WO2019235541A1 - バリア性及び延伸性を有する塗膜を形成するためのコーティング剤及びその使用 - Google Patents
バリア性及び延伸性を有する塗膜を形成するためのコーティング剤及びその使用 Download PDFInfo
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- WO2019235541A1 WO2019235541A1 PCT/JP2019/022410 JP2019022410W WO2019235541A1 WO 2019235541 A1 WO2019235541 A1 WO 2019235541A1 JP 2019022410 W JP2019022410 W JP 2019022410W WO 2019235541 A1 WO2019235541 A1 WO 2019235541A1
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- 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
- B65D23/00—Details of bottles or jars not otherwise provided for
- B65D23/08—Coverings or external coatings
- B65D23/0807—Coatings
- B65D23/0814—Coatings characterised by the composition of the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/14—Making preforms characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/071—Preforms or parisons characterised by their configuration, e.g. geometry, dimensions or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
-
- 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
- B65D23/00—Details of bottles or jars not otherwise provided for
- B65D23/08—Coverings or external coatings
- B65D23/0807—Coatings
- B65D23/0814—Coatings characterised by the composition of the material
- B65D23/0821—Coatings characterised by the composition of the material consisting mainly of polymeric materials
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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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
- C09D7/20—Diluents or solvents
-
- 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
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0861—Other specified values, e.g. values or ranges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3064—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7158—Bottles
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
Definitions
- the present invention relates to a coating agent for forming a coating film having barrier properties and stretchability, comprising polyvinyl alcohol (hereinafter abbreviated as PVA) and layered double hydroxide (hereinafter abbreviated as LDH), and Regarding its use.
- PVA polyvinyl alcohol
- LDH layered double hydroxide
- Patent Document 1 discloses that the barrier property of a resin container is improved by applying a coating agent containing PVA as a main component.
- a coating agent containing PVA as a main component.
- PVA polyvinyl alcohol
- the amount of PVA applied can be reduced by adding inorganic particles having barrier properties, but in this case, the coating film formed by the coating agent containing inorganic particles can withstand stretching. The problem that it becomes easy to raise
- JP 2005-306410 A Japanese Patent No. 5022038 JP 2017-65149 A JP 2017-64640 A
- the problem to be solved by the present invention is to provide a coating agent for forming a coating film having barrier properties and stretchability, and to use the coating agent to have high barrier properties and to prevent film breakage during stretching. It is providing the resin-made container which has the surface in which the coating film which is hard to raise
- a coating agent for forming a coating film having barrier properties and stretchability comprising polyvinyl alcohol (PVA) and layered double hydroxide (LDH).
- PVA polyvinyl alcohol
- LDH layered double hydroxide
- the coating agent according to 1 or 2 wherein the LDH is a magnesium acetate type Mg—Al LDH.
- the coating agent according to any one of 1 to 3 wherein the coating agent contains about 8 wt% to about 13 wt% PVA with respect to the total amount of the coating agent.
- the coating agent according to any one of 1 to 4 further comprising an alcohol.
- PVA polyvinyl alcohol
- LDH layered double hydroxide
- the LDH is a magnesium acetate type Mg—Al-based LDH.
- a preform for a plastic bottle comprising a mouth part that becomes an opening of a plastic bottle, a cylindrical body part, and a bottom part that closes the cylindrical body part, wherein polyvinyl alcohol (PVA) and layered double hydroxide
- PVA polyvinyl alcohol
- LDH barrier layer containing a product
- a method for producing a preform for a plastic bottle A step of preparing a preform comprising a mouth portion that becomes an opening of a plastic bottle, a cylindrical body portion, and a bottom portion that closes the cylindrical body portion; and any one of 1 to 6 on the outer surface of the preform A method comprising coating the described coating agent and drying it to form a barrier layer.
- a method for producing a plastic bottle comprising a step of blow-molding a preform for a plastic bottle produced by the method according to 20.
