JP2009233969A - Laminated body and packaging bag - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated body capable of suppressing deterioration of a heat seal layer due to the content and obtaining a packaging bag having no influence on the quality of the content. <P>SOLUTION: The laminated body is provided with a barrier layer (B) on one side of a polyester-based resin film (A), the polyester-based resin film (C) on the barrier layer (B), and a heat seal layer (D) having 10-100 μm thickness on the polyester-based resin film (C). The heat seal layer (D) applies a heat seal polyester-based resin solution having 5-100 poise of 40 mass% cyclohexanone solution viscosity at 25°C to the part for heat sealing with a screen printing method. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminate and a packaging bag using the laminate, and more specifically, is suitably used for filling a liquid or powder, and particularly a laminate suitably used for filling cosmetics and the same. It relates to the packaging bag used.

  Conventionally, a heat-sealable resin layer is laminated on a biaxially stretchable base film having heat resistance such as a biaxially stretched polypropylene film, a biaxially stretched polyester film, and a biaxially stretched polyamide film as a packaging bag for liquid filling. There is known a packaging bag formed by heat sealing the heat-sealable resin layer of the multilayer film formed into a bag shape. For example, JP 2003-119303 A discloses a film-like laminate comprising a biaxially stretched polyester film layer comprising polyethylene terephthalate and a thermoplastic polyester elastomer, and a polyolefin film layer having heat sealability. Further obtained liquid filling bags are disclosed. In such a liquid filling bag, a heat-sealable resin layer is formed on the entire innermost layer, and the liquid content is always in contact with the heat-sealable resin layer. For this reason, low-molecular additives from the heat-sealable resin layer bleed into the liquid content and affect the quality of the liquid content, or specific components in the liquid content sorb on the heat-sealable resin layer, Furthermore, there is a problem that a part of the specific component enters the heat-sealable resin layer and causes deterioration of the heat-sealable resin layer and deterioration of the liquid content.

  For example, when the contents are cosmetics, certain components having affinity for the packaging material in the composition (known oil-soluble vitamins represented by vitamins A, D, E and derivatives thereof, and other known oils) When a soluble medicinal component, aroma component, a known oil-soluble UV absorber, etc. are blended, the container is limited to a container using a material that does not sorb the specific component such as glass or biaxially stretched PET. In a container using other materials, such as polyethylene, at least a part of the specific component is sorbed on the inner surface layer of the packaging material, and as a result, the contents change over time or the inner surface There was a problem that the layer deteriorated.

Therefore, methods that use polyethylene terephthalate copolymer, polyacrylonitrile, ethylene vinyl alcohol copolymer, etc. as heat sealable resins that do not affect the quality of the contents, such as ethylene / vinyl acetate copolymer resin and acrylic resin Although methods such as providing a heat-sealable resin layer in the heat-sealing part have been studied, all of them are inferior in heat-sealability, sealing strength, pressure resistance, etc., and can be leaked particularly when filling liquid contents There was sex and was inappropriate. There is also a problem that it is expensive in terms of cost.
JP 2003-119303 A

  The object of the present invention is to solve the above-mentioned problems of the prior art, not to affect the quality of the contents, to suppress deterioration of the heat-sealable resin layer due to the contents, and to fill a substance containing liquid or oil-soluble components In addition, the present invention provides a laminate capable of obtaining a suitable packaging bag and a packaging bag using the laminate.

  In the present invention, (1) a polyester resin film (A) is provided with a barrier layer (B) on one surface, and a polyester resin film (C) is provided on the surface of the barrier layer (B). A laminate in which a heat seal layer (D) having a thickness of 10 to 100 μm is provided on a resin film (C), and the heat seal layer (D) has a viscosity of 5 mass% cyclohexanone at 25 ° C. of 5 It is related with the laminated body formed by apply | coating only the part which heat-sealable polyester resin solution of -100 poise to the heat seal.

  In the present invention, (2) the heat-sealable polyester resin has a glass transition temperature (Tg) of 50 ° C. to 100 ° C. and a glass transition temperature (Tg) of −30 ° C. The laminate according to (1) above, comprising at least one selected from polyester resins (d2) at 20 ° C.

  In the present invention, (3) the heat-sealable polyester resin has a glass transition temperature (Tg) of 50 to 100 ° C. and a polyester resin (d1) of 10 to 50% by weight and a glass transition temperature (Tg). The laminate according to (1) or (2) above, comprising 90 to 50% by weight of a polyester-based resin (d2) that is −30 to 20 ° C.

  Moreover, this invention is (4) The said barrier layer is formed with the vapor deposition film of aluminum foil or a metal oxide, The lamination | stacking as described in any one of said (1)-(3) characterized by the above-mentioned. About the body.

  The present invention also provides (5) an adhesive layer (between the polyester resin film (A) and the barrier layer (B), and between the barrier layer (B) and the polyester resin film (C), respectively. E) is provided, It relates to the laminated body as described in any one of said (1)-(4) characterized by the above-mentioned.

