Plastic bottle preform and method for production thereof

Abstract

Provided is a PET bottle preform in which delamination is suppressed and a method for the production of the preform. An anchor layer containing a polyester-based urethane resin is formed on an outer surface of the preform.

Claims

1. A preform for a plastic bottle comprising a mouth serving as an opening of the plastic bottle, a cylindrical body, and a bottom enclosing the cylindrical body, wherein the preform has a coating film in which an anchor layer containing a polyester-based urethane resin is formed on an outer surface of the preform, and wherein a barrier layer containing polyvinyl alcohol and a leveling agent is formed on the anchor layer.

2. The preform according to claim 1, wherein a protective layer containing polyvinyl butyral (PVB) is formed on the barrier layer.

3. The preform according to claim 1, wherein the polyester-based urethane resin has a glass transition temperature (Tg) of approximately 65° C. to less than approximately 90° C.

4. The preform according to claim 1, wherein the polyester-based urethane resin has a glass transition temperature (Tg) of approximately 80° C. to approximately 85° C.

5. A plastic bottle comprising a mouth serving as an opening of the plastic bottle, a cylindrical body, and a bottom enclosing the cylindrical body, wherein the plastic bottle has a coating film in which an anchor layer containing a polyester-based urethane resin is formed on an outer surface of the preform, and wherein a barrier layer containing polyvinyl alcohol and a leveling agent is formed on the anchor layer.

6. The plastic bottle according to claim 5, wherein a protective layer containing polyvinyl butyral (PVB) is formed on the barrier layer.

7. The plastic bottle according to claim 5, wherein the polyester-based urethane resin has a glass transition temperature (Tg) of approximately 65° C. to less than approximately 90° C.

8. The plastic bottle according to claim 5, wherein the polyester-based urethane resin has a glass transition temperature (Tg) of approximately 80° C. to approximately 85° C.

9. A method for the production of a preform for a plastic bottle, the method comprising the steps of: preparing a preform comprising a mouth serving as an opening of the plastic bottle, a cylindrical body, and a bottom enclosing the cylindrical body, and coating an outer surface of the preform with an anchor coating agent containing a polyester-based urethane resin and drying to form an anchor layer, and coating the anchor layer with a solution containing polyvinyl alcohol and a leveling agent and drying to form a barrier layer.

10. The method according to claim 9, further comprising the step of coating the barrier layer with a polyvinyl butyral (PVB) solution and drying to form a protective layer.

11. The method according to claim 9, wherein the polyester-based urethane resin has a glass transition temperature (Tg) of approximately 65° C. to less than approximately 90° C.

12. The method according to claim 9, wherein the polyester-based urethane resin has a glass transition temperature (Tg) of approximately 80° C. to approximately 85° C.

13. A method for the production of a plastic bottle, comprising a step of blow-molding a preform for a plastic bottle produced by the method according to claim 9.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic view of a method for the production of a plastic bottle according to the present invention.

DESCRIPTION OF EMBODIMENTS

(2) As used herein, the phrase “plastic bottle” encompasses polyethylene terephthalate (PET), polypropylene (PP), and polyethylene (PE) bottles, and is not limited to PET bottles.

(3) A first embodiment of the present invention provides a preform for a plastic bottle comprising a mouth serving as an opening of the plastic bottle, a cylindrical body, and a bottom enclosing the cylindrical body, wherein the preform has a coating film in which an anchor layer containing a polyester-based urethane resin is formed on an outer surface of the preform.

(4) In the preform according to the present invention, a barrier layer containing polyvinyl alcohol (PVA) is formed on the anchor layer, and a protective layer containing polyvinyl butyral (PVB) is preferably further formed on the barrier layer.

(5) Polyester-based urethane resins are produced by reacting a polyester polyol and a polyisocyanate in the presence of a low molecular weight diol, diamene, etc., as necessary. The polyester-based urethane resin used in the present invention typically has a glass transition temperature (Tg) of approximately 65° C. to less than approximately 90° C. and preferably has a glass transition temperature (Tg) of approximately 80° C. to approximately 85° C. The polyester-based urethane resin used in the present invention is preferably water-dispersible. Examples of such polyester-based urethane resins include Takelac™ W-5030 (Mitsui Chemicals, Inc.), WS-5000 (Mitsui Chemicals, Inc.), and WS-5984 (Mitsui Chemicals, Inc.).