- a coating agent for forming a coating film having a barrier property and stretchability, and a resin container having a surface on which a coating film having a high barrier property and hardly causing film breakage during stretching is formed.
- FIG. 1 is a graph showing oxygen permeability of a PET bottle having a coating film formed using a coating solution containing PVA and LDH having a predetermined concentration under a predetermined temperature and humidity condition.
- FIG. 2 is a graph showing the change over time in the viscosity of each coating solution (PVA 13% + LDH 5%, PVA 13% + LDH 5% + IPA 5%, and PVA 13% + LDH 5% + ethanol 5%).
- FIG. 3 is a FIB-SIM image of a cross section near the center of the bottle shape after blow molding. A portion that appears white in the PVA + LDH layer indicates a portion where LDH is dispersed (existing).
- FIG. 4 is a TEM image of a cross section near the center of the bottle shape after blow molding.
- a coating agent for forming a coating film having barrier properties and stretchability which comprises PVA and LDH.
- plastic container means a container made of synthetic resin for storing beverages and foods, and includes, for example, a plastic bottle.
- Plastic bottles include polyethylene terephthalate (PET), polypropylene (PP), and polyethylene (PE) bottles, with PET bottles being preferred.
- PVA has the following chemical formula and significantly reduces the gas permeability of the substrate (especially O 2 and CO 2 ), thereby increasing the shelf life of packaged foods, soft drinks or beverages such as beer. Used for improvement.
- LDH is a double hydroxide in which a trivalent metal ion is dissolved in a divalent metal hydroxide. Since the hydroxide basic layer has a positive charge, a laminate in which negatively charged anions are sandwiched between layers. It has a structure. LDH has the property of incorporating atoms, molecules, and ions (guest materials) into the layer space (intercalation) while retaining the two-dimensional basic layer (host layer) by the host-guest reaction. It has been studied in various fields such as ion exchangers, flame retardant additives, drug carriers, and cement additives.
- LDH is classified as a kind of clay mineral, and there are several types of natural minerals that are produced in small quantities, but the most commonly used is hydrotalcite, which is Mg 6 Al. It is represented by the composition formula of 2 (OH) 16 CO 3 .4H 2 O.
- LDH is represented by the following general formula, and its crystal structure is a regular octahedral hydroxide layer in which a part of a divalent metal ion is replaced by a trivalent metal ion. It has a structure in which basic layers and intermediate layers made of interlayer anions and interlayer water are alternately stacked.
- M 2+ is a divalent metal ion such as Mg, Mn, Fe, Co, Ni, Cu, or Zn
- M 3+ is a trivalent metal ion such as Al, Cr, Fe, Co, or In. It is.
- the hydroxide basic layer has a positive charge by substituting a part of the divalent metal ion with the trivalent metal ion, and in order to compensate for the charge, an anion is taken into the intermediate layer to maintain electrical neutrality. . Water molecules are also taken in between the layers as interlayer water.
- A is A n- is an anion of the intermediate layer, Cl -, NO 3-, CO 3 2-, COO - and the like, it is possible to exchange the type.
- the LDH used in the present invention is not particularly limited, but a magnesium acetate type Mg—Al based LDH in which Mg acetate is intercalated in the intermediate layer is preferable.
- Such LDH can be purchased from Teika Co., Ltd. under the trade name T-HT A610 (composition formula: Mg 6 Al 2 (OH) 18 Mg (CH 3 COO) 2 .nH 2 O), for example.
- Examples of the solvent that can be used for preparing the coating agent according to the present invention include water, methanol, ethanol, IPA, MEK, acetone, ethylene glycol, triethylene glycol, glycerin, acetamide, dimethylamide, dimethylacetamide, dimethylsulfoxide, and cyclohexanone. , Tetrahydrofuran, DMSO, pyridine, and / or combinations thereof.
- the concentration of LDH in the coating agent according to the present invention is typically about 3 wt% to about 7 wt%, preferably about 5 wt%, as a relative concentration with respect to PVA.
- the concentration of PVA in the coating agent according to the present invention is typically about 8 wt% to about 13 wt%, preferably about 10 wt%, as an absolute concentration based on the total amount of the coating agent.
- the coating agent according to the present invention may further contain alcohol. Since LDH has a viscosity-imparting effect, the viscosity of the coating agent containing LDH may increase due to changes over time, but the increase in viscosity can be suppressed by adding alcohol to the coating agent.
- the alcohol used in the present invention is not particularly limited, and examples thereof include isopropyl alcohol, ethanol, and / or a combination thereof, and isopropyl alcohol is particularly preferable.
- the concentration of the alcohol in the coating agent according to the present invention is typically about 3 wt% to about 13 wt%, preferably about 5 wt%, as a relative concentration with respect to the solvent.
- a resin container or a plastic bottle preform characterized by having a coating film on which a barrier layer containing PVA and LDH is formed.
- the preform for a plastic bottle is an intermediate product before being blow-molded into a plastic bottle, and includes a mouth part that becomes an opening of the plastic bottle, a cylindrical body part, and a bottom part that closes the cylindrical body part.
- the resin container or plastic bottle preform according to the present invention is obtained by coating the surface of the resin container or preform with the above-described coating agent according to the present invention and drying it to form a barrier layer. .
- a coating method known in the art such as a dipping method, a blow method, a spray method, a coater method, and a transfer method, or a dispenser coating method using a slot die should be used.
- a coating method known in the art such as a dipping method, a blow method, a spray method, a coater method, and a transfer method, or a dispenser coating method using a slot die should be used.
- the slot die type coating method is disclosed in detail in Patent Documents 3 and 4, and a resin container or preform is held in a horizontal direction, the resin container or preform is rotated around an axis, and rotated. This is achieved by discharging the coating liquid in a sheet form from the slot of the dispenser toward the resin container or preform.
- a coating method variation in the film thickness of the coating formed on the resin container or preform is reduced, and bubbles are generated in the coating liquid applied to the resin container or preform. This can be suppressed.
- the resin container or the preform surface Prior to the coating step, is preferably subjected to plasma, corona or electron beam treatment. Such pretreatment can enhance the adhesion of the coating agent to the substrate.
- the drying means of a coating agent is not specifically limited, It is preferable to implement by a heater and ventilation (normal temperature or hot air). In order to shorten the heating and drying time of the coating agent, it is effective to heat from the inside of the film by selecting a heat source having a heating wavelength suitable for the absorption wavelength of the solvent and the hydroxyl group. From this point, it is preferable to use a carbon heater that generates near-infrared to mid-infrared. In addition, in order to efficiently remove evaporated water without cooling the membrane, a carbon heater that generates near-infrared to mid-infrared light is used together with a far-infrared heater, blowing (room temperature), or blowing hot air. Also good.
- the drying temperature is preferably from room temperature to 80 ° C. If it is 100 ° C. or higher, the solution may boil, and if it exceeds 80 ° C., the substrate may be whitened or deformed due to overheating.
- a coating film having a barrier layer containing PVA and uniformly dispersing LDH is formed on the surface of the resin container or preform.
- the thickness of the barrier layer of the resin container is typically about 2 ⁇ m to about 8 ⁇ m.
- a plastic bottle is manufactured by subjecting the preform according to the present invention to stretch blow molding. Therefore, as a further aspect of the present invention, there is provided a method for producing a plastic bottle obtained by blow molding the preform for plastic bottle according to the present invention.
