WO2020004287A1 - Bouteille vide à soufflage direct dotée d'une couche de lubrifiant liquide sur la surface interne, et aliment émulsifié de type huile dans l'eau en bouteille - Google Patents

Bouteille vide à soufflage direct dotée d'une couche de lubrifiant liquide sur la surface interne, et aliment émulsifié de type huile dans l'eau en bouteille Download PDF

Info

Publication number
WO2020004287A1
WO2020004287A1 PCT/JP2019/024810 JP2019024810W WO2020004287A1 WO 2020004287 A1 WO2020004287 A1 WO 2020004287A1 JP 2019024810 W JP2019024810 W JP 2019024810W WO 2020004287 A1 WO2020004287 A1 WO 2020004287A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
liquid
resin layer
bottle
oxygen barrier
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.)
Ceased
Application number
PCT/JP2019/024810
Other languages
English (en)
Japanese (ja)
Inventor
啓佑 丹生
洋介 阿久津
智啓 田口
小松　威久男
長野　学
翔太 川▲崎▼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kewpie Corp
Toyo Seikan Group Holdings Ltd
Mebius Packaging Co Ltd
Toyo Seikan Co Ltd
Original Assignee
Toyo Seikan Kaisha Ltd
Kewpie Corp
Mebius Packaging Co Ltd
Toyo Seikan Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toyo Seikan Kaisha Ltd, Kewpie Corp, Mebius Packaging Co Ltd, Toyo Seikan Co Ltd filed Critical Toyo Seikan Kaisha Ltd
Publication of WO2020004287A1 publication Critical patent/WO2020004287A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/60—Salad dressings; Mayonnaise; Ketchup
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
    • B65D1/32—Containers adapted to be temporarily deformed by external pressure to expel contents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
    • B65D85/72—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for edible or potable liquids, semiliquids, or plastic or pasty materials