Moreover, the present invention is a two-component curable adhesive in which (6) the adhesive layer (E) includes a main agent mainly composed of a urethanized polyester resin and a curing agent mainly composed of a polyisocyanate resin, The laminate according to (5) above, wherein an adhesive having a compounding ratio (mass ratio) with the main agent / curing agent of 100/10 to 100/30 is applied.

  In addition, the present invention provides (7) a packaging bag, wherein the heat seal layer surfaces of the laminate according to any one of (1) to (6) are overlapped and heat sealed. About.

  The present invention also relates to (8) the packaging bag described in (7) above, wherein the packaging bag is for liquid filling.

  The present invention also relates to (9) the packaging bag according to (7), wherein the packaging bag is for powder filling.

  The present invention also relates to (10) the packaging bag according to any one of (7) to (9), wherein the packaging bag is for filling a substance containing an oil-soluble component.

  The present invention also relates to (11) the packaging bag according to (10), wherein the substance containing the oil-soluble component is a cosmetic.

  According to the present invention, there is provided a laminated body that does not affect the quality of the contents, can suppress deterioration of the heat-sealable resin layer due to the contents, and can obtain a packaging bag suitable for filling a liquid or powder, and A packaging bag using the same can be provided. Further, according to the present invention, substances containing oil-soluble components, for example, contents such as oil-soluble vitamins, oil-soluble ultraviolet absorbers, cosmetics, chemicals, and spices containing oil-soluble components such as aroma components. However, since the heat-sealable resin layer does not deteriorate and does not affect the quality of the contents, the packaging form is limited to glass containers and plastic containers that do not sorb the contents. Diversification can be achieved.

  Hereinafter, the present invention will be described in detail.

  The laminate of the present invention is provided with a barrier layer (B) on one surface of the polyester resin film (A), and a polyester resin film (C) on the surface of the barrier layer (B). A laminate in which a heat seal layer (D) having a thickness of 10 to 100 μm is provided on a resin film (C), and the heat seal layer (D) has a viscosity of 5 mass% cyclohexanone at 25 ° C. of 5 It is characterized in that a heat-sealable polyester resin solution of ˜100 poise is applied only to a portion to be heat-sealed by a screen printing method.

  In the laminate of the present invention, the polyester-based resin film (A) is a base film, and the thickness is not particularly limited but is preferably 5 to 50 μm. The polyester resin film (A) may be a stretched polyester resin film or an unstretched polyester resin film. The polyester-based resin constituting the polyester-based resin film (A) is preferably a grade that can withstand conditions such as heat and pressure when heat-sealing by a die roll method at the time of bag making.

  Examples of polyester resins include thermoplastic resins produced by polycondensation of one or more aromatic saturated dicarboxylic acids having a benzene nucleus as a basic skeleton such as terephthalic acid and one or more saturated dihydric alcohols. Polyester resins can be used. Examples of the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4,4-dicarboxylic acid, and other dicarboxylic acids. Examples of the saturated dihydric alcohol include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, and neopentyl glycol. Aliphatic glycols such as aliphatic glycol and cyclohexanedimethanol, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, naphthalenediol, and other aromatic diols can be used. In the present invention, the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, One or more aliphatic saturated dicarboxylic acids such as dodecanoic acid may be added and copolycondensed. In the present invention, other dihydric or polyhydric alcohols may be added to the saturated dihydric alcohol to perform copolycondensation.

  Specific examples of the polyester resin include thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, thermoplastic polybutylene terephthalate resin produced by polycondensation of terephthalic acid and tetramethylene glycol, terephthalic acid and Thermoplastic polycyclohexanedimethylene terephthalate resin produced by polycondensation with 1,4-cyclohexanedimethanol, thermoplastic polyethylene terephthalate resin produced by copolycondensation of terephthalic acid, isophthalic acid and ethylene glycol, terephthalic acid and ethylene glycol Polyethylene terephthalate resin, terephthalic acid, isophthalic acid, ethylene glycol, and propylene produced by copolycondensation of 1,4-cyclohexanedimethanol Thermoplastic polyethylene terephthalate resin produced by copolycondensation of a recall, polyester polyol resins, and other like can be used.

  In the laminate of the present invention, a barrier layer (B) is provided on one surface of the polyester resin film (A). Such a barrier layer (B) has a barrier property against oxygen gas and water vapor and protects the contents filled in the packaging bag from deterioration, and further has a barrier property against odors and preserves the contents. Maintains fragrance. Although the thickness in particular of this barrier layer (B) is not restrict | limited, 5-15 micrometers is preferable. The barrier layer (B) is formed of an aluminum foil or a metal oxide vapor deposition film. The metal oxide vapor deposition film is, for example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), A vapor deposition film formed by vapor-depositing a metal oxide such as titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) on one surface of the thin film can be used. Among these, an aluminum foil or a vapor-deposited film of a metal oxide such as silicon (Si) or aluminum (Al) is preferable. Examples of thin films for depositing metal oxides include polyethylene resins, polypropylene resins, cyclic polyolefin resins, fluorine resins, polystyrene resins, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride. Resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyamide resin such as various nylons, polyimide resin, polyaryl naphthalate resin Silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin, and other various resin films or films It is possible to use the door. Among these, a polyester resin film is awarded. In the present invention, as the metal oxide vapor deposition film, the metal to be used or the metal oxide is used in one kind or a mixture of two or more kinds, and the metal oxide vapor deposition film mixed with different materials. Can also be configured. The metal oxide vapor-deposited film may be, for example, a single-layer film or a two-layer metal oxide vapor-deposited film formed by a chemical vapor deposition method, a physical vapor deposition method, or a combination of both. It can be produced by forming a multilayer film or a composite film composed of the above. As the chemical vapor deposition method, for example, a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like is used. For example, physical vapor deposition methods such as a vacuum deposition method, a sputtering method, an ion plating method, and an ion cluster beam method are used. When the barrier layer (B) is formed of a metal oxide vapor-deposited film, that is, when the metal oxide is vapor-deposited on one side of the thin film, the metal oxide vapor-deposited surface is a polyester resin. Laminate so as to be in contact with the film (A).

  In the laminate of the present invention, a polyester resin film (C) is provided on the surface of the barrier layer (B). The polyester resin film (C) is the innermost layer of the packaging bag and is a part in contact with the contents, and the thickness is not particularly limited, but is preferably 5 to 50 μm. The polyester resin constituting the polyester resin film (C) is preferably a grade having few additives in consideration of the influence on the contents, and is a biaxially stretched polyester resin having no heat sealable property. Preferably there is. As this polyester-type resin, what was mentioned above as a polyester-type resin which comprises a polyester-type resin film (A) is used.

  In the present invention, a heat seal layer (D) having a thickness of 10 to 100 μm, preferably 20 to 60 μm, is provided on the polyester resin film (C). When the thickness of the heat seal layer (D) is less than 10 μm, the seal strength is low and the pressure resistance is insufficient, and when it exceeds 100 μm, delamination of the heat seal layer is likely to occur. Here, the thickness of the heat seal layer (D) is a thickness in a state where a heat sealable polyester resin solution is applied on the polyester resin film (C) and dried.

The heat seal layer (D) is screen-printed only on the portion where heat-sealing a heat-sealable polyester resin solution having a viscosity of 5 to 100 poise, preferably 10 to 50 poise, at 25 ° C. is 40% by mass cyclohexanone solution. Apply. When the solution viscosity is less than 5 poise, the sharpness of the edge portion of the part-coated pattern is impaired, and when it exceeds 100 poise, the wettability with respect to the polyester resin film (C) is deteriorated, and the heat-sealable polyester The transfer failure of the system resin occurs. The solution viscosity here is a value measured with a B-type viscometer at 25 ° C. using a cyclohexanone solution containing 40% by mass of a heat-sealable polyester resin.
The resin forming the heat seal layer (D) is mainly composed of a heat sealable polyester resin, and the polyester resin is the one described above as the polyester resin constituting the polyester resin film (A). Used.

The heat-sealable polyester resin preferably contains at least one selected from a polyester resin having a high glass transition temperature (Tg) and a polyester resin having a low glass transition temperature (Tg), and has a glass transition temperature (Tg) of 50. It is more preferable that it contains at least one selected from a polyester resin (d1) having a temperature of -100 ° C and a polyester resin (d2) having a glass transition temperature (Tg) of -30 to 20 ° C. It is even more preferable that both the polyester-based resin (d1) and the polyester-based resin (d2) are included in terms of achieving both the adhesive strength to the adhesive) and the high cohesive strength of the heat-sealed portion after heat sealing.
The glass transition temperature (Tg) of the polyester resin (d1) having a high glass transition temperature is preferably 50 to 100 ° C., more preferably 60 to 80 ° C. in order to develop a high cohesive force of the heat seal part. . The glass transition temperature (Tg) of the polyester resin (d2) having a low glass transition temperature is preferably −30 to 20 ° C., more preferably −10 in order to develop an adhesive force to the polyester resin film (C). -10 ° C.

  When the polyester-based resin (d1) and the polyester-based resin (d2) are used in combination, their blending ratio is 10 to 50% by weight for the polyester-based resin (d1) and 90 to 50% by weight for the polyester-based resin (d2). The polyester resin (d1) is preferably 10 to 30% by mass, and the polyester resin (d2) is more preferably 90 to 70% by mass.

  In the laminate of the present invention, the heat for the polyester resin film (C) can be obtained by blending the polyester resin having a high glass transition temperature and the polyester resin having a low glass transition temperature in the above ratio as described above. It becomes easy to achieve both the adhesive strength of the seal layer (D) and the cohesive strength of the heat seal portion, which is a measure of pressure resistance when the bag is formed. The polyester resin having a low glass transition temperature has high adhesive strength to the polyester resin film (C), but sufficient pressure resistance when formed into a bag shape cannot be obtained due to insufficient cohesive strength of the resin itself. On the other hand, a polyester resin having a high glass transition temperature is excellent in cohesive force, but has insufficient adhesion to the polyester resin film (C). Therefore, by blending them at an appropriate blending ratio, it is possible to achieve both adhesive force and cohesive force with respect to the polyester resin film (C).

