WO2016185804A1 - 表面にゲル状被覆を有する構造体 - Google Patents
表面にゲル状被覆を有する構造体 Download PDFInfo
- Publication number
- WO2016185804A1 WO2016185804A1 PCT/JP2016/060136 JP2016060136W WO2016185804A1 WO 2016185804 A1 WO2016185804 A1 WO 2016185804A1 JP 2016060136 W JP2016060136 W JP 2016060136W WO 2016185804 A1 WO2016185804 A1 WO 2016185804A1
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- WO
- WIPO (PCT)
- Prior art keywords
- gel
- coating
- slipperiness
- oil
- container
- Prior art date
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Classifications
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/746—Slipping, anti-blocking, low friction
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- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
Definitions
- the present invention relates to a structure having a gel-like coating on its surface, and more particularly to a structure suitably used as a container.
- Containers that contain liquid contents are required to discharge the contents regardless of the material of the container.
- a low viscosity liquid such as water
- such discharge is hardly a problem.
- a viscous material such as mayonnaise or ketchup
- it may be a plastic container but glass. Whether it is a made container, this discharge is a serious problem. That is, such contents are not quickly discharged by tilting the container, and adhere to the container wall, and thus cannot be used up to the end. Especially, a considerable amount of contents are placed at the bottom of the container. Remains without being discharged.
- Patent Documents 1 and 2 various techniques for improving slipperiness with respect to viscous substances by forming an oil film on the surface of a molded body such as a container have been proposed (for example, Patent Documents 1 and 2). According to such a technique, the slipperiness can be drastically improved as compared with the case where an additive such as a lubricant is added to the synthetic resin forming the surface of the molded body, and thus is currently attracting attention.
- the effective life of the slipperiness exhibited by the oil film is short, and the slipperiness decreases after a long period of time.
- problems such as the contents sticking to the surface have occurred. This tendency is particularly noticeable when the material that slides down the surface is an emulsion, particularly a mayonnaise-like food with low oil content.
- the present applicant has previously described a packaging container containing an oil-in-water emulsion typified by mayonnaise-like food, and an oil film is formed on the inner surface of the container in contact with the oil-in-water emulsion.
- a packaging container has been proposed (Japanese Patent Application No. 2014-023425).
- the present applicant has also disclosed a packaging material characterized in that a liquid film is formed on the inner surface in contact with the contents, and solid particles having a particle diameter of 300 ⁇ m or less are dispersed in the liquid film. (Japanese Patent Application No. 2014-126877).
- Japanese Patent Application No. 2014-126877 Japanese Patent Application No. 2014-126877.
- an object of the present invention is to provide a structure in which a lubricity coating for improving slipperiness such as slipperiness is formed and the effect of improving the slipperiness is sustained and stably exhibited.
- Another object of the present invention is to provide a structure that is particularly used as a container in which an emulsion is accommodated as a content and has excellent slidability with respect to the emulsion.
- the inventors of the present invention have conducted many experiments on the slipperiness with respect to viscous substances, and as a result of studying them, by mixing fine fixed particles in an oily liquid and forming a gel-like coating on the surface, The inventors have found that the slipperiness of various viscous substances, particularly emulsions, is high, and that the slipperiness can be stably exhibited over a long period of time, thereby completing the present invention.
- the gel-like coating has a viscosity of 35 to 250 mPa ⁇ s (25 ° C.) measured at a rotation speed of 20 rpm.
- the oily liquid forming the gel-like coating has a contact angle (20 ° C.) with respect to the substrate surface of 45 ° or less and a viscosity (25 ° C.) of 100 mPa ⁇ s or less, (3) the oily liquid is an edible oil; (4)
- the fine solid particles are fat and oil particles, (5) the gel-like coating is formed on the substrate surface in an amount of 1.00 to 3.70 mg / cm 2 ; (6)
- the substrate surface is made of synthetic resin or glass, (7)
- the base material is a container, and the gel-like coating is formed on the inner surface in contact with the contents, Is preferred.
- the viscosity is measured by a rotational viscometer, but the oily liquid is a Newtonian fluid, and the viscosity is not limited to the rotational viscometer, An appropriate viscometer is selected and measured according to the viscosity of the oily liquid.