Definitions

  • the present invention particularly relates to a direct blow empty bottle in which a viscous hydrated substance such as various dressings, mayonnaise, and mayonnaise-like foods is filled and used as a content.
  • Plastic is widely used in various applications because it is easy to mold and can be easily molded into various forms.
  • a direct blow bottle in which the inner surface of the container wall is formed of an olefin resin such as low-density polyethylene is a container for accommodating viscous slurry-like or paste-like contents from the viewpoint that the contents are easily squeezed out. It is preferably used as
  • Patent Documents 1 to 3 propose a plastic container having a liquid layer formed on an inner surface in contact with the contents.
  • This container has succeeded in significantly improving the slipperiness with respect to the contents by forming a liquid layer (lubricating liquid layer) of a liquid immiscible with the contents as compared with the conventionally known ones.
  • a liquid layer lubricating liquid layer
  • the contents can be quickly discharged out of the container without adhering or remaining on the inner wall of the container.
  • Patent Literature 4 has a lubricant layer on the surface of a plastic base layer and suppresses the diffusion of a lubricant under the base layer.
  • a multilayer container provided with a liquid diffusion preventing layer for blocking.
  • the liquid diffusion preventing layer can be formed of a typical ethylene-vinyl alcohol copolymer as an oxygen barrier resin, it is possible to originally secure sufficient oxygen barrier properties.
  • the water diffusion preventing layer Since such a liquid diffusion preventing layer is formed at a position close to the inner surface of the container, when the content is a water-containing substance, the water diffusion preventing layer depends on the ethylene content of the ethylene / vinyl alcohol copolymer in the liquid diffusion preventing layer. However, there is still room for improvement in that it may be deteriorated due to the influence of and may not be able to exhibit sufficient oxygen barrier properties. In addition, the decrease in the oxygen barrier property causes not only the oxidative deterioration of the contents but also the oxidative deterioration of the lubricating liquid layer formed on the inner surface of the container. There is also a problem that the effect cannot be sufficiently exhibited.
  • Patent Literature 5 discloses a container in which a liquid film (lubricating liquid layer) of an oily liquid is formed on the inner surface. It has been proposed to provide two oxygen barrier layers comprising ethylene vinyl alcohol having a certain density and a glass transition point at a certain distance from each other. That is, of the two oxygen barrier layers, the oxygen barrier layer (first oxygen barrier resin layer) provided on the side closer to the inner surface resin layer serving as the base of the liquid layer exhibits the oxygen barrier property and the liquid diffusion preventing function, The oxygen barrier layer (second oxygen barrier resin layer) located on the side away from the inner resin layer has a layer structure that mainly exhibits oxygen barrier properties.
  • the first oxygen barrier resin layer effectively prevents the liquid formed on the inner surface resin layer from permeating and diffusing, and at the same time, develops the oxygen barrier property. Even if the barrier property is deteriorated, a decrease in the oxygen barrier property can be effectively avoided because the second oxygen barrier resin layer is present.
  • an object of the present invention is to provide a direct blow bottle containing a water-containing substance and having a lubricating liquid layer on the inner surface of the bottle, wherein the bottle wall has an oxygen barrier layer having a liquid diffusion preventing function, and Oxidative degradation of the lubricating liquid layer provided on the inner surface of the bottle is effectively suppressed, and in combination with suppression of the penetration of the lubricating liquid into the bottle, the lubricating liquid layer stably improves the lubricity of water-containing substances over a long period of time.
  • An object of the present invention is to provide a direct blow empty bottle that can be developed.
  • a lubricating liquid coating layer formed of a lubricating liquid for improving lubricity with respect to the water-containing substance, an inner resin layer serving as a base of the coating layer, and a liquid diffusion preventing oxygen for preventing diffusion of the lubricating liquid
  • the barrier layer, the oxygen absorption layer, the oxygen barrier layer and the outer resin layer are formed in this order from the inner surface to the outer surface
  • the water-containing substance is an oil-in-water emulsified food having a viscosity of 30 Pa ⁇ s or more
  • the inner resin layer is formed of low-density polyethylene, and the inner resin layer is formed to have a thickness of 15 to 45% by mass relative to the total mass of the bottle excluding the lubricant coating layer.
  • a direct blow empty bottle is provided.
  • the liquid diffusion preventing oxygen barrier layer is made of an ethylene / vinyl alcohol copolymer.
  • the liquid diffusion preventing oxygen barrier layer contains an ethylene / vinyl alcohol copolymer, low density polyethylene, and a compatibilizer.
  • the lubricant coating layer is formed with a thickness of 1.0 to 35.0 g / m 2 .
  • An oily liquid is used as the lubricating liquid.
  • Edible oil is used as the oily liquid.
  • the vegetable oil contained in the emulsified food is selected as the edible oil.
  • the inner resin layer is free of a lubricant, or the amount of the lubricant added is smaller than that of the outer resin layer. (8) Part of the lubricating liquid has penetrated into the inner resin layer.
  • the direct blow empty bottle of the present invention is used for an application in which a hydrated substance is filled as a content, and a lubricant coating layer formed by a lubricant for improving lubricity with respect to the hydrated substance has a bottle.
  • the bottle wall which is provided on the inner surface and has such a lubricating liquid coating layer on the inner surface, has an inner resin layer, a liquid diffusion preventing oxygen barrier layer, an oxygen absorption layer, an oxygen barrier And an outer resin layer.
  • the liquid diffusion preventing oxygen barrier layer is disposed below the inner resin layer which is the base of the lubricating liquid coating layer. . Therefore, the penetration and diffusion of the lubricating liquid forming the lubricating liquid coating layer into the bottle are effectively suppressed, and the temporal disappearance of the lubricating liquid coating layer is effectively avoided.
  • the liquid diffusion preventing oxygen barrier layer contains an ethylene / vinyl alcohol copolymer exhibiting oxygen barrier properties, and the outer surface side of the liquid diffusion preventing oxygen barrier layer has a function of preventing permeation of oxygen. Having two layers, namely, an oxygen absorbing layer and an oxygen barrier layer. Therefore, even when the oxygen barrier property of the liquid diffusion preventing oxygen barrier layer disposed at a position close to the content that is a water-containing substance is reduced by moisture, the above-described oxygen absorption layer and oxygen barrier layer are present. Therefore, sufficient oxygen barrier properties are maintained.
  • the inner resin layer is formed of low-density polyethylene, it exhibits appropriate permeability and wettability to a lubricating liquid.
  • Such an inner resin layer is formed to have a thickness of 15 to 45% by mass with respect to the total mass of the bottle excluding the lubricant coating layer. Therefore, the lubricating liquid coating layer is widely distributed so as to cover the entire inner resin layer, and the lubricating liquid permeates into the inner resin layer in an appropriate amount. It does not fall off and is kept stable.
  • the loss of the lubricating liquid coating layer due to permeation into the bottle, the deterioration of the properties due to oxidative deterioration are effectively prevented, and the falling off from the inner surface of the bottle is also effectively prevented.
  • the lubricating liquid coating layer stably exhibits a decrease in lubricity, and the viscous hydrated substance can always be smoothly discharged.
  • the direct-blow empty bottle of the present invention which is used by being filled with a hydrated substance, has a lubricating liquid coating layer, an inner resin layer, a liquid diffusion preventing oxygen barrier layer, a regrind layer, from the inner surface side to the outer surface side of the bottle. It has an oxygen absorbing layer, an oxygen barrier layer and an outer resin layer.
  • the water-containing substance to be filled as the content is not particularly limited as long as it contains water, and may be various foods, cosmetics, pharmaceuticals, and the like.
  • oil-in-water emulsified foods such as various dressings, mayonnaise or mayonnaise-like foods, and oil-in-water emulsified foods containing ingredients are suitable.
  • the hydrous substance in which the effect of the present invention is maximized is, of course, a viscous substance.
  • the viscosity at 25 ° C. of the above-mentioned various hydrous substances is 30 Pa ⁇ s or more. Is a substance.
  • mayonnaise in order to be able to most effectively avoid the deterioration of food quality due to the lubricating liquid described below, mayonnaise, mayonnaise-like food, oil-in-water emulsion such as oil-in-water emulsion food containing ingredients. Food is most suitable as a hydrated substance to be filled into empty bottles.
  • the lubricating liquid coating layer provided on the inner surface of the above-described empty bottle of the present invention is a lubricating liquid that improves lubricity with respect to the above-mentioned hydrated substance, that is, a liquid that exhibits water repellency with respect to the hydrated substance.
  • This is a layer formed by applying to a layer (that is, the inner surface of an empty bottle).
  • Such lubricating liquids are typically fluorinated surfactants, silicone oils, or various oily liquids, such as fatty acid triglycerides, edible oils, etc., provided that they are high boiling liquids (for example, having a boiling point of 200 ° C. or higher). It is a target.
  • an oily liquid that does not adversely affect the human body or the flavor of the food, particularly an edible oil is preferably used.
  • the above-mentioned edible oils include soybean oil, rapeseed oil, olive oil, rice oil, corn oil, rapeseed oil, sesame oil, palm oil, castor oil, avocado oil, coconut oil, almond oil, walnut oil, maize oil, etc.
  • Edible vegetable oils and fats, and MCT medium chain fatty acid triglyceride
  • the edible vegetable oils and fats contained in such an oil-in-water emulsified food even when discharged together with such an emulsified food, its flavor, etc. It is optimal in that it does not impair the quality.
  • the application of the lubricating liquid to the inner resin layer surface is performed by spraying the lubricating liquid supply nozzle inserted into the empty bottle after the direct blow molding.
  • the lubricating liquid coating layer usually has a liquid amount of 1.0 to 35.0 g / m 2 , preferably 1.5 to 25.0 g / m 2 , and more preferably 5 to 20.0 g / m 2. Is formed in a thickness falling within the range. That is, if the amount of the liquid is small, sufficient lubricity cannot be imparted to the hydrated substance as the content, while if the amount of the liquid is excessively large, the liquid easily falls off and the like. This is because there is a possibility that the fluctuation of the diameter becomes large, and it becomes impossible to secure stable lubrication.
  • a lubricating liquid is blended in a resin composition for forming an inner resin layer, and a lubricating liquid layer is formed by bleeding the lubricating liquid from the inner resin layer. It is difficult to adjust the thickness of the lubricating liquid layer on the surface (the amount of the lubricating liquid). For this reason, in the present invention, means for coating a lubricating liquid on the inner resin layer by spraying is adopted.
  • the inner resin layer that forms the inner surface of the direct blow empty bottle of the present invention is a layer serving as a base of the above-mentioned lubricating liquid coating layer, and therefore has a high lubricating liquid. It is necessary that the lubricating liquid has a property of adequately penetrating while exhibiting wettability. From such a viewpoint, in the present invention, the inner resin layer is formed of low-density polyethylene.
  • low-density polyethylene is a polyethylene having a density of 0.91 to 0.93 g / cm 3 , and the inner resin layer formed using such low-density polyethylene has the above-described properties.
  • This is a layer suitable as a base for the lubricating liquid coating layer.
  • a medium-density or high-density polyethylene whose density is larger than the above range, since the lubricating liquid does not sufficiently penetrate into the inner resin layer, for example, the anchor effect is low, and the lubricating liquid coating layer having a certain thickness may be retained. It will be difficult.
  • the inner resin layer is formed by using an ultra-low density polyethylene having a density lower than the above range, a large amount of the lubricating liquid penetrates, and as a result, a large amount of the lubricating liquid needs to be sprayed.
  • the liquid may fall off, or the thickness of the lubricating liquid coating layer may decrease with time, making it difficult to form a lubricating liquid coating layer having a stable thickness.
  • an olefin resin other than polyethylene, such as polypropylene is used, the wettability to a lubricating liquid, such as vegetable oil, is poorer than that of polyethylene, and a certain thickness so as to cover the entire surface of the inner resin layer. This makes it difficult to form a lubricant coating layer.
  • melt flow rate (MFR) at 190 ° C. is generally in the range of 0.3 to 1.0 g / 10 min.
  • a known additive for example, a bleeding additive such as a lubricant
  • a bleeding additive such as a lubricant
  • the inner resin layer using LDPE, in which the amount of such a bleeding additive that reduces the wettability is small (for example, the amount of the additive is 500 ppm or less), in particular, a lubricant-free LDPE.
  • commercially available LDPE may contain a lubricant typified by a fatty acid amide for the purpose of ensuring releasability.
  • LDPE Even in such a lubricant LDPE, if the compounding amount is 500 ppm or less, particularly less than 300 ppm, it can be used as it is as an LDPE for forming the inner resin layer, and if the compounding amount is large, for example, a lubricant-free It can be blended with LDPE and used for forming the inner resin layer.
  • LDPE which is commercially available without a lubricant is expensive and is suitable for applications such as pharmaceuticals, but is not suitable for food applications containing mayonnaise or mayonnaise-like food in terms of cost.
  • the inner resin layer may be formed of LDPE in which a small amount of lubricant is compounded, and the amount of the lubricant in such an inner resin layer is compounded in the outer resin layer described later. Less than the amount of lubricant.
  • the inner resin layer is formed to have a thickness of 15 to 45% by mass, preferably 20 to 40% by mass, based on the total weight of the bottle excluding the lubricant coating layer. That is, when the thickness of the inner resin layer is smaller than the above range, during direct blow molding, disadvantages such as breakage are likely to occur at the pinch-off at the end of the melt-extruded cylindrical preform, and Also, the drop strength of the bottle to be dropped is reduced. Further, when the thickness of the inner resin layer is larger than the above range, the amount of the lubricating liquid that permeates the inner resin layer becomes excessively large, and it is difficult to maintain the thickness of the lubricating liquid coating layer in a predetermined range. turn into.
  • the liquid-diffusion-preventing oxygen barrier layer provided below (on the outer surface side of) the inner resin layer ensures the oxygen barrier property and at the same time prevents the lubricating liquid from penetrating from the lubricating liquid coating layer into the inner resin layer. This layer is provided to prevent further diffusion and penetration.
  • Such a liquid diffusion preventing oxygen barrier layer is made of an ethylene / vinyl alcohol copolymer (EVOH) known as an oxygen barrier resin, and may further contain low density polyethylene (LDPE).
  • EVOH ethylene / vinyl alcohol copolymer
  • LDPE low density polyethylene
  • Such EVOH is a saponified product of an ethylene / vinyl acetate copolymer, and is used to convert an ethylene / vinyl acetate copolymer having an ethylene content of 20 to 60 mol% to a saponification degree of 96 mol% or more, particularly 99 mol% or more. It is obtained by saponification so that In particular, it is known that the smaller the ethylene content, the higher the oxygen barrier property is exhibited. From such a viewpoint, EVOH having an ethylene content of 20 to 60 mol%, particularly 25 to 50 mol%, is suitably used. Further, such an EVOH has a high density of 1.00 g / cm 3 or more, and a high glass transition point (Tg) of 35 ° C. or more.
  • LDPE is also used for the above-mentioned inner resin layer.
  • the liquid diffusion preventing oxygen barrier layer containing EVOH having poor adhesion to the inner resin layer and the inner resin layer are used.
  • the adhesion to the layer is enhanced, and further, the adhesion to the regrind layer described later is also enhanced, and high adhesion strength can be secured.
  • LDPE also has a high moisture resistance (for example, a water absorption of 0.1% or less as measured by ASTM D570), and has a function of suppressing contact between EVOH and moisture and suppressing deterioration of EVOH due to moisture. ing.
  • the liquid diffusion preventing oxygen barrier layer contains EVOH and LDPE
  • EVOH: LDPE at a mass ratio of 95: 5 to 50:50, particularly 90:10 to 60:40. . That is, by setting the amount of EVOH to be equal to or more than that of LDPE, the oxygen barrier property and the liquid diffusion preventing property of EVOH can be effectively exhibited. For example, when the amount of LDPE is larger than the above range, the oxygen barrier property and the liquid diffusion preventing property are reduced. When the amount of LDPE is in the above range, excellent oxygen barrier properties can be secured by utilizing the oxygen barrier properties of EVOH.
  • the amount of LDPE used is less than the above range, the adhesiveness between the inner resin layer or the regrind layer is reduced, and between the inner resin layer or the regrind layer and the liquid barrier oxygen barrier layer. Delamination tends to occur easily.
  • such a liquid diffusion preventing oxygen barrier layer contains a compatibilizer in addition to EVOH and LDPE.
  • This compatibilizer is used for compatibilizing EVOH and LDPE, which have poor adhesion to each other, and preventing phase separation between the two.
  • the compatibilizer include carboxylic acids such as maleic acid, itaconic acid and fumaric acid or anhydrides thereof, maleic acid-polyethylene copolymer, maleic anhydride-polyethylene copolymer, amide, ester and the like.
  • Graft-modified olefin resin ethylene- (meth) acrylic acid copolymer; ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer having a saponification degree of 20 to 100%, ethylene content of 85% or more Ethylene-vinyl alcohol copolymer, hydrotalcite compound; ionomer (ion-crosslinked olefin copolymer); and the like.
  • an ionomer is particularly preferably used.
  • Such an ionomer that is, an ion-crosslinked olefin copolymer is an ionic salt in which a part or all of the carboxyl groups in a copolymer of ethylene and an ⁇ , ⁇ -unsaturated carboxylic acid is neutralized with a metal cation. It is.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid include unsaturated carboxylic acids having 3 to 8 carbon atoms, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, maleic acid monomethyl ester, and maleic acid. Acid monomethyl ester and the like can be mentioned.
  • unsaturated carboxylic acids having 3 to 8 carbon atoms such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, maleic acid monomethyl ester, and maleic acid. Acid monomethyl ester and the like can be mentioned.
  • an ethylene- (meth) acrylic acid copolymer or an ethylene- (meth) acrylate- (meth) acrylic acid copolymer is preferable.
  • the above-mentioned compatibilizer is preferably used in an amount of 1 to 49 parts by mass, particularly 5 to 30 parts by mass per 100 parts by mass of the total amount of EVOH and LDPE. If the ionomer is used in excess, not only the properties required for EVOH and LDPE will be impaired, but also the cost will increase and there is no merit. If the amount of the ionomer is too small, the phase separation between EVOH and LDPE is likely to occur, and the oxygen barrier property, liquid permeation prevention property and adhesiveness may be unstable.
  • the above-mentioned liquid diffusion preventing oxygen barrier layer usually has a thickness of about 1 ⁇ m or more, or about 3 to 80 ⁇ m, particularly about 7 to 50 ⁇ m in order to sufficiently exhibit the liquid barrier property and the oxygen barrier property. Preferably, it is formed.
  • mixing of the above EVOH with LDPE and further with a compatibilizer can be easily performed by, for example, melt-kneading in a kneading section provided in an extruder.
  • the regrind layer is provided in order to recycle scraps such as burrs and blanks generated during the molding of the bottle, and therefore is derived from the LDPE derived from the inner resin layer and the liquid diffusion preventing oxygen barrier layer.
  • EVOH further contains an oxygen absorbent derived from an oxygen absorbing layer described later.
  • scrap is usually used in a mixture with virgin LDPE used for forming the inner resin layer or olefin-based resin used for forming the outer resin layer.
  • scrap is blended in an amount of about 10 to 60 parts by weight per 100 parts by weight of olefin resin of virgin.
  • Such a regrind layer preferably has a thickness of 60% by mass or less of the thickness of the bottle wall (total thickness of each layer excluding the lubricating liquid coating layer) in order to avoid performance degradation due to the regrind layer.
  • the oxygen absorbing layer is made of an oxygen absorbing agent, and the oxygen absorbing agent is dispersed in a matrix resin to form the oxygen absorbing layer as needed.
  • the above-mentioned oxygen absorbent is usually composed of an oxidizing organic component, and a transition metal catalyst component is used in combination as necessary. That is, the oxidizing organic component exhibits a function of blocking oxygen by absorbing and oxidizing the oxygen (oxygen absorbing ability), and the transition metal catalyst component is appropriately blended to promote the oxidation of the oxidizing organic component. Things.
  • Such an oxygen absorbent is known, for example, from JP-A-2002-240813.
  • the oxidizing organic component includes, for example, a polymer containing an ethylenically unsaturated group.
  • This polymer has a carbon-carbon double bond, and this double bond portion is easily oxidized by oxygen, whereby oxygen is absorbed and trapped.
  • Such an ethylenically unsaturated group-containing polymer is, for example, one derived from a polyene as a monomer, and suitable examples of the polyene used as the monomer are not limited thereto. However, the following can be exemplified.
  • Conjugated dienes such as butadiene and isoprene; 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7- Linear non-conjugated dienes such as methyl-1,6-octadiene; Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene And cyclic non-conjugated dienes such as dicyclopentadiene; Trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-is
  • a homopolymer of the above-mentioned polyene, or a random copolymer or a block copolymer obtained by combining two or more kinds of the above-mentioned polyenes or other monomers can be used as the oxidizing polymer.
  • Examples of other monomers to be copolymerized with the polyene include ⁇ -olefins having 2 to 20 carbon atoms, specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1- Nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like can be exemplified.
  • polystyrene-butadiene rubber examples include polybutadiene (BR), polyisoprene (IR), natural rubber (NR), nitrile-butadiene rubber (NBR), styrene- Butadiene rubber (SBR), chloroprene rubber, ethylene-propylene-diene rubber (EPDM) and the like are suitable, but of course, are not limited thereto.
  • the iodine value is preferably 100 or more, particularly about 120 to 196.
  • the above-mentioned oxidizing polymer and its copolymer preferably have a viscosity at 40 ° C. in the range of 1 to 200 Pa ⁇ s from the viewpoint of moldability.
  • a cyclized product of an oxidative polymer obtained by cyclizing a polymer derived from the above-mentioned polyene in the presence of an acid catalyst can also be used as an oxidizable organic component.
  • an acid catalyst used in the cyclization reaction conventionally known acid catalysts can be used. Examples thereof include sulfuric acid, fluoromethanesulfonic acid, difluoromethanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, and an alkyl group having 2 to 18 carbon atoms. Or an organic sulfonic acid compound such as an anhydride or an alkyl ester thereof.
  • the cyclized oxidizing polymer described above a cyclized product of polybutadiene, a cyclized product of polyisoprene, a cyclized product of natural rubber, and the like are preferable, but are not limited thereto.
  • the weight average molecular weight (Mw) is preferably in the range of 10,000 to 500,000 in terms of polystyrene.
  • the transition metal catalyst appropriately used is used to promote the oxidation of the oxidizable organic component, as described above, and is generally expressed in terms of transition metal per oxidizable organic component. In a range of 0 to 10000 ppm, and is used in the form of a low-valent inorganic, organic or complex salt of a transition metal.
  • the transition metal is preferably a Group VIII metal of the periodic table such as iron, cobalt, and nickel.
  • copper a Group I metal such as silver, tin, titanium, and zirconium. It may be a Group IV metal, a Group V metal such as vanadium, a Group VI metal such as chromium, or a Group VII metal such as manganese.
  • cobalt is particularly preferable because it remarkably promotes oxygen absorption (oxidation of the oxidizing organic component).
  • Examples of the inorganic salts of the transition metal include halides such as chlorides, sulfur oxysalts such as sulfates, nitrogen oxysalts such as nitrates, phosphorus oxysalts such as phosphates, and silicates. .
  • Examples of the organic salt of the transition metal include a carboxylate, a sulfonate, and a phosphonate, and the carboxylate is preferable for the purpose of the present invention.
  • Specific examples thereof include acetic acid, propionic acid, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3,5,5 -Trimethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, lindelic acid, tuzunic acid, petroselinic acid, oleic acid, linoleic acid, linolenic acid And transition
  • Transition metal complexes include complexes with ⁇ -diketones or ⁇ -keto acid esters.
  • ⁇ -diketones and ⁇ -keto acid esters include the following. Acetylacetone, Ethyl acetoacetate, 1,3-cyclohexadione, Methylenebis-1,3-cyclohexadione, 2-benzyl-1,3-cyclohexadione, Acetyltetralone, Palmitoyltetralone, Stearoyltetralone, Benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetyl-1,3-cyclohexadione, Benzoyl-p-chlorobenzoylmethane, Bis (4-methylbenzoyl) methane, Bis (2-hydroxybenzoyl) methane, Benzoyl acetone, Tribenzoylmethane, Dia
  • such an oxygen-absorbing layer is generally set to a thickness of 1 to 10% by mass, especially 3 to 8% by mass of the thickness of the bottle wall (total thickness of each layer excluding the lubricant coating layer). It is suitable.
  • an oxygen barrier layer is provided on the outer surface side of the oxygen absorbing layer. That is, in the present invention, since the oxygen absorption layer and the oxygen barrier layer are provided on the outer surface side of the liquid diffusion preventing oxygen barrier layer, it is possible to more reliably prevent the permeation of oxygen. Even when the oxygen barrier property of the preventive oxygen barrier layer is reduced by moisture in the hydrated substance as the content, the oxidation of the lubricating liquid coating layer due to the permeation of oxygen from the outer surface can be effectively prevented. Further, since the oxygen barrier layer is located at a position distant from the inner surface of the bottle, a decrease in the oxygen barrier property due to the water-containing substance as the content is effectively avoided.
  • Such an oxygen barrier layer is formed of an oxygen barrier resin known per se.
  • an oxygen barrier resin EVOH and polyamide used for the liquid diffusion preventing oxygen barrier layer described above are representative.
  • EVOH is a saponified product of an ethylene-vinyl acetate copolymer, and is obtained by converting an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol% to a saponification degree of 96 mol. %, Especially 99 mol% or more.
  • EVOH having an ethylene content of 20 to 60 mol%, particularly 25 to 50 mol% is preferably used similarly to the liquid diffusion preventing oxygen barrier layer.
  • polyamides examples include polyamides such as nylon 6, nylon 6.6, nylon 6 / 6,6 copolymer, meta-xylylene diadipamide (MXD6), nylon 6,10, nylon 11, nylon 12, nylon 13, and the like. Can be mentioned.
  • polyamides those having an amide group number of 5 to 50, particularly 6 to 20 per 100 carbon atoms are preferable in that they have high oxygen barrier properties.
  • these polyamides preferably have a relative viscosity of 1.1 or more, particularly 1.5 or more, measured at 30 ° C. in concentrated sulfuric acid (concentration: 1.0 g / dl).
  • the oxygen barrier layer is preferably set to a thickness of 1 to 10% by mass, particularly 3 to 8% by mass of the thickness of the bottle (total thickness of each layer excluding the lubricant coating layer).
  • the outer resin layer located on the outer surface of the bottle can be formed of various thermoplastic resins, but generally has properties such as flexibility and squeeze properties required for a direct blow bottle.
  • olefin resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium or high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, etc. It is preferable to be formed by Of course, a random or block copolymer of ⁇ -olefins such as ethylene, propylene, 1-butene and 4-methyl-1-pentene may be used.
  • polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyethylene isophthalate can also be used.
  • a lubricant is blended in the outer resin layer in order to prevent the bottles from being transported and the bottles from sticking to each other.
  • Typical examples of such a lubricant include fatty acid amides such as stearic acid amide, oleic acid amide, erucic acid amide, and behenic acid amide, liquid paraffin, and organopolysiloxane.
  • fatty acid amides such as stearic acid amide, oleic acid amide, erucic acid amide, and behenic acid amide, liquid paraffin, and organopolysiloxane.
  • 100 to 1000 ppm in the outer resin layer It is blended in a ratio of about.
  • known additives such as a pigment, a colorant, and an ultraviolet absorber may be added to the outer resin layer.
  • the thickness of such an outer resin layer is usually set appropriately according to the thickness of each layer so that the thickness of the bottle wall (total thickness of each layer excluding the lubricant coating layer) is 10 to 200 ⁇ m.
  • An adhesive layer can be provided.
  • the adhesive resin used for forming such an adhesive layer is known per se, and for example, has a carbonyl group (> C) O) in a main chain or a side chain of 1 to 100 meq / 100 g, particularly 10 to 100 meq / 100 g.
  • Resins contained in the amount of resin specifically, olefin resins graft-modified with carboxylic acids such as maleic acid, itaconic acid, fumaric acid or anhydrides, amides, esters, etc .; ethylene-acrylic acid copolymers; An ion-crosslinked olefin copolymer; an ethylene-vinyl acetate copolymer; and the like are used as the adhesive resin.
  • the thickness of such an adhesive layer may be such that an appropriate adhesive force can be obtained, and is generally 0.5 to 20 ⁇ m, preferably about 1 to 8 ⁇ m.
  • a liquid diffusion preventing oxygen barrier layer may be provided as the above-mentioned adhesive layer.