(6) PVA can significantly reduce the gas permeability of the substrate (particularly O.sub.2 and CO.sub.2), thereby improving the shelf life of the contained food or beverage such as soft drink or beer. However, the applications of coatings composed of PVA alone are limited due to the hygroscopicity thereof. Thus, polyvinyl acetals, for example, PVB, have been found to be suitable as the top-coating (protective layer) for the PVA layer (barrier layer) and have been used. PVA polymers and PVB polymers have similar polymer backbone chains, as illustrated in the following chemical formulas:

(7) ##STR00001##
and are compatible in a wide range of mixtures.

(8) Another embodiment of the present invention provides a method for the production of a preform for a plastic bottle, the method comprising the steps of preparing a preform comprising a mouth serving as an opening of the plastic bottle, a cylindrical body, and a bottom enclosing the cylindrical body, and coating an outer surface of the preform with an anchor coating agent containing a polyester-based urethane resin and drying to form an anchor layer.

(9) The method according to present invention preferably further includes the step of coating the anchor layer with a PVA solution and drying to form a barrier layer and the step of coating the barrier layer with a PVB solution and drying to form a protective layer.

(10) The above method is a method for producing a preform according to the present invention, in which the above-mentioned anchor coating agent, PVA, and PVB are used.

(11) Examples of solvents which can be used for the preparation of the PVA solution include water, methanol, ethanol, IPA, MEK, acetone, ethylene glycol, triethylene glycol, glycerin, acetamide, dimethylamide, dimethyl acetamide, dimethyl sulfoxide, cyclohexanone, tetrahydrofuran, DMSO, pyridine, and/or combinations thereof.

(12) Examples of solvents which can be used for the preparation of the PVB solution include methanol, ethanol, n-propanol, IPA, n-butanol, octanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, acetone, MEK, MIBK, cyclohexanone, isophorone, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, ethyl ether, dioxane, tetrahydrofuran, toluene, xylene, pyridine, dimethyl sulfoxide, acetic acid, terpineol, butyl carbitol, butyl carbitol acetate, and/or combinations thereof.

(13) The concentration of PVA in the solution is preferably approximately 1 to approximately 30 wt % and the concentration of PVB in the solution is preferably approximately 0.1 to approximately 50 wt %.

(14) For the coating in each of the above steps, in addition to, for example, coating methods which are well known in the art such as dipping (immersion) methods, blow methods, spray methods, coater methods, and transfer methods, a dispenser coating method using a slot-die can be used.

(15) Slot-die coating methods are disclosed in detail in Patent Literature 5 and 6, which are achieved by holding a preform horizontally, rotating the preform about an axis, and spraying the coating solution in a planar manner from a dispenser slot toward the rotating preform. Though variations in the film thickness of the coating formed on the preform can be reduced and the occurrence of bubbles in the coating liquid applied to the preform can be suppressed by using such a coating method, when the anchor layer is coated with a barrier material such as PVA, there is a problem in that uniform application cannot be achieved. However, such coating defects can be prevented by adding a leveling agent to the barrier material. The leveling agent which can be used in the present invention is preferably a siloxane, a silicone resin, or a fluororesin. Examples of such leveling agents include DYNOL-980 (Air Products), KP-104 and KP-110 (Shinetsu Silicone), and Megafak F-477 and RS-72-K (DIC Corporation).

(16) In the method for the production of a preform according to the present invention, prior to coating with an anchor coating agent, the preform surface is preferably plasma, corona, or electron beam treated. Due to such pretreatment, adhesion of the anchor layer to the substrate can be strengthened. However, such pretreatment is an optional additional step and in the present invention, in most cases, it is possible to produce a preform having a mechanically stable coating which can be stretch blow-molded without the occurrence of cracks or delamination without pretreatment.

(17) The drying means in each of the above steps is not particularly limited as long as each layer is formed, but it is preferably carried out with a heater and blowing air (ambient temperature or hot air). In order to shorten the heating and drying time of the coating solution, 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 water, which is the solvent, and the hydroxyl group. From this viewpoint, it is preferable to use a carbon heater which generates near-infrared to mid-infrared rays. Furthermore, in order to efficiently remove the evaporated water without cooling the film, a far-infrared heater, blowing air (ambient temperature), or hot air may be used in combination along with the use of a carbon heater which generates near-infrared to mid-infrared rays.