- the structure of the present invention is provided with a gel-like coating formed of an oily liquid and fine solid particles on its surface, it has excellent slipperiness (initial slipperiness) against various viscous water-containing substances. In addition, the deterioration over time is effectively avoided, and the durability of slipperiness is excellent. Such excellent initial slipperiness and sustainability of slipperiness are effectively exhibited even for viscous emulsions such as mayonnaise-like foods.
- a predetermined gel-like coating is formed on the inner surface of the container (base material) according to the present invention, as shown in Example 1 described later. Furthermore, when this mayonnaise-like food is filled into the structure, even after storage at 40 ° C. for 2 months, it exhibits the same activity (slidability) as that immediately after filling. On the other hand, when the oil film is not formed on the inner surface of the container (base material) only with the oily liquid used for forming the gel-like coating, the contents (mayonnaise) are stored at 40 ° C. for 2 weeks. The slipperiness for food-like foods has declined significantly.
- the gel-like coating is formed on the surface of the substrate, when the viscous water-containing material flows on the gel-like coating, the contact with the viscous water-containing material is caused by the stress (load). Oily liquid is liberated at the interface and exhibits excellent slipperiness. At the same time, the interface between the gel-like coating and the surface of the molded body is hardly subjected to stress (load), does not move from the surface of the molded body, and is stably held. to continue. That is, even when a viscous water-containing substance repeatedly flows on the gel-like coating, the gel-like coating is hardly consumed. As a result, it is considered that not only the initial slip property is excellent, but also the excellent sustainability of the slip property can be obtained.
- the structure of the present invention exhibits excellent slipperiness with respect to viscous water-containing materials, and also has excellent sustainability, such water-containing materials, mayonnaise, ketchup, various dressings and the like It is particularly preferably used as a container for storing a viscous fluid material, particularly a material having a viscosity (25 ° C.) of 1260 mPa ⁇ s or more (measured with a tuning fork viscometer).
- the structure of the present invention comprises a base material 1 molded into a shape according to the use and a gel-like coating 3 formed on the surface thereof.
- the material of the substrate 1 is not particularly limited as long as the gel-like coating 3 can be held on the surface thereof, and has a form according to the application by any material such as resin, glass or metal. It only has to have.
- the base material 1 is a pipe for flowing such a water-containing substance, It is preferable that the container has a form such as a container or a container lid for accommodating it, and the gel-like coating 3 is formed on the surface in contact with such a water-containing substance.
- the surface of the base material 1 (the ground surface of the gel-like coating 3) is made of a synthetic resin.
- Such a synthetic resin may be any thermoplastic resin or thermosetting resin that can be molded, but is generally easy to mold and in the gel-like coating 3. From the viewpoint of having a high affinity with the oily liquid and being able to hold the gel-like coating 3 containing such an oily liquid more stably, a thermoplastic resin is preferable. As such a thermoplastic resin, the following can be illustrated, for example.
- Olefin resins such as low density polyethylene, high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene or ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene Random or block copolymers, cyclic olefin copolymers, etc .; Ethylene / vinyl copolymers, such as ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / vinyl chloride copolymer, etc .; Styrenic resin such as polystyrene, acrylonitrile / styrene copolymer, ABS, ⁇ -methylstyrene / styrene copolymer, etc .; Vinyl resins such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymers, polymethyl acrylate, polymethyl methacryl
- thermoplastic resins described above olefin resins and polyester resins used as container materials for storing viscous contents are suitable, and olefin resins are optimal. That is, since the olefin resin has a lower glass transition point (Tg) and higher molecular mobility at room temperature than a polyester resin such as PET, a part of the oily liquid forming the gel-like coating 3 is used. It is optimal in that it penetrates into the interior and thereby keeps the gel-like coating 3 stably on the surface.
- Tg glass transition point
- PET polyester resin
- the olefin-based resin is highly flexible and is also used for the application of a squeeze bottle (squeeze bottle) by direct blow molding described later, from the viewpoint of applying the structure of the present invention to such a container. Also olefin resins are suitable.
- the base material 1 may have a single layer structure of the thermoplastic resin as described above, or may be a laminate of the thermoplastic resin and paper, and a plurality of thermoplastic resins. May have a multi-layer structure in which are combined.
- the structure of the present invention is excellent in slipperiness and persistence for viscous water-containing materials, it is effectively applied to applications where such water-containing materials flow in contact with the gel-like coating 3. It is most suitable that it is used as a container in which a water-containing substance is accommodated, that is, the base material 1 has the form of a container in that the advantages of the present invention can be enjoyed to the maximum.
- the substrate 1 has the form of a container
- an oxygen barrier layer or an oxygen is appropriately interposed as an intermediate layer through an adhesive resin layer. It is possible to adopt a structure in which an absorption layer is laminated and a resin of the same type as a base resin (olefin resin or polyester resin) that forms the inner surface is laminated on the outer surface side.
- the oxygen barrier layer in such a multilayer structure is formed of, for example, an oxygen barrier resin such as ethylene-vinyl alcohol copolymer or polyamide. As long as the oxygen barrier property is not impaired, Other thermoplastic resins may be blended.
- the oxygen absorbing layer is a layer containing an oxidizing polymer and a transition metal catalyst, as described in JP-A No. 2002-240813, etc., and the oxidizing polymer is oxygenated by the action of the transition metal catalyst. As a result, the oxygen is absorbed and the permeation of oxygen is blocked.
- an oxidizable polymer and a transition metal catalyst are described in detail in the above-mentioned JP-A No.
- oxidizable polymer examples include Olefin resins having tertiary carbon atoms (eg, polypropylene, polybutene-1, etc., or copolymers thereof), thermoplastic polyesters or aliphatic polyamides; xylylene group-containing polyamide resins; ethylenically unsaturated group-containing polymers ( For example, a polymer derived from a polyene such as butadiene).
- the inorganic salt, organic acid salt, or complex salt of transition metals, such as iron, cobalt, and nickel are typical.
- Adhesive resins used for bonding the layers are known per se, for example, olefin resins graft-modified with carboxylic acids such as maleic acid, itaconic acid, fumaric acid or their anhydrides, amides, esters, etc .; An ethylene-acrylic acid copolymer; an ion-crosslinked olefin copolymer; an ethylene-vinyl acetate copolymer; and the like are used as the adhesive resin.
- the thickness of each layer described above may be set to an appropriate thickness according to the characteristics required for each layer.
- a ligide layer in which scraps such as burrs generated when the substrate 1 having a multilayer structure as described above is blended with a virgin resin such as an olefin resin as an inner layer.
- a virgin resin such as an olefin resin
- the base material 1 a container having an inner surface formed of a polyester resin or a polyester resin and an outer surface formed of a polyester resin or an olefin resin.
- the shape of the container used as the substrate 1 is not particularly limited, and has a shape corresponding to the container material, such as a cup or cup shape, a bottle shape, a bag shape (pouch), a syringe shape, an acupoint shape, or a tray shape. Alternatively, it may be stretch-molded or molded by a method known per se.
- FIG. 2 shows a direct blow bottle which is the most preferable form of the substrate 1 of the present invention.
- a bottle 10 indicated as a whole has a neck 11 provided with a thread, a trunk wall 15 connected to the neck 11 via a shoulder 13, and a bottom wall 17 closing the lower end of the trunk wall 15.
- the gel-like coating 3 is formed on the inner surface of such a bottle (base material 1).
- Such a bottle 10 is preferably used for containing a viscous substance, and squeezes the body wall 15 to discharge the viscous substance contained therein. If the gel-like coating 3 is formed and the slipperiness and the sustainability of the contents are improved, such contents can be discharged quickly, and the entire amount is discharged. It is also possible to use up everything.
- the gel-like coating 3 provided on the surface of the substrate 1 as described above is formed from an oily liquid and fine solid particles.
- the gel coating 3 preferably has thixotropic properties.
- the oily liquid used for the formation of the gel-like coating 3 exhibits slipperiness with respect to the water-containing substance and functions as a lubricant.
- Such an oily liquid must naturally be a non-volatile liquid having a low vapor pressure under atmospheric pressure, for example, a high boiling point liquid having a boiling point of 200 ° C. or higher. This is because when a volatile liquid is used, it easily evaporates and disappears with time, and it becomes difficult to form the gel-like coating 3.
- the contact angle (20 ° C.) with respect to the surface is 45 ° or less and the viscosity (25 ° C.) is 100 mPa ⁇ s or less. That is, whether the surface material of the substrate 1 is made of synthetic resin, glass, or metal, the gel-like coating 3 may be formed using an oily liquid that satisfies the above physical properties.
- the lubricating effect is higher as the surface tension is significantly different from the material to be slidable (for example, the container contents in a container).
- an oily liquid having a surface tension in the range of 10 to 40 mN / m, particularly 16 to 35 mN / m in terms of improving the slipperiness with respect to the viscous water-containing substance.
- Typical examples include liquid paraffin, synthetic paraffin, fluorinated liquid, fluorinated surfactant, silicone oil, fatty acid triglyceride, and various vegetable oils.
- edible oil when the substance to be slidable is food (for example, mayonnaise or ketchup), edible oil is suitable.
- edible oils include soybean oil, rapeseed oil, olive oil, rice oil, corn oil, ben flower oil, sesame oil, palm oil, castor oil, avocado oil, coconut oil, almond oil, walnut oil, and bean oil. And salad oil.
- the fine solid particles used in combination with the above-mentioned oily liquid impart thixotropic properties to the oily liquid, and the particle diameter must be 50 ⁇ m or less, particularly 30 ⁇ m or less. is there. That is, the solid particles form a network structure in an oily liquid, and in order to give a gel that exhibits thixotropic properties or a structure close to a gel, the solid particles are fine as described above. It must have a particle size. This is because when the particle diameter is large, a network structure in which the particles are connected cannot be formed.
- the above particle diameter can be measured by, for example, a laser diffraction scattering method or microscope observation, and means a so-called secondary particle diameter (aggregated particle diameter).
- inorganic particles such as metal particles and metal oxides may be formed of various organic materials and inorganic materials. It is preferably organic particles, for example, olefin wax, rice wax, carnauba wax, various celluloses, organic resin cured products (for example, cured products obtained by curing polyfunctional acrylic monomers), and the like, In particular, rice wax is most suitable because it can be used for foods without restriction.
- the gel-like coating 3 using the oily liquid and fine solid particles described above is prepared by mixing both and stirring under strong shear. That is, strong stirring may be performed so that a network structure of fine solid particles is formed.
- the gel-like film 3 thus obtained preferably has a viscosity of 35 to 250 mPa ⁇ S measured using a rotational viscometer at a rotational speed of 20 rpm and 25 ° C. If it is less than 35 mPa ⁇ S, it will be difficult to hold in the molded body 1 for a long time, and the slipperiness with time will be low. If it is greater than 250 mPa ⁇ S, the sliding speed will be slow, and the performance may not be fully exhibited.
- the gel-like coating 3 prepared by mixing and stirring 5 parts by mass of fine solid particles with 100 parts by mass of the oily liquid has a viscosity of 124 mPa ⁇ S at a rotation speed of 20 rpm and at a rotation speed of 2 rpm.
- the viscosity is 243 mPa ⁇ S, and it has a thixotropic property that the viscosity is smaller as the rotational speed is larger.
- the initial slip property can be increased and the sustainability can be greatly improved.
- the thixotropy is small (the difference in viscosity is small)
- the amount of oil that oozes out on the surface when the water-containing substance flows on the gel-like coating 3 tends to be low, and the initial slipping property tends to be low.
- the gel-like coating 3 on one surface is not stably maintained, and each time a substance flows on the gel-like coating 3, the slipperiness tends to decrease, and the durability of the slipperiness may be unsatisfactory. There is.
- the above-described stirring temperature, shear rate, stirring time, and the like may be appropriately adjusted. Usually, however, per 100 parts by mass of fine solid particles.
- the oily liquid is preferably mixed in an amount of about 0.5 to 10 parts by mass, particularly about 1 to 10 parts by mass.
- the gel-like coating 3 can be formed by using various means according to the surface shape of the substrate 1. However, since the gel-like coating 3 has thixotropic properties, spray spraying is possible. Therefore, it is desirable to form the gel-like coating 3 by spraying on the surface of the predetermined substrate 1 by spraying.
- the gel-like coating 3 thus formed is desirably formed on the surface of the substrate 1 in an amount of 1.00 to 3.70 mg / cm 2 . That is, if this amount is too small, the slipperiness and sustainability of the gel-like coating 3 will be unsatisfactory, and even if it is formed more than necessary, no further slipperiness or sustainability will be obtained, and the cost will increase. Rather, the gel-like coating 3 tends to fall off from the surface of the substrate 1 due to its weight.
- the viscosity (25 ° C.) is 100 mPa ⁇ s or more (measured with a tuning fork viscometer).
- Containers that contain viscous water-containing substances particularly used as direct blow containers, such as mayonnaise, ketchup, aqueous glue, honey, various sauces, mustards, dressings, jams, chocolate syrups, milky lotions, It is most suitable as a filling bottle for viscous contents such as liquid detergents, shampoos and rinses.
- the present invention will be described in the following experimental examples.
- the container, gel-like film, and contents used in each example and comparative example are as follows.
- a multilayer direct blow bottle having a multilayer structure having the following layer structure and having an internal capacity of 400 g was provided.
- Inner layer Low density polyethylene resin (LDPE)
- Intermediate layer ethylene-vinyl alcohol copolymer (EVOH)
- Outer layer Low density polyethylene resin (LDPE)
- Adhesive layer (between inner and outer layers and intermediate layer): acid-modified polyolefin
- Oily liquid Medium chain fatty acid added salad oil Viscosity: 33 mPa ⁇ s (25 ° C) Contact angle (20 ° C.): 18 degrees
- Solid particles Carnauba wax Using a homogenizer, the above solid particles are finely dispersed in the above oily liquid in the amount ratio shown in Table 1 at room temperature (25 ° C.). A coating solution was prepared, and the coating amount shown in Table 1 was applied uniformly on the inner surface of the container using an air spray to form a gel film.
- the evaluation method of slipperiness using the contents of each example and each comparative example is as follows. ⁇ Slippery evaluation> A spray nozzle was inserted into the bottle to the bottom, and the gel-like film was pulled up while spraying to apply to the entire side wall from the bottom of the bottle. In a bottle with a gel-like film formed on the inner surface of this container, 400 g of mayonnaise-like food, which is the contents, is filled in a conventional manner, the bottle mouth is heat sealed with aluminum foil, and sealed with a cap to fill the filled bottle. Obtained. The filled bottle filled with the contents was stored at 23 ° C. for 1 week (initial bottle).
- Example 1 The gel-like film was applied to the molded bottle with the application amount shown in Table 1, and the slip property was evaluated.
- Comparative Example 1 The oily liquid similar to the gel-like film was applied to the molded bottle with the application amount shown in Table 1, and the slipperiness was evaluated.
- Comparative Example 2 The liquid which mixed the oil-like liquid similar to a gel-like coating
- the prepared liquid was not a gel because the solid particles were not fine solid particles.
- the slipperiness of the contents is improved, and the slipperiness is maintained even after long-term storage at a high temperature. It was confirmed that the formed molded article was excellent in slipping of the contents and maintained the performance for a long time. Further, simply mixing the oily liquid and the solid particles in the gel film resulted in a decrease in slipperiness over time, and the same result as in the case without the solid particles was obtained. From this, it was confirmed that it is important that the solid particles become fine solid particles and become a gel.
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Abstract
Description
かかる技術によれば、成形体表面を形成する合成樹脂に滑剤などの添加剤を加える場合と比較して、滑り性を飛躍的に高めることができるため、現在注目されている。
また、本出願人は、内容物と接触する内面に液膜が形成されており、該液膜には、粒子径が300μm以下の固体粒子が分散されていることを特徴とする包装材も先に提案している(特願2014-126877号)。
しかるに、本出願人が先に提案したこれらの技術においても、滑り性の経時的低下という問題は有効に解決されていない。
本発明の他の目的は、特に乳化物が内容物として収容される容器として使用され、かかる乳化物に対する滑り性の持続性に優れた構造体を提供することにある。
(1)ゲル状被覆は、回転数20rpmで測定した粘度が35~250mPa・s(25℃)であること、
(2)前記ゲル状被覆を形成する油性液体が、基材表面に対する接触角(20℃)が45°以下であり且つ100mPa・s以下の粘度(25℃)を有していること、
(3)前記油性液体が食用油であること、
(4)前記微細固体状粒子が、油脂粒子であること、
(5)前記ゲル状被覆が、1.00~3.70mg/cm2の量で基材表面に形成されていること、
(6)前記基材表面が、合成樹脂製またはガラス製であること、
(7)前記基材が容器であり、内容物と接触する内面に前記ゲル状被覆が形成されていること、
が好適である。
尚、本発明において、上記のゲル状被覆は非ニュートン流体であるため、回転粘度計により粘度が測定されるが、油性液体は、ニュートン流体であり、その粘度は回転粘度計に限定されず、油性液体が有する粘度に応じて、適当な粘度計を選択して測定される。
一方、ゲル状被覆とせず、上記ゲル状被覆の形成に用いた油性液体のみで油膜を容器(基材)内面に形成したに過ぎない場合には、40℃、2週間保存で内容物(マヨネーズ様食品)に対する滑り性が大幅に低下してしまっている。
即ち、単なる油膜により滑り性を高めている場合には、この油膜を通る粘稠な含水物質によって油膜が表面から徐々に掻き取られていく。このため、初期段階では、油膜による滑り性が有効に発現するが、油膜上を粘稠な含水物質が流れるごとに油膜が消耗していき、この結果、滑り性は次第に低下していくこととなり、その持続性は不満足なものなってしまう。
しかるに、本発明では、基材表面にゲル状被覆が形成されているため、このゲル状被覆上を粘稠な含水物質が流れるとき、その応力(荷重)によって、粘稠な含水物質との接触界面では油性液体が遊離して優れた滑り性を発揮すると同時に、ゲル状被覆と成形体表面との界面側では、応力(荷重)をほとんど受けず、成形体表面から動かず、安定に保持され続ける。即ち、ゲル状被覆上を粘稠な含水物質が繰り返し流れた場合にも、ゲル状被覆はほとんど消耗しない。この結果、初期滑り性が優れているばかりか、優れた滑り性の持続性が得られるものと考えられるのである。
基材1は、その表面にゲル状被覆3を保持することが可能である限り、その材質は特に制限されず、樹脂製、ガラス製、金属製等の任意の材質により用途に応じた形態を有していればよい。
特に、本発明の構造体は、ゲル状被覆3により、粘稠な含水物質に対して優れた滑り性を示すという観点から、基材1は、このような含水物質を流すための配管や、これを収容する容器や容器蓋などの形態を有していることが好適であり、このような含水物質と接触する面に、上記のゲル状被覆3が形成される。
このような熱可塑性樹脂としては、例えば、以下のものを例示することができる。
オレフィン系樹脂、例えば、低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、ポリ1-ブテン、ポリ4-メチル-1-ペンテンあるいはエチレン、プロピレン、1-ブテン、4-メチル-1-ペンテン等のα-オレフィン同士のランダムあるいはブロック共重合体、環状オレフィン共重合体など;
エチレン・ビニル系共重合体、例えば、エチレン・酢酸ビニル共重合体、エチレン・ビニルアルコール共重合体、エチレン・塩化ビニル共重合体等;
スチレン系樹脂、例えば、ポリスチレン、アクリロニトリル・スチレン共重合体、ABS、α-メチルスチレン・スチレン共重合体等;
ビニル系樹脂、例えば、ポリ塩化ビニル、ポリ塩化ビニリデン、塩化ビニル・塩化ビニリデン共重合体、ポリアクリル酸メチル、ポリメタクリル酸メチル等;
ポリアミド樹脂、例えば、ナイロン6、ナイロン6-6、ナイロン6-10、ナイロン11、ナイロン12等;
ポリエステル樹脂、例えば、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート、ポリエチレンナフタレート、及びこれらの共重合ポリエステル等;
ポリカーボネート樹脂;
ポリフエニレンオキサイド樹脂;
生分解性樹脂、例えば、ポリ乳酸など;
勿論、成形性が損なわれない限り、これらの熱可塑性樹脂のブレンド物を、下地樹脂として使用することもできる。
即ち、オレフィン系樹脂は、PET等のポリエステル樹脂と比較してガラス転移点(Tg)が低く、室温下での分子の運動性が高いため、ゲル状被覆3を形成する油性液体の一部が内部に浸透し、これにより、ゲル状被覆3を表面に安定に保持するという点で最適である。
さらに、オレフィン系樹脂は、可撓性が高く、後述するダイレクトブロー成形による絞り出し容器(スクイズボトル)の用途にも使用されており、本発明の構造体をこのような容器に適用するという観点からもオレフィン系樹脂は適している。
また、酸素吸収層は、特開2002-240813号等に記載されているように、酸化性重合体及び遷移金属系触媒を含む層であり、遷移金属系触媒の作用により酸化性重合体が酸素による酸化を受け、これにより、酸素を吸収して酸素の透過を遮断する。このような酸化性重合体及び遷移金属系触媒は、上記の特開2002-240813号等に詳細に説明されているので、その詳細は省略するが、酸化性重合体の代表的な例は、第3級炭素原子を有するオレフィン系樹脂(例えばポリプロピレンやポリブテン-1等、或いはこれらの共重合体)、熱可塑性ポリエステル若しくは脂肪族ポリアミド;キシリレン基含有ポリアミド樹脂;エチレン系不飽和基含有重合体(例えばブタジエン等のポリエンから誘導される重合体);などである。また、遷移金属系触媒としては、鉄、コバルト、ニッケル等の遷移金属の無機塩、有機酸塩或いは錯塩が代表的である。
上述した各層の厚みは、各層に要求される特性に応じて、適宜の厚みに設定されればよい。
図2において、全体として10で示されるこのボトルは、螺条を備えた首部11、肩部13を介して首部11に連なる胴部壁15及び胴部壁15の下端を閉じている底壁17を有しており、このようなボトル(基材1)の内面にゲル状被覆3が形成されることとなる。
かかるボトル10は、粘稠な物質の収容に好適に使用され、胴部壁15をスクイズすることにより、内部に収容された粘稠な物質を排出するというものであり、このようなボトルの内面にゲル状被覆3が形成され、内容物に対する滑性及びその持続性が向上していれば、このような内容物を速やかに排出することができるし、しかも、その全量を排出し、該内容物を使い切ることも可能となる。
本発明において、上記のような基材1の表面に設けられるゲル状被覆3は、油性液体と微細固体状粒子とから形成される。そして、ゲル状被覆3はチキソトロピー性を有していることが好ましい。
このような油性液体は、当然、大気圧下での蒸気圧が小さい不揮発性の液体、例えば沸点が200℃以上の高沸点液体でなければならない。揮発性液体を用いた場合には、容易に揮散して経時と共に消失し、ゲル状被覆3を形成することが困難となってしまうからである。
即ち、粘稠な含水物質に対する滑り性を高めるという点で、表面張力が10乃至40mN/m、特に16乃至35mN/mの範囲にある油性液体を用いるのが良く、このような油性液体としては、流動パラフィン、合成パラフィン、フッ素系液体、フッ素系界面活性剤、シリコーンオイル、脂肪酸トリグリセライド、各種の植物油などが代表的である。特に滑り性の対象となる物質が食品類(例えばマヨネーズやケチャップ)である場合には、食用油が好適である。
かかる食用油の具体例としては、大豆油、菜種油、オリーブオイル、米油、コーン油、べに花油、ごま油、パーム油、ひまし油、アボガド油、ココナッツ油、アーモンド油、クルミ油、はしばみ油、サラダ油などを例示することができる。
尚、上記の粒子径は、例えばレーザ回折散乱法や、マイクロスコープ観察などにより測定することができ、所謂二次粒子径(凝集粒子径)を意味する。
また、例えば、油性液体100質量部に対し、微細固体粒子5質量部を混合し、攪拌して作成したゲル状被膜3は、回転数20rpmでは、粘度が124mPa・Sであり、回転数2rpmでは、粘度が243mPa・Sであり、回転数が大きいほど粘度が小さいというチキソトロピー性を有している。このように、チキソトロピー性を有することで、初期滑り性を大きくし且つその持続性を大きく向上させることができる。例えば、チキソトロピー性が小さい(粘度差が小さい)と、ゲル状被覆3上を含水物質が流れたときに表面に滲み出る油量が少なく、初期滑り性が低くなる傾向があり、しかも、成形体1表面でのゲル状被覆3が安定に保持されず、ゲル状被覆3上を物質が流れるごとに、滑り性が低下していく傾向が大きく、滑り性の持続性が不満足となってしまう恐れがある。
各実施例、比較例にて使用した容器、ゲル状被膜、内容物は次のとおりである。
下記の層構成を有する多層構造を有し、且つ内容量400gの多層ダイレクトブローボトルを供した。
内層:低密度ポリエチレン樹脂(LDPE)
中間層:エチレン-ビニルアルコール共重合体(EVOH)
外層:低密度ポリエチレン樹脂(LDPE)
接着層(内外層と中間層との間):酸変性ポリオレフィン
油性液体:中鎖脂肪酸添加サラダ油
粘度:33mPa・s(25℃)
接触角(20℃):18度
固体状粒子:カルナバワックス
ホモジナイザーを使用し、室温(25℃)で、上記の固体状粒子を、表1に示す量割合で上記の油性液体に微分散化させて塗布液を調製し、表1に示す塗布量を、エアースプレーを用いて容器の内面に均一となるように塗布してゲル状被膜を形成した。
接触角;
容器内面を上面にしてゲル状被膜に使用した油性液体を10mg落とし、20℃、50%RH、接触角計(協和界面科学(株)社DropMaster700)にて測定した。
粘度;
粘度は、ビーカーに入れた測定物質に、B型デジタル粘度計のスピンドルとガードを入れ、25℃にて、回転数20rpmでスピンドルを1分間回転させ、粘度測定を行った。
卵1個(50g)と酢15ccと塩2.5ccを混ぜた後、さらに食用油150ccを混ぜ合わせて、実験用のマヨネーズ様食品を作成した。各実施例、比較例では、必要量の内容物を作成して使用した。
<滑り性評価>
ボトル内に、噴霧ノズルを底まで挿入し、ゲル状被膜を噴霧しながら引き上げることによりボトル底部から側壁全面に塗布した。この容器内面にゲル状被膜が形成されているボトル内に、内容物であるマヨネーズ様食品を常法で400g充填し、ボトル口部をアルミ箔でヒートシールし、キャップで密封して充填ボトルを得た。
内容物が充填された充填ボトルを23℃で1週間保管した(初期ボトル)。
表1に示す各保管期間・温度にて保管されたボトルについて、胴部を押し、ボトル口部を通して内容物を最後まで搾り出した後、このボトル内に空気を入れ形状を復元させた。
次いで、このボトルを倒立(口部を下側)にして1時間保管した後のボトル胴部壁の内容物滑り性の程度(胴部壁に内容物が付着していない程度)を測定し、次の式で内容物付着率を計算した。
内容物付着率(%)
=(内容物が付着している表面積/ボトル胴部壁表面積)×100
上記で計算された内容物付着率から、滑り性を次の基準で評価した。
〇:内容物付着率が10%未満
△:内容物付着率が10%以上で50%未満
×:内容物付着率が50%以上
<固体状粒子径測定>
作成したゲル状被膜をマイクロスコープで観察し、画像処理して粒小径を測定した。最大粒子径をゲル状被膜の粒子径とした。
成形したボトルに、ゲル状被膜を、表1中の塗布量で塗布し、滑り性を評価した。
〔比較例1〕
成形したボトルに、ゲル状被膜と同様の油性液体を、表1中の塗布量で塗布し、滑り性を評価した。
〔比較例2〕
成形したボトルに、ゲル状被覆と同様の油性液体と固体粒子(粒子径85μm)を混合した液を表1中の塗布量で塗布し、滑り性を評価した。作成した液体は、固体粒子が微細固体状粒子ではないため、ゲル状ではなかった。
3:ゲル状被覆
Claims (8)
- 所定の形状に成形されている基材の表面にゲル状被覆が形成されている構造体であって、該ゲル状被覆は、粒子径が50μm以下の微細固体状粒子と油性液体とから形成されていることを特徴とする構造体。
- 前記ゲル状被覆は、回転数20rpmで測定した粘度が35~250mPa・s(25℃)である請求項1記載の構造体。
- 前記油性液体が、前記基材表面に対する接触角(20℃)が45°以下であり且つ100mPa・s以下の粘度(25℃)を有している請求項2記載の構造体。
- 前記油性液体が食用油である請求項3記載の構造体。
- 前記微細固体粒子が、油脂粒子である請求項1記載の構造体。
- 前記ゲル状被覆が、1.00~3.70mg/cm2の量で基材表面に形成されている請求項1記載の構造体。
- 前記基材表面が、合成樹脂製またはガラス製である請求項1記載の構造体。
- 前記基材が容器であり、内容物と接触する内面に前記ゲル状被覆が形成されている請求項1記載の構造体。
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RU2671908C1 (ru) | 2018-11-07 |
CA2983718A1 (en) | 2016-11-24 |
AU2016263863A1 (en) | 2017-12-07 |
KR102008384B1 (ko) | 2019-08-07 |
EP3299311A1 (en) | 2018-03-28 |
JP6001726B1 (ja) | 2016-10-05 |
CA2983718C (en) | 2020-06-02 |
KR20170139106A (ko) | 2017-12-18 |
JP2016216105A (ja) | 2016-12-22 |
AU2016263863B2 (en) | 2019-05-16 |
EP3299311A4 (en) | 2019-04-10 |
US20180162580A1 (en) | 2018-06-14 |
US10710764B2 (en) | 2020-07-14 |
CN107614392A (zh) | 2018-01-19 |
CN107614392B (zh) | 2019-05-03 |
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