  • LDPE having a function of improving the adhesion between EVOH and the olefin-based resin is compounded, and further, by the addition of an ionomer that functions as a compatibilizer, such adhesion is further enhanced. Because there is. In particular, by providing this liquid diffusion preventing oxygen barrier layer as an adhesive layer, the oxygen barrier properties can be further improved.
  • the lubricating liquid coating layer described above is LB
  • the inner resin layer is INR
  • the liquid diffusion preventing oxygen barrier layer is LQBA
  • the regrind layer is RG
  • the oxygen absorbing layer is AbO
  • the oxygen barrier layer is
  • BO the outer resin layer
  • the adhesive layer is AD
  • the present invention is not limited thereto, but may have the following basic layer configuration and other layer configurations.
  • the direct blow empty bottle of the present invention having such a layer configuration is formed by forming a tube-shaped preform by co-extrusion using the resin or the resin composition forming each layer described above, and forming one end of the preform. Is closed by pinch-off, and in this state, a blow fluid such as air is supplied into the preform to shape the bottle, and finally, a predetermined lubricant is sprayed and sprayed into the bottle to coat the inside of the bottle with the lubricant. It can be manufactured by forming a layer.
  • Such a direct-blow empty bottle of the present invention exhibits excellent lubricity with respect to a hydrated substance for a long period of time, and even if this hydrated substance is viscous, it can be quickly discharged and the content in the bottle is reduced. It is also possible to effectively prevent the remaining of the contents, and to use up all the contents. In addition, while the contents contain moisture, the oxygen barrier property is maintained for a long time, and the contents and the lubricating liquid coating layer (lubricating liquid) can be effectively prevented from being oxidized and deteriorated. Can be maintained for a long time.
  • Lubricating liquid Cooking oil (rapeseed oil manufactured by Nisshin Oillio Co., Ltd.)
  • Inner surface resin layer Low-density polyethylene without lubricant (density 0.922 g / cm 3 )
  • Liquid diffusion preventing oxygen barrier layer Ethylene / vinyl alcohol copolymer (density 1.20 g / cm 3 ), low density polyethylene (density 0.922 g / cm 3 ) and ionomer are melted in a weight ratio of 7: 3: 1. After kneading, a pelletized product was used.
  • Regrind layer A dry blend of 50 parts by weight of scrap at the time of bottle production and 50 parts by weight of low-density polyethylene used for the outer resin layer was used.
  • Oxygen absorbing layer 100 parts by weight of low-density polyethylene, 5 parts by weight of a styrene resin, and 350 ppm of cobalt neodecanoate as a transition metal catalyst in terms of cobalt were blended, melt-kneaded, and pelletized.
  • Oxygen barrier layer same as liquid diffusion preventing oxygen barrier layer
  • Outer surface resin layer low-density polyethylene (density 0.922 g / cm 3 , lubricant addition amount 300 ppm)
  • Kewpie half viscosity manufactured by Kewpie Co., Ltd. (using a BH type viscometer, rotation speed: 2 rpm, rotor: No. 6, the viscosity was converted from the reading after two rotations under the measurement conditions of room temperature of 25 ° C.): 125 Pa ⁇ s
  • Example 1 Using the five extruders, a multilayer parison of the following five types and six layers was molded, and a multilayer bottle having an internal capacity of 300 g and a total mass of 15 g was obtained by direct blow molding using the multilayer parison.
  • the above multi-layer bottle was coated with a lubricating liquid and further filled with contents, and various tests were performed. The results are shown in Table 1 together with the inner resin layer ratio and the amount of lubricating liquid applied.
  • Examples 2 to 7 and Comparative Examples 1 and 2 A multilayer bottle was molded and subjected to various tests in the same manner as in Example 1, except that the inner surface resin layer ratio and the amount of the lubricating liquid applied were changed as shown in Table 1, and the results are also shown in Table 1. .
  • the ratio of the inner resin layer was changed by changing the thickness (% by mass) of the regrind layer so as not to change the total mass.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Nutrition Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Laminated Bodies (AREA)
  • Seasonings (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne une bouteille vide à soufflage direct destinée à stocker une substance contenant de l'eau et possédant une couche de lubrifiant liquide sur la surface interne de la bouteille, une paroi de bouteille possédant une couche barrière à l'oxygène possédant une fonction de prévention de diffusion de liquide. La bouteille vide à soufflage direct est apte à supprimer efficacement une détérioration par oxydation de la couche de lubrifiant liquide formée sur la surface interne de la bouteille, et à améliorer de manière stable le pouvoir lubrifiant de la substance contenant de l'eau par la couche de lubrifiant liquide sur une longue période de temps, conjointement avec la suppression de la perméation du lubrifiant dans la bouteille. La présente invention est caractérisée en ce que la bouteille vide à soufflage direct, devant être utilisée en étant remplie d'une substance contenant de l'eau, est produite par formation d'une couche de revêtement lubrifiant liquide formée par un lubrifiant liquide destinée à un pouvoir lubrifiant amélioré de la substance contenant de l'eau, d'une couche de résine de surface interne servant de base de la couche de revêtement, d'une couche barrière à l'oxygène de prévention de diffusion de liquide destinée à empêcher la diffusion du lubrifiant, d'une couche d'absorption d'oxygène, d'une couche barrière à l'oxygène et d'une couche de résine de surface externe dans cet ordre, à partir de la surface interne vers la surface externe, la couche de résine de surface interne étant formée à l'aide d'un polyéthylène basse densité, et la couche de résine de surface interne étant formée à une épaisseur de 15 à 45 % en masse par rapport à la masse totale de la bouteille, à l'exclusion de la couche de revêtement de lubrifiant.
PCT/JP2019/024810 2018-06-29 2019-06-21 Bouteille vide à soufflage direct dotée d'une couche de lubrifiant liquide sur la surface interne, et aliment émulsifié de type huile dans l'eau en bouteille Ceased WO2020004287A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018124361A JP2020001773A (ja) 2018-06-29 2018-06-29 内面に潤滑液コーティング層を備えたダイレクトブロー空ボトルおよびボトル詰め水中油型乳化食品
JP2018-124361 2018-06-29

Publications (1)

Publication Number Publication Date
WO2020004287A1 true WO2020004287A1 (fr) 2020-01-02

Family

ID=68986910

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/024810 Ceased WO2020004287A1 (fr) 2018-06-29 2019-06-21 Bouteille vide à soufflage direct dotée d'une couche de lubrifiant liquide sur la surface interne, et aliment émulsifié de type huile dans l'eau en bouteille

Country Status (2)

Country Link
JP (1) JP2020001773A (fr)
WO (1) WO2020004287A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7773031B2 (ja) * 2021-09-30 2025-11-19 キョーラク株式会社 プラスチック容器

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015100968A (ja) * 2013-11-22 2015-06-04 東洋製罐グループホールディングス株式会社 粘稠性を有する内容物を収容するための包装容器
JP2016190654A (ja) * 2015-03-31 2016-11-10 キョーラク株式会社 油性内容物用プラスチック容器
WO2017006906A1 (fr) * 2015-07-09 2017-01-12 東洋製罐グループホールディングス株式会社 Récipient contenant une surface intérieure formée à partir d'une couche de résine à base d'oléfine
JP2018090314A (ja) * 2016-12-07 2018-06-14 東洋製罐グループホールディングス株式会社 流動物が収容されているパッケージ

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017018290A (ja) * 2015-07-09 2017-01-26 東ソー株式会社 複室容器

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015100968A (ja) * 2013-11-22 2015-06-04 東洋製罐グループホールディングス株式会社 粘稠性を有する内容物を収容するための包装容器
JP2016190654A (ja) * 2015-03-31 2016-11-10 キョーラク株式会社 油性内容物用プラスチック容器
WO2017006906A1 (fr) * 2015-07-09 2017-01-12 東洋製罐グループホールディングス株式会社 Récipient contenant une surface intérieure formée à partir d'une couche de résine à base d'oléfine
JP2018090314A (ja) * 2016-12-07 2018-06-14 東洋製罐グループホールディングス株式会社 流動物が収容されているパッケージ

Also Published As

Publication number Publication date
JP2020001773A (ja) 2020-01-09

Similar Documents

Publication Publication Date Title
KR100958688B1 (ko) 기체 차단성이 우수한 다층 구조체
JP6587823B2 (ja) 表面に固体粒子が分布している容器
KR20130113483A (ko) 다층 플라스틱 용기
CA2526098C (fr) Structure multicouche pour emballage
JP5019000B2 (ja) 多層構造体
WO2020004287A1 (fr) Bouteille vide à soufflage direct dotée d'une couche de lubrifiant liquide sur la surface interne, et aliment émulsifié de type huile dans l'eau en bouteille
WO2019031171A1 (fr) Récipient moulé par soufflage utilisé avec un film d'huile formé sur une surface intérieure
CN100537371C (zh) 包装容器
JP3903997B2 (ja) 包装容器
JP2004025664A (ja) 酸素バリヤー性多層構造体
KR102061241B1 (ko) 액층을 표면에 갖는 구조체
JP5268014B2 (ja) 酸素吸収性樹脂組成物用ペレット及び酸素吸収性樹脂組成物
JP6364964B2 (ja) 含液膜構造体の製造方法及び含液膜延伸成形構造体
JP4211346B2 (ja) 酸素吸収樹脂ペレット、その製法及びこのペレットを用いた多層容器の製法
JP2003266619A (ja) 酸素バリヤー性に優れた多層構造物
JP2007076365A (ja) 酸素吸収性樹脂物品形成用ペレット及びその製造方法
JP6417721B2 (ja) 包装体
JP6205963B2 (ja) 多層構造プラスチック容器
JP4258303B2 (ja) 包装体
JP2005067609A (ja) 多層構造包装体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19825679

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19825679

Country of ref document: EP

Kind code of ref document: A1