- Example 1 Preparation of coating solution (no addition of alcohol)] 447.5 g of pure water was weighed into a large glass container, and 2.5 g of powder of MgH-acetate type LDH (T-HT A610, Taker) was added thereto to obtain a solution. This was stirred with a stirrer at 300 rpm for 30 minutes to completely dissolve LDH. 50 g of powder of PVA (Exeval (registered trademark) 390, Kuraray) was weighed and added to the LDH solution prepared above. A thermostatic bath was prepared, hot water was added, and the set temperature of the heater was set to 95 ° C. In the thermostat, the LDH solution obtained above was stirred at 300 rpm with a stirrer.
- PVA Exeval (registered trademark) 390, Kuraray
- Example 2 Preparation of coating solution (with addition of alcohol)
- a large glass container 397.5 g of pure water was weighed and 2.5 g of MgH-acetate type LDH (T-HT A610, Taker) powder was added thereto to obtain a solution. This was stirred with a stirrer at 300 rpm for 30 minutes to completely dissolve LDH.
- 50 g of PVA powder (Exeval (registered trademark) 390, Kuraray) was weighed and added to the LDH solution prepared above.
- a thermostatic bath was prepared, hot water was added, and the set temperature of the heater was set to 95 ° C. In the thermostat, the LDH solution obtained above was stirred at 300 rpm with a stirrer.
- Example 3 Evaluation of barrier property against LDH concentration
- the outer surface of a 500 ml PET bottle preform (24 g) was irradiated with plasma for about 3 seconds using an atmospheric plasma irradiation surface modification device (PS-1200AW, manufactured by Wedge Corporation), and then heated to 50 ° C. in an oven. . Thereafter, each coating solution (PVA 13% + LDH 0%, PVA 13% + LDH 3%, PVA 13% + LDH 5%) prepared by fixing the PVA concentration to 13% using the same method as in Example 1 while keeping the preform at 50 ° C. , PVA 13% + LDH 7%) once or twice and dried in an oven at 50 ° C. for 1 hour.
- PS-1200AW atmospheric plasma irradiation surface modification device
- a preform having a coating film of each coating solution was stretch blow molded under a conventional condition with a stretch blow molding machine to produce a PET bottle.
- the oxygen permeability of the PET bottle was measured with a MOCON oxygen permeability measuring device (manufactured by MOCON, OXTRAN-2 / 61).
- MOCON MOCON oxygen permeability measuring device
- Table 1 and FIG. 1 it was found that the coating amount can be reduced by about 50% by adding 5% LDH.
- the drying time can be shortened by almost half. If the LDH is less than 3%, the barrier effect is low, and if the LDH exceeds 7%, the overspec is used, and there is a concern that the viscosity of the solution may increase.
- Example 4 Evaluation of barrier property against PVA concentration
- the outer surface of a 500 ml PET bottle preform (24 g) was irradiated with plasma for about 3 seconds using an atmospheric plasma irradiation surface modification device (PS-1200AW, manufactured by Wedge Corporation), and then heated to 50 ° C. in an oven. .
- each coating solution PVA 8% + LDH 5%, PVA 10% + LDH 5%, PVA 11.5%
- each coating solution prepared by fixing the LDH concentration to 5% using the same method as in Example 1 while keeping the preform at 50 ° C. + LDH 5%, PVA 13% + LDH 5%
- dipped once or twice and dried in an oven at 50 ° C. for 1 hour.
- a preform having a coating film of each coating solution was stretch blow molded under a conventional condition with a stretch blow molding machine to produce a PET bottle.
- the oxygen permeability of the PET bottle was measured with a MOCON oxygen permeability measuring device (manufactured by MOCON, OXTRAN-2 / 61).
- MOCON MOCON oxygen permeability measuring device
- Table 2 since the coating amount per dipping increased as the PVA concentration increased, the barrier property tended to increase in proportion. Considering the barrier improvement effect having cost merit and the ease of handling, the PVA concentration of 10% is considered to be the optimum concentration.
- Example 5 Evaluation of viscosity suppression effect of alcohol
- each coating solution PVA 13% + LDH 5%, PVA 13% + LDH 5% + IPA 5%, PVA 13% + LDH 5% + ethanol 5%
- PVA 13% + LDH 5% + ethanol 5% each coating solution was prepared and the change in viscosity over time was examined.
- the viscosity of the solution to which only PVA and LDH were added increased with time, but it was found that the increase in the viscosity of the solution could be suppressed by adding alcohol.
- the effect of suppressing viscosity was greater with IPA than with ethanol.
- Example 6 FIB-SIM observation
- a 500 ml PET bottle preform (24 g) was dipped twice in the coating solution described in Example 1, dried, and then blow-molded to obtain a FIB processing apparatus ( This was cut with Seiko Instruments, SM12050), and the image was observed with FIB-SIM. As shown in FIG. 3, it was observed that nano-order LDH was uniformly dispersed in the barrier layer.
- Example 7 TEM observation
- a 500 ml PET bottle preform (24 g) was dipped twice in the coating solution described in Example 1, dried, and then blow-molded to obtain a TEM device (Japan)
- the image was observed with a Thunder, JEM-220OFS.
- FIG. 4 it was observed that rod-shaped LDH having a large aspect ratio was dispersed in the same direction in PVA. With such a structure, it is presumed that the maze effect appears and the barrier property is improved.
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Abstract
Description
しかしながら、コーティングのバリア材料としてPVAを用いて所望のバリア性を得るためには、PVAの塗布量を増やす必要があるが、PVAの塗布量の増加は、乾燥時間の延長による生産性の悪化や、乾燥工程での泡の発生、乾燥不良等といったデメリットをもたらす。一方で、バリア性を有する無機粒子を添加することでPVAの塗布量を減らすことができるが、この場合には、無機粒子を含有するコーティング剤によって形成された塗膜は延伸に耐えることができずに膜切れを起こし易くなるという問題が生じる。
[1] バリア性及び延伸性を有する塗膜を形成するためのコーティング剤であって、ポリビニルアルコール(PVA)及び層状複水酸化物(LDH)を含むことを特徴とするコーティング剤。
[2] 前記コーティング剤中にPVAに対して約3重量%~約7重量%のLDHが含まれる、1に記載のコーティング剤。
[3] 前記LDHが酢酸マグネシウム型Mg-Al系LDHである、1又は2に記載のコーティング剤。
[4] 前記コーティング剤中にコーティング剤の全量に対して約8重量%~約13重量%のPVAが含まれる、1~3のいずれかに記載のコーティング剤。
[5] アルコールをさらに含む、1~4のいずれかに記載のコーティング剤。
[6] 前記アルコールが、イソプロピルアルコール又はエタノールである、5に記載のコーティング剤。
[7] ポリビニルアルコール(PVA)及び層状複水酸化物(LDH)を含むバリア層が形成された塗膜を有することを特徴とする、樹脂製容器。
[8] 前記バリア層中にPVAに対して約3重量%~約7重量%のLDHが含まれる、7に記載の樹脂製容器。
[9] 前記LDHが酢酸マグネシウム型Mg-Al系LDHである、7又は8に記載の樹脂製容器。
[10] 前記バリア層中にコーティング剤の全量に対して約8重量%~約13重量%のPVAが含まれる、7~9のいずれかに記載の樹脂製容器。
[11] 前記バリア層中にアルコールをさらに含む、7~10のいずれかに記載の樹脂製容器。
[12] 前記アルコールが、イソプロピルアルコール又はエタノールである、11に記載の樹脂製容器。
[13] 前記樹脂製容器がプラスチックボトルである、7~12のいずれかに記載の樹脂製容器。
[14] プラスチックボトルの開口となる口部と、円筒状胴部と、該円筒状胴部を閉塞する底部とからなるプラスチックボトル用プリフォームであって、ポリビニルアルコール(PVA)及び層状複水酸化物(LDH)を含むバリア層が形成された塗膜を有することを特徴とする、プリフォーム。
[15] 前記バリア層中にPVAに対して約3重量%~約7重量%のLDHが含まれる、14に記載のプリフォーム。
[16] 前記LDHが酢酸マグネシウム型Mg-Al系LDHである、14又は15に記載のプリフォーム。
[17] 前記バリア層中にコーティング剤の全量に対して約8重量%~約13重量%のPVAが含まれる、14~16のいずれかに記載のプリフォーム。
[18] 前記バリア層中にアルコールをさらに含む、14~17のいずれかに記載のプリフォーム。
[19] 前記アルコールが、イソプロピルアルコール又はエタノールである、18に記載のプリフォーム。
[20] プラスチックボトル用プリフォームの製造方法であって、
プラスチックボトルの開口となる口部と、円筒状胴部と、該円筒状胴部を閉塞する底部とからなるプリフォームを用意する工程、及び
前記プリフォームの外表面に1~6のいずれかに記載のコーティング剤をコーティングし、これを乾燥させてバリア層を形成させる工程
を含むことを特徴とする方法。
[21] 20に記載の方法によって製造されたプラスチックボトル用プリフォームをブロー成形する工程を含む、プラスチックボトルの製造方法。
[M2+ 1-xM3+ x(OH)2]X+[An- x/n・yH2O]
ここで、M2+は、Mg、Mn、Fe、Co、Ni、Cu、Znなどの二価金属イオンであり、M3+は、Al、Cr、Fe、Co、Inなどの三価金属イオンである。水酸化物基本層は二価金属イオンの一部を三価金属イオンが置換することにより正電荷をもち、その電荷を補うために中間層へ陰イオンを取り込んで電気的中性を保っている。また層間には、層間水として水分子も取り込まれている。中間層の陰イオンであるAn-は、Cl-、NO3-、CO3 2-、COO-などであり、種類によっては交換が可能である。また、xは、x=[M3+]/([M2+]+[M3+])であって、通常x=0.2~0.33であり、yは0より大きい実数である。
M(II)1-xM(III)x(OH)2
(式中、M(II)はMgであり、M(III)はAlであり、x=0.2~0.33である)の金属複水酸化物よりなる基本層と、該基本層間の中間層にインターカレートされたMgの酢酸塩及び層間水より構成される。このようなLDHは、例えば、商品名T-HT A610(組成式:Mg6Al2(OH)18Mg(CH3COO)2・nH2O)として、テイカ株式会社から購入することができる。
大きめのガラス容器に純水447.5gを量り取り、そこに酢酸Mg型LDH(T-HT A610,テイカ)の粉末を2.5g添加し溶液を得た。これを攪拌機にて300rpmで30分間攪拌してLDHを完全に溶解させた。
PVA(エクセバール(登録商標)390,クラレ)の粉末50gを量り取り、これを上記で作成したLDH溶液に添加した。恒温槽を準備して、お湯を入れヒーターの設定温度を95℃に設定した。当該恒温槽中で、上記で得られたLDH溶液を攪拌機にて300rpmで攪拌した。水温が95℃に到達したのを確認した後、1時間攪拌した。PVAの溶け残りがある場合は、攪拌機の速度を適宜上げて、溶液が完全に透明になるまで攪拌した。ヒーターのスイッチを切り、300rpmで攪拌しながら溶液の温度を徐々に下げ、常温(23℃)に下がるまで攪拌を継続した。
上記により作製したコーティング溶液中の各成分の重量と濃度は以下のとおりである。
重量(g) 濃度(重量%) 相対濃度(重量%)
PVA 50 10.05
LDH 2.5 0.556 5(PVAに対して)
水 447.5
合計 500
大きめのガラス容器に純水397.5gを量り取り、そこに酢酸Mg型LDH(T-HT A610,テイカ)の粉末を2.5g添加し溶液を得た。これを攪拌機にて300rpmで30分間攪拌してLDHを完全に溶解させた。
PVAの粉末(エクセバール(登録商標)390,クラレ)50gを量り取り、これを上記で作成したLDH溶液に添加した。恒温槽を準備して、お湯を入れヒーターの設定温度を95℃に設定した。当該恒温槽中で、上記で得られたLDH溶液を攪拌機にて300rpmで攪拌した。水温が95℃に到達したのを確認した後、1時間攪拌した。PVAの溶け残りがある場合は、攪拌機の速度を適宜上げて、溶液が完全に透明になるまで攪拌した。ヒーターのスイッチを切り、300rpmで攪拌しながら溶液の温度を徐々に下げ、常温(23℃)に下がるまで攪拌を継続した。
上記とは別容器に、純水50gとIPA(和光純薬)50gを量り取り、軽く手で攪拌して混合した後、その全量を上記で得られた混合溶液に添加した。常温にて、300rpmで30分間攪拌した。
上記により作製したコーティング溶液中の各成分の重量と濃度は以下のとおりである。
重量(g) 濃度(重量%) 相対濃度(重量%)
PVA 50 10.05
LDH 2.5 0.556 5(PVAに対して)
水 422.5
IPA 25 5(水に対して)
合計 500
500ml用PETボトル用プリフォーム(24g)の外表面に大気中プラズマ照射表面改質装置(ウエッジ株式会社製、PS-1200AW)にて約3秒間プラズマ照射した後、オーブン中で50℃に加熱した。その後、プリフォームを50℃に保ちながら、実施例1と同様の方法を用いてPVA濃度を13%に固定して作成した各コーティング溶液(PVA13%+LDH0%、PVA13%+LDH3%、PVA13%+LDH5%、PVA13%+LDH7%)に1又は2回ディッピングし、50℃のオーブン中で1時間乾燥させた。各コーティング溶液の塗膜を有するプリフォームを延伸ブロー成形機にて、慣用の条件で延伸ブロー成形し、PETボトルを製造した。
MOCON酸素透過率測定装置(MOCON社製、OXTRAN-2/61)によりPETボトルの酸素透過度を測定した。
500ml用PETボトル用プリフォーム(24g)の外表面に大気中プラズマ照射表面改質装置(ウエッジ株式会社製、PS-1200AW)にて約3秒間プラズマ照射した後、オーブン中で50℃に加熱した。その後、プリフォームを50℃に保ちながら、実施例1と同様の方法を用いてLDH濃度を5%に固定して作成した各コーティング溶液(PVA8%+LDH5%、PVA10%+LDH5%、PVA11.5%+LDH5%、PVA13%+LDH5%)に1又は2回ディッピングし、50℃のオーブン中で1時間乾燥させた。各コーティング溶液の塗膜を有するプリフォームを延伸ブロー成形機にて、慣用の条件で延伸ブロー成形し、PETボトルを製造した。
MOCON酸素透過率測定装置(MOCON社製、OXTRAN-2/61)によりPETボトルの酸素透過度を測定した。
実施例1及び2と同様の方法を用いて、各コーティング溶液(PVA13%+LDH5%、PVA13%+LDH5%+IPA5%、PVA13%+LDH5%+エタノール5%)を作成し、粘度の経時変化を調べた。
図2にからもわかるように、PVAとLDHのみを添加した溶液の粘度は時間の経過により上昇したが、アルコールを添加することにより溶液の粘度の上昇を抑制できることがわかった。粘度の抑制効果は、エタノールよりもIPAの方が大きかった。
500ml用PETボトル用プリフォーム(24g)を実施例1に記載のコーティング溶液に2回ディッピングし、乾燥させた後、これをブロー成形することにより得られたPETボトルの中心付近をFIB加工装置(セイコーインスツルメンツ社製、SM12050)で切削加工し、FIB-SIMにて像の観察を行った。
図3に示されるとおり、ナノオーダーのLDHがバリア層に均一に分散していることが観察された。
500ml用PETボトル用プリフォーム(24g)を実施例1に記載のコーティング溶液に2回ディッピングし、乾燥させた後、これをブロー成形することにより得られたPETボトルの中心付近をTEM装置(日本雷子社製、JEM-220OFS)にて像の観察を行った。
図4に示されるとおり、アスペクト比の大きい棒状のLDHがPVA中に同方向に分散していることが観察された。このような構造により、迷路効果が発現し、バリア性が向上するものと推察される。
Claims (21)
- バリア性及び延伸性を有する塗膜を形成するためのコーティング剤であって、ポリビニルアルコール(PVA)及び層状複水酸化物(LDH)を含むことを特徴とするコーティング剤。
- 前記コーティング剤中にPVAに対して約3重量%~約7重量%のLDHが含まれる、請求項1に記載のコーティング剤。
- 前記LDHが酢酸マグネシウム型Mg-Al系LDHである、請求項1又は2に記載のコーティング剤。
- 前記コーティング剤中にコーティング剤の全量に対して約8重量%~約13重量%のPVAが含まれる、請求項1~3のいずれか1項に記載のコーティング剤。
- アルコールをさらに含む、請求項1~4のいずれか1項に記載のコーティング剤。
- 前記アルコールが、イソプロピルアルコール又はエタノールである、請求項5に記載のコーティング剤。
- ポリビニルアルコール(PVA)及び層状複水酸化物(LDH)を含むバリア層が形成された塗膜を有することを特徴とする、樹脂製容器。
- 前記バリア層中にPVAに対して約3重量%~約7重量%のLDHが含まれる、請求項7に記載の樹脂製容器。
- 前記LDHが酢酸マグネシウム型Mg-Al系LDHである、請求項7又は8に記載の樹脂製容器。
- 前記バリア層中にコーティング剤の全量に対して約8重量%~約13重量%のPVAが含まれる、請求項7~9のいずれか1項に記載の樹脂製容器。
- 前記バリア層中にアルコールをさらに含む、請求項7~10のいずれか1項に記載の樹脂製容器。
- 前記アルコールが、イソプロピルアルコール又はエタノールである、請求項11に記載の樹脂製容器。
- 前記樹脂製容器がプラスチックボトルである、請求項7~12のいずれか1項に記載の樹脂製容器。
- プラスチックボトルの開口となる口部と、円筒状胴部と、該円筒状胴部を閉塞する底部とからなるプラスチックボトル用プリフォームであって、ポリビニルアルコール(PVA)及び層状複水酸化物(LDH)を含むバリア層が形成された塗膜を有することを特徴とする、プリフォーム。
- 前記バリア層中にPVAに対して約3重量%~約7重量%のLDHが含まれる、請求項14に記載のプリフォーム。
- 前記LDHが酢酸マグネシウム型Mg-Al系LDHである、請求項14又は15に記載のプリフォーム。
- 前記バリア層中にコーティング剤の全量に対して約8重量%~約13重量%のPVAが含まれる、請求項14~16のいずれか1項に記載のプリフォーム。
- 前記バリア層中にアルコールをさらに含む、請求項14~17のいずれか1項に記載のプリフォーム。
- 前記アルコールが、イソプロピルアルコール又はエタノールである、請求項18に記載のプリフォーム。
- プラスチックボトル用プリフォームの製造方法であって、
プラスチックボトルの開口となる口部と、円筒状胴部と、該円筒状胴部を閉塞する底部とからなるプリフォームを用意する工程、及び
前記プリフォームの外表面に請求項1~6のいずれか1項に記載のコーティング剤をコーティングし、これを乾燥させてバリア層を形成させる工程
を含むことを特徴とする方法。 - 請求項20に記載の方法によって製造されたプラスチックボトル用プリフォームをブロー成形する工程を含む、プラスチックボトルの製造方法。
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