  In the laminate of the present invention, the contact between the heat seal layer (D) and the content is suppressed by applying the heat sealable polyester resin solution only to the heat seal portion, and the quality of the content and the heat seal layer are changed. Can be prevented.

  The heat-sealable polyester resin solution is obtained by dissolving a heat-sealable polyester resin in a solvent, and the concentration of the heat-sealable polyester resin is appropriately adjusted, but the solution viscosity is in the range of 5 to 100 poise. If it is inside, the one where a solid content is higher is preferable. The solvent is not particularly limited as long as it dissolves the heat-sealable polyester resin. For example, aliphatic hydrocarbons such as hexane, cyclohexane, heptane, alcohols, N-methyl-2-pyrrolidone, γ- Polar aprotic solvents such as butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ethers such as tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone and cyclohexanone, ethyl acetate And esters such as propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.

  Among these, esters and ketones are preferable from the viewpoint of the solubility of the heat-sealable polyester resin and the solvent detachability after printing.

  In the present invention, the heat-sealable polyester resin solution is applied by a screen printing method. By applying by a screen printing method, a thick heat seal layer of 10 μm or more can be applied in one step on the polyester resin film (C). In a method other than the screen printing method, for example, in order to apply a thick heat seal layer having a thickness of 10 μm or more by a gravure printing method, printing must be repeated 5 to 10 times. Examples of the screen printing method include a flat screen printing method and a rotary screen printing method. Among these, the rotary screen printing method is a polyester resin in which a heat seal layer (D) having a thickness of 10 to 100 μm is continuously formed. The film (C) is preferable in that it can be easily part-coated in a lattice form on the film (C). As the shape of the package, there are many ones that are heat-sealed in three directions other than the folded side (three-side sealed bag) and ones that are heat-sealed in four directions (four-side sealed bag). Since these packages have a lattice shape when the film is unfolded, the rotary screen printing method uses a lattice-designed plate that matches this.

  The mechanism of the rotary screen printing machine is to make a metal hollow cylindrical screen plate with small holes according to the pattern in a cylindrical cylinder of metal, stainless steel, nickel, etc. This is a mechanism that is equipped with a metal squeegee (magnet roll), feeds ink into the screen with the pressure of compressed air, and prints by the rotary method. The feature of rotary screen printing is that printing is performed by the rotational movement of the plate in the same way as gravure printing, so that high-speed and endless printing is possible. In addition, since the thickness and the aperture ratio of the screen plate can be freely changed, it is possible to print up to a coating amount that is impossible with gravure printing, so that a thickness of 10 to 10 on the polyester resin film (C). A 100 μm heat seal layer (D) can be provided. In the rotary screen system, in the case of a plate shape, that is, a mesh, an aperture ratio, a cylinder thickness, and a lacquer plate, each factor of the lacquer thickness determines the coating amount, the sharpness of an image, and the like. The conditions for performing the rotary screen printing are appropriately selected, and there are a lacquer plate having 100 mesh, an aperture ratio of 11%, and a lacquer thickness of 90 μm.

  In the present invention, the method for laminating the polyester resin film (A), the barrier layer (B), and the polyester resin film (C) is not particularly limited, but known methods such as an extrusion lamination method and a dry lamination method can be used. Although it is used, a method of bonding using an adhesive by a dry lamination method or a non-solation lamination method is preferable. Specifically, an adhesive layer (E) may be provided between the polyester resin film (A) and the barrier layer (B) and between the barrier layer (B) and the polyester resin film (C). preferable.

  The adhesive layer (E) is made of an adhesive, and is not particularly limited as long as the adhesive is a laminate adhesive, and includes a main agent mainly composed of a urethanized polyester resin and a curing agent mainly composed of a polyisocyanate resin. A liquid curable adhesive is preferred. The compounding ratio (mass ratio) with the main agent / curing agent is preferably 100/10 to 100/30.

  The urethanized polyester resin that is the main component of the main agent is obtained, for example, by reacting a polyester polyol and an organic polyisocyanate with an NCO / OH (equivalent ratio) of less than 1, preferably 0.9 or less. Examples of the polyester polyol used include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or dialkyl esters thereof or mixtures thereof, and examples include ethylene glycol, propylene glycol, diethylene glycol, butylene. Glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, etc. Polyester polyol or polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone), etc., obtained by reacting with glycols or mixtures thereof And polyester polyols obtained by ring-opening polymerization of amines. Examples of the organic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2, Aliphatic diisocyanates such as 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate; 1,4-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethyl Cyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane Cycloaliphatic diisocyanates such as isocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane; m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4′-toluidine diisocyanate, dianidine diisocyanate, 4,4′-diphenyl ether diisocyanate, etc. Aromatic diisocyanates; 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3- Aromatic aliphatic diisocyanates such as 1,4-bis (1-isocyanate-1-methylethyl) benzene or mixtures thereof; triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanate benzene Organic triisocyanate such as 2,4,6-triisocyanate toluene; polyisocyanate monomer of organic tetraisocyanate such as 4,4′-diphenyldimethane-2,2′-5,5′-tetraisocyanate It is done.