(18) The drying temperature in each of the steps described above is preferably ambient temperature to 80° C. At 100° C. or higher, there is a risk of boiling of the solution, and if the temperature exceeds 80° C., there is a risk that the substrate will whiten or deform due to overheating.

(19) A plastic bottle is produced by stretch blow-molding the preform according to the present invention. Thus, yet another embodiment of the present invention provides a plastic bottle obtained by blow-molding the preform for a plastic bottle according to the invention and a method for the production thereof.

EXAMPLES

Example 1: Suppression of Delamination by Anchor Coating Agent

(20) The outer surfaces of preforms for a 500 ml PET bottle (24 g) were irradiated with plasma for approximately 3 seconds using an atmospheric plasma irradiation surface modifier (PS-1200AW, produced by Wedge, Co.), and thereafter were heated to 50° C. in an oven. Thereafter, the preforms were dipped once in the respective types of anchor coating agents and dried in a 50° C. oven for approximately 30 minutes to form an anchor layer. After drying, the preforms were dipped once into a 10% PVA solution while being maintained at 50° C. and were dried for 1 hour in a 50° C. oven. The PVA solution was prepared by charging PVA powder (Exeval™ HR-3010, produced by Kuraray, Co., Ltd.) into a beaker provided with a heating device and a stirrer, adding room temperature water thereto to achieve a concentration of 10 wt %, heating the mixture to a solution temperature of 95° C. while stirring, and continuing stirring until the PVA was completely dissolved. The steps of dipping into the above PVA solution and drying were repeated to form a barrier layer. After drying, the preform was dipped once into a PVB solution while being maintained at 50° C. and dried in a 50° C. oven for 30 minutes to form a protective layer. The PVB solution was produced by charging PVB powder (Mobitol™ B-30HH, produced by Kuraray, Co., Ltd.; glass transition temperature 63° C.) into a beaker provided with a heating device and a stirrer, adding ethanol (99.5%) thereto to achieve a concentration of 5 wt %, and while stirring at ambient temperature, continuing stirring until the PVB was completely dissolved. PET bottles were produced by stretch blow-molding, under conventional conditions, the preforms having a coating film on which each layer was formed with a stretch blow-molding machine. Citric acid and baking soda were added to the PET bottles, which were then filled with 4.2 GV of carbonated water. The PET bottles filled with the carbonated water were stored in a constant temperature room at 23° C. and 50% RH, and the presence or absence of delamination was confirmed.

(21) Table 1 below shows the barrier material (PVA) applicability and delamination resistance when each anchor coating agent was used. As the anchor coating agent, in addition to W5030 and WS5000 described above, W6010, W6020, W6061, and WPB341, which are polyethylene-based urethane resins produced by Mitsui Chemical, Inc., Stipulli, which is a styrol-based resin produced by Osaka Printing Ink Mfg., Co., Ltd., AD373MW, which is a polyethyleneimine-based resin produced by Toyo Morton, Seikadyne, which is a polybutadiene-based resin produced by Dainichiseika Chemicals, Co., Ltd., and Z-565, Z-730, Z-687, Z-880, and RZ-105, which are polyethylene-based resins produced by Goo Chemical Co., Ltd., were used.

(22) TABLE-US-00001 TABLE 1 Barrier Material Anchor (PVA) Coating Resin Applic- Days to Tg Agent Type ability Delamination (° C.) N/A 3 Days PVB Butyral Good 1 Month 63 W5030 Urethane Good 6 Months 85 WS5000 Urethane Good 1 Month 65 or more W6010 Urethane Poor 90 W6020 Urethane Poor 90 W6061 Urethane Good 21 WPB341 Urethane Good 1 Week 115 Stipulli Styrol 1 Week 30 AD373MW Polyethyleneimine Good 3 Days — Seikadyne Polybutadiene Good 3 Days — Z-565 Polyester Good 1 Month 64 Z-730 Polyester Poor 46 Z-687 Polyester Good 2 Weeks 110 Z-880 Polyester Good 2 Weeks 20 RZ-105 Polyester Good 1 Month 62

(23) It was confirmed that WS5000 and W5030, which are polyester-based urethane resins and which have a Tg of 65° C. to less than 90° C., had a delamination resistance of one month or more and could withstand practical use. Among them, it was confirmed that W5030 had a delamination resistance of 6 months and the coating agent did not peel after a long period of time.