersion, and laminate |
| JP6769210B2 (en) * | 2016-09-26 | 2020-10-14 | 王子ホールディングス株式会社 | Oil-resistant paper and its manufacturing method |
| JP7063814B2 (en) * | 2016-09-30 | 2022-05-09 | 日本製紙株式会社 | Paper barrier material |
| WO2019069963A1 (en) * | 2017-10-04 | 2019-04-11 | 日本製紙株式会社 | Barrier material |
-
2021
- 2021-07-15 CN CN202180055771.9A patent/CN116034033A/en active Pending
- 2021-07-15 DE DE112021004880.5T patent/DE112021004880T5/en active Pending
- 2021-07-15 WO PCT/JP2021/026552 patent/WO2022059324A1/en active Application Filing
- 2021-07-15 KR KR1020237004784A patent/KR20230069087A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230069087A (en) | 2023-05-18 |
| DE112021004880T5 (en) | 2023-06-29 |
| WO2022059324A1 (en) | 2022-03-24 |
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