  Examples of the polyisocyanate resin that is the main component of the curing agent include adducts, isocyanurates, and burettes derived from the above organic polyisocyanates. The adduct body can be produced by reacting each diisocyanate compound with a trihydric or higher alcohol. Examples of trihydric or higher alcohols include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexatriol, 1,2,4-butanetriol, sorbitol, pentaerythritol and the like.

An isocyanurate body consists of a trimer of each diisocyanate compound as shown by the following general formula (1).

  The burette body is represented by the formula R—NH—CO—NR—CO—NH—R, but after reacting two molecules of each diisocyanate compound with one molecule of water, another molecule of each diisocyanate compound is reacted. Or two molecules of each diisocyanate compound and one molecule of a primary amine compound can be reacted.

  In the laminate of the present invention, an adhesive layer (E) is provided between the polyester resin film (A) and the barrier layer (B), and between the barrier layer (B) and the polyester resin film (C). Although it is a preferable form to provide, it is not specifically limited as a method of producing such a laminated body. For example, first, an adhesive is applied to both sides of the barrier layer (B) to provide an adhesive layer (E), then a polyester resin film (A) is applied to one side of the adhesive layer (E), and the adhesive layer (E) A method comprising laminating a polyester resin film (C) on the other surface and providing a heat seal layer (D) on the polyester resin film (C) can be mentioned.

  In the present invention, the polyester resin film (A) can be back printed with an ink to provide an ink layer (F). Ink is a display ink, and prints product names, contents display, designs, etc. by gravure. In plastic laminated films that fill foods, the ink is stipulated by the Food Sanitation Law so that it does not touch food directly, and it is generally sandwiched in the opposite side of food or in a multilayer film .

As an embodiment of the present invention, a cross-sectional view of a laminate is shown in FIG. In the laminate of FIG. 1, an adhesive layer (E), a barrier layer (B), an adhesive layer (E), and a polyester resin film (C) are laminated on a polyester resin film (A) provided with an ink layer (F). It is a laminate formed by providing a heat seal layer (D) only on a portion where the heat seal layer (D) is heat sealed on the polyester resin film (C). Each layer in FIG. 1 is shown formally, and its thickness is not limited to FIG.
The packaging bag of the present invention is characterized in that the heat seal layer (D) surface of the laminate is opposed and heat sealed. The heat sealing method is a method in which a heated metal is pressed against the superimposed heat seal layer (D) directly or through a heat-resistant film or a buffer material and welded by heat conduction. The heat seal method includes a hot plate seal (bar seal), a rotary roll seal, a belt seal (band seal), and a fusing seal. Bar seals are the most common method using hot plates heated to a constant temperature. The conditions for heat sealing vary depending on the type of sealant or heat sealing method selected, but generally the hot plate is heated to 180-220 ° C.

  The form of a packaging bag is not specifically limited, For example, various forms, such as a three-side seal bag, a four-side seal bag, a gusset packaging bag, a pillow packaging bag, are illustrated. Common forms are a three-sided seal bag, a four-sided seal bag, and the like, which are produced using, for example, a known die roll type automatic filling and packaging machine.

  The package of the present invention thus produced can be used for filling various articles, but is a packaging bag that does not affect the quality of the contents and suppresses the deterioration of the heat-sealable resin layer due to the contents. Therefore, it is possible to fill the contents of liquids and powders, especially for cosmetics and chemicals containing oil-soluble ingredients that are easy to sorb on the heat-seal resin layer of packaging bags, and also for packaging of contents such as spices Also suitable.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the examples and comparative examples, “part” and “%” mean “part by mass” and “% by mass” unless otherwise specified.

Reference example 1
100 parts polyester resin (Toyobo Co., Ltd., trade name: Byron 200, Mn = 17000) having a glass transition temperature (Tg) of 67 ° C in a four-necked flask, polyester resin (Tyobo Co., Ltd., manufactured by Toyobo Co., Ltd.) , Trade name: Byron 630, Mn = 23000) and 600 parts of cyclohexanone were added and completely dissolved at 50 ° C. over 1 hour to obtain a heat-sealable polyester resin solution (hereinafter referred to as heat-sealant HS-1). Created.). It was 80 poise when the solution viscosity of 25 degreeC of heat-sealant HS-1 was measured with the B-type viscosity meter.

Reference example 2
Reference Example 1 except that 100 parts of a polyester resin having a Tg of 67 ° C. (trade name: Byron 240, Mn = 15000) manufactured by Toyobo Co., Ltd. is used instead of 100 parts of the polyester resin having a Tg of 67 ° C. in Reference Example 1. In the same manner as in No. 1, a heat-sealable polyester resin solution (hereinafter referred to as heat-seal agent HS-2) was prepared. It was 70 poise when the solution viscosity of 25 degreeC of heat-sealing agent HS-2 was measured with the B-type viscosity meter.

Reference example 3
To a four-necked flask, 400 parts of a polyester resin having a glass transition temperature (Tg) of 67 ° C. (manufactured by Toyobo Co., Ltd., trade names: Byron 200, Mn = 17000) and 600 parts of cyclohexanone are added, and the mixture is heated at 50 ° C. for 1 hour. Completely dissolved, a heat-sealable polyester resin solution (hereinafter referred to as heat-seal agent HS-3) was prepared. It was 70 poise when the solution viscosity of 25 degreeC of heat-sealant HS-3 was measured with the B-type viscosity meter.

Reference example 4
To a four-necked flask, 400 parts of a polyester resin having a glass transition temperature (Tg) of 7 ° C. (trade name: Byron 630, Mn = 23000) manufactured by Toyobo Co., Ltd. and 600 parts of cyclohexanone are added, and the mixture is heated at 50 ° C. for 1 hour. Completely dissolved, a heat-sealable polyester resin solution (hereinafter referred to as heat-seal agent HS-4) was prepared. It was 80 poise when the solution viscosity of 25 degreeC of heat sealant HS-4 was measured with the B-type viscosity meter.

Reference Example 5
In a four-necked flask, 400 parts of an ethylene vinyl acetate copolymer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., trade name: Everflex 45X, Mn = 31000) having a glass transition temperature (Tg) of −28 ° C. and 600 parts of cyclohexanone In addition, it was completely dissolved at 50 ° C. over 1 hour to prepare a heat-sealable resin solution (hereinafter referred to as heat-sealant HS-5). It was 80 poise when the solution viscosity of 25 degreeC of heat-sealing agent HS-5 was measured with the B-type viscosity meter.

Reference Example 6
To a four-necked flask, 400 parts of an acrylic resin having a glass transition temperature (Tg) of 45 ° C. (manufactured by Soken Chemical Co., Ltd., trade name: Thermolac EF-32, Mn = 60000) and 600 parts of cyclohexanone were added, and It was completely dissolved over 1 hour to prepare a heat sealable resin solution (hereinafter referred to as heat sealant HS-6). It was 40 poise when the solution viscosity of 25 degreeC of heat-sealing agent HS-6 was measured with the B-type viscosity meter.

Reference Example 7
200 parts of polyester resin (trade name: Byron 220, Mn = 3000) having a glass transition temperature (Tg) of 53 ° C. in a four-necked flask and Tg of 10 ° C. (made by Toyobo Co., Ltd.) , Trade name: Byron GK680, Mn = 6000) and 200 parts of cyclohexanone were added and completely dissolved at 50 ° C. over 1 hour to obtain a heat-sealable polyester resin solution (hereinafter referred to as heat-sealant HS-7). Created.). It was 3 poise when the solution viscosity of 25 degreeC of heat-sealant HS-7 was measured with the B-type viscosity meter.

Reference Example 8
360 parts polyester resin having a glass transition temperature (Tg) of -17 ° C in a four-necked flask (trade name: Byron 516, Mn = 30000) manufactured by Toyobo Co., Ltd., polyester resin having a Tg of 67 ° C (Toyobo Co., Ltd.) Manufactured, trade name: Byron 270, Mn = 23000) and cyclohexanone 600 parts are added and completely dissolved at 50 ° C. over 1 hour to obtain a heat-sealable polyester resin solution (hereinafter referred to as heat-sealant HS-). 8). It was 120 poise when the solution viscosity of 25 degreeC of heat-sealing agent HS-8 was measured with the B-type viscosity meter.

Example 1
Urethane polyester two-component curable adhesive (trade name: TM-585 / CAT, manufactured by Toyo Morton Co., Ltd.) on both sides of a 9 μm thick aluminum foil (trade name: AlN30H-0, manufactured by Sun Aluminum Industry Co., Ltd.) -10) was applied to a dry coating thickness of 3.5 μm, and a 12 μm polyester film (manufactured by Toyobo Co., Ltd., trade name: Toyobo Ester Film E5102) was laminated thereon by a dry lamination method. Only on the heat seal part of one polyester film surface of this laminate, heat sealant HS-1 is applied with a rotary screen system, 100 mesh, hole area ratio 11%, lacquer thickness 90 μm plate speed 50 m / min. It apply | coated so that dry coating thickness might be set to 40 micrometers on conditions, the heat seal layer was formed in the grid | lattice form as shown in FIG. 2, and the laminated body 1 was created.

Example 2
12 μm thick aluminum vapor-deposited polyester film (Toyo Metallizing Co., Ltd., trade name: VM-1310) on both sides of urethanated polyester-based two-component curable adhesive (Toyo Morton Co., Ltd., trade name: TM-250HV / CAT) -RT86) was applied so that the dry coating thickness was 3.5 μm, and a 12 μm-thick polyester film (manufactured by Toyobo Co., Ltd., trade name: Toyobo Ester Film E5102) was laminated thereon by a dry lamination method. Next, only on the heat seal part of the polyester film surface laminated on the aluminum vapor deposition surface side, heat sealant HS-2 is applied with a rotary screen system, 100 mesh, hole area ratio 11%, lacquer thickness 90 μm plate speed 50 m / Min. Was applied so that the dry coating thickness was 40 μm, a heat seal layer was formed, and laminate-2 was prepared.

Example 3
12 μm thick silica-deposited polyester film (Mitsubishi Resin Co., Ltd., trade name: Tech Barrier T) on both sides of urethanated polyester-based two-component curable adhesive (Toyo Morton Co., Ltd., trade name: TM-250HV / CAT-) RT86) was applied to a dry coating thickness of 3.5 μm, and a 12 μm thick polyester film (manufactured by Toyobo Co., Ltd., trade name: Toyobo Ester Film E5102) was laminated thereon by a dry lamination method. Subsequently, only the heat seal part of the polyester film surface laminated | stacked on the silica vapor deposition surface side was apply | coated with the rotary screen system so that the dry application thickness might be set to 40 micrometers, and the laminated body-3 was created. .

Example 4
A laminate 4 was prepared in the same manner as in Example 1 except that the heat sealant HS-3 was used instead of the heat sealant HS-1. The coating amount of the heat seal layer was 40 μm in dry coating thickness.

Example 5
A laminate 5 was prepared in the same manner as in Example 1 except that the heat sealant HS-4 was used instead of the heat sealant HS-1. The coating amount of the heat seal layer was 40 μm in dry coating thickness.

Comparative Example 1
A laminate-6 was prepared in the same manner as in Example 1 except that the heat sealant HS-5 was used instead of the heat sealant HS-1. The coating amount of the heat seal layer was 40 μm in dry coating thickness.

Comparative Example 2
A laminate 7 was prepared in the same manner as in Example 1 except that the heat sealant HS-6 was used instead of the heat sealant HS-1. The coating amount of the heat seal layer was 40 μm in dry coating thickness.

Comparative Example 3
A laminate-8 was prepared in the same manner as in Example 1 except that the rotary screen system conditions were changed so that the heat seal layer was applied in a dry coating thickness of 5 μm. The coating amount of the heat seal layer was 5 μm in dry coating thickness.

Comparative Example 4
A laminate 9 was prepared in the same manner as in Example 1 except that the heat sealant HS-7 was used instead of the heat sealant HS-1. The coating amount of the heat seal layer was 40 μm in dry coating thickness. The heat seal part of the obtained laminate 9 lacked sharp edges.

Comparative Example 5
A laminate 10 was produced in the same manner as in Example 1 except that the heat sealant HS-8 was used instead of the heat sealant HS-1. As for the coating amount of the heat seal layer, the dry mass dry coating thickness was 40 μm. As for the heat seal part of the obtained laminated body-10, the uniform coating surface was not obtained.

Comparative Example 6
A laminate 11 was prepared by performing the same operation as in Example 1 except that the operation of applying the heat sealant in Example 1 was repeated three times. The coating amount of the heat seal layer was 120 μm in dry coating thickness.

Comparative Example 7
Urethane polyester two-component curable adhesive (trade name: TM-585 / CAT, manufactured by Toyo Morton Co., Ltd.) on both sides of a 9 μm thick aluminum foil (trade name: AlN30H-0, manufactured by Sun Aluminum Industry Co., Ltd.) -10) was applied so that the dry coating thickness was 3.5 μm, and a 12 μm thick polyester film (manufactured by Toyobo Co., Ltd., trade name: Toyobo Ester Film E5102) was laminated thereon by a dry lamination method. One side of the polyester film of this laminate was coated with a urethanized polyester-based two-component curable adhesive (trade name: TM-585 / CAT-10, manufactured by Toyo Morton Co., Ltd.) so that the dry coating thickness was 3.5 μm. On top of that, a polyethylene film having a thickness of 50 μm (trade name: TUX L-LDPE film FC-D # 50, manufactured by Tosero Co., Ltd.) was laminated by a dry laminating method to prepare a laminate-12. .

Comparative Example 8
Instead of polyethylene film (trade name: TUX L-LDPE film FC-D # 50, manufactured by Tosero Co., Ltd.), a polypropylene film (product name: GHC # 40, manufactured by Tosero Co., Ltd.) having a thickness of 40 μm is used. Except for using it, the same operation as in Comparative Example 7 was carried out to prepare a laminate-13.

The laminates 1 to 13 obtained in Examples 1 to 5 and Comparative Examples 1 to 8 were evaluated in the following manner. The results are shown in Table 1.

(Acid resistance test)
After the heat-seal layer surfaces of the obtained laminates were opposed to each other, they were heat-sealed at 150 ° C., 2 kg / cm, and 1 second to prepare a 10 × 6 cm ² pouch. After 150 cc of vinegar having a concentration of 2% was filled, the opening was sealed under the same heat sealing conditions as above. The pouch was heat sterilized at 30 rpm, 135 ° C. for 30 minutes under a pressure of 0.3 Mpa, and the seal strength of the heat-sealed portion was measured before and after the heat sterilization. The seal strength is measured by cutting the sealed pouch from the edge portion toward the center of the pouch into a width of 15 mm and a length of 50 mm, and using a tensile tester (manufactured by Tester Sangyo) at 20 ° C. and 65% RH atmosphere. Lower, peeling angle T type, peeling speed 30cm / min.

(Aging stability test)
As an ultraviolet absorber, 0.05 part of 2-ethylhexyl paramethoxycinnamate, 0.05 part of glyceryl tri-2-ethylhexanoate as an ester oil, and polyoxyethylene alkyl ether phosphate (8E) as a surfactant O.) 0.02 part, polyoxyethylene sorbitan monooleate (20E.O.) 0.01 part, sorbitan sesquioleate 0.03 part, alcohol, 10 parts ethanol, water 89. 84 parts were mixed and the mixed solution assumed by cosmetics was created.

After the heat-seal layer surfaces of the obtained laminates were opposed to each other, they were heat-sealed under the conditions of 150 ° C., 2 kg / cm, and 1 second to prepare a 10 × 6 cm ² pouch, and the above-mentioned mixture as the contents After filling 3.5 cc of the solution, the opening was sealed under the same heat sealing conditions as described above. After the pouch was stored at 40 ° C. for 1 month, the residual ratio of the UV absorber in the mixed solution was measured using a spectrophotometer (Shimadzu UV-2500PC) in order to estimate the amount of the UV absorber absorbed on the pouch. (%) Was measured.

  From Table 1, it can be seen that Examples 1 to 5 show high seal strength before and after the heat sterilization treatment, and the contents are not adsorbed on the heat seal layer, so that deterioration can be suppressed. It can be seen that Comparative Example 1 using ethylene vinyl acetate copolymer resin as the heat sealant is inferior in seal strength. It can be seen that Comparative Example 2 using an acrylic resin as the heat sealant is inferior in seal strength. It can be seen that Comparative Example 3 in which the heat seal layer is thin is inferior in seal strength. It can be seen that Comparative Example 4 using a heat-sealable polyester resin solution having a low viscosity is inferior in appearance of the coated surface. It can be seen that Comparative Example 5 using a heat-sealable polyester resin solution having a high viscosity is inferior in appearance of the coated surface. It can be seen that Comparative Example 6 having a thick heat seal layer is inferior in sealing strength after the heat sterilization treatment. In Comparative Examples 7 and 8 in which the heat seal layer is provided on the entire surface of the polyester film, it is understood that the contents are adsorbed on the heat seal layer and the deterioration cannot be suppressed.

It is sectional drawing which shows one Example of the laminated body of this invention. It is the schematic which shows an example of the coating pattern of a heat seal agent.

Claims (11)

  A barrier layer (B) is provided on one surface of the polyester resin film (A), a polyester resin film (C) is provided on the surface of the barrier layer (B), and the polyester resin film (C) is provided on the polyester resin film (C). A heat-sealing property in which a heat seal layer (D) having a thickness of 10 to 100 μm is provided, and the heat seal layer (D) has a 40 mass% cyclohexanone solution viscosity at 25 ° C. of 5 to 100 poise. A laminate comprising a polyester resin solution applied to only a portion to be heat-sealed by a screen printing method.   The heat-sealable polyester resin includes a polyester resin (d1) having a glass transition temperature (Tg) of 50 to 100 ° C. and a polyester resin (d2) having a glass transition temperature (Tg) of −30 to 20 ° C. The laminate according to claim 1, comprising at least one selected.   The heat-sealable polyester resin is a polyester having a glass transition temperature (Tg) of 50 to 100 ° C. and a polyester resin (d1) of 10 to 50% by weight and a glass transition temperature (Tg) of −30 to 20 ° C. The laminate according to claim 1, comprising 90 to 50% by weight of a resin based resin (d2).   The said barrier layer is formed with the vapor deposition film of the aluminum foil or the metal oxide, The laminated body as described in any one of Claims 1-3 characterized by the above-mentioned.   An adhesive layer (E) is provided between the polyester resin film (A) and the barrier layer (B), and between the barrier layer (B) and the polyester resin film (C). The laminate according to any one of claims 1 to 4.   The adhesive layer (E) is a two-component curable adhesive containing a main component mainly composed of a urethanized polyester resin and a curing agent mainly composed of a polyisocyanate resin, and a mixing ratio of the main agent / curing agent. 6. The laminate according to claim 5, wherein an adhesive having a (mass ratio) of 100/10 to 100/30 is applied.   A packaging bag, wherein the heat-seal layer surfaces of the laminate according to any one of claims 1 to 6 are opposed to each other and heat-sealed.   The packaging bag according to claim 7, wherein the packaging bag is for filling a liquid material.   The packaging bag according to claim 7, wherein the packaging bag is for powder filling.   The packaging bag according to any one of claims 7 to 9, wherein the packaging bag is for filling a substance containing an oil-soluble component.   The packaging bag according to claim 10, wherein the substance containing the oil-soluble component is a cosmetic.

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