JP2002068202A - Ultraviolet-shielding bottle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a UV-shielding bottle having UV-shielding layers which are formed throughout the entire surfaces of a body and a bottom of the bottle, excellent in UV-shielding properties and also in appearance characteristics of the bottle, and further excellent in recycling properties of the bottle. SOLUTION: The UV-shielding bottle comprises a bottle base having a mouth, a body and a bottom, a heat-shrinkable UV-shielding film layer covering an outer surface of the body of the bottle base, and a peelable UV-shielding ink layer applied to the outer surface of the bottom of the bottle base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bottle having an ultraviolet blocking layer on its outer surface, and more particularly to a bottle having excellent appearance characteristics, ultraviolet blocking performance and excellent recyclability.

[0002]

2. Description of the Related Art Conventionally, glass or plastic bottles colored brown, brown, green or the like have been widely used for distribution of beer, wine, sake, carbonated drinks and the like. That is, in these beverages, discoloration is caused by ultraviolet rays, or the flavor components tend to be decomposed or deteriorated, and the flavor tends to decrease. In the colored bottle, the transmission of ultraviolet rays through the vessel wall is suppressed, and the flavor is maintained. Things.

However, in plastic bottles,
Recycling of used bottles is obligatory, and coloring the plastic itself that constitutes the bottles is a major obstacle in recycling collected bottles. For this reason, various means for imparting ultraviolet blocking properties to the bottle without coloring the bottle base have been studied.

For example, Japanese Utility Model Publication No. 61-8529 discloses a heat-shrinkable film printed with an ink having an ultraviolet-absorbing effect or a heat-shrinkable film polymerized with an adhesive having an ultraviolet-absorbing effect. FIG. 1 shows a shrink-wrapped container, and FIG. 1 shows a bottle body whose outer surface is shrink-wrapped.

[0005]

However, in the above-mentioned coating method using a heat-shrinkable film, it is difficult to coat the bottom part smoothly, even if it is easy to coat a body part having a substantially constant diameter. However, it is not possible to prevent the transmission of ultraviolet rays from the uncoated bottom. Further, if the coating is applied to the bottom part by force, the film is hardened in a wrinkled state in this part, and the appearance of the bottle becomes poor, and the self-sustainability of the bottle is impaired.

Accordingly, an object of the present invention is to form an ultraviolet shielding layer over the entire surface of the body and bottom of the bottle, thereby providing excellent ultraviolet shielding properties, excellent bottle appearance, and recycling of the bottle. Another object of the present invention is to provide a UV-shielding bottle which is excellent in water resistance. Another object of the present invention is to collect and reuse used bottles.
It is an object of the present invention to provide an ultraviolet-shielding bottle which can be easily separated from the bottle by peeling off the ultraviolet-shielding layer.

[0007]

According to the present invention, a mouth,
A bottle base having a body and a bottom, a heat-shrinkable ultraviolet shielding film layer coated on the outer surface of the body of the bottle base, and a peelable ultraviolet shielding ink applied to the outer surface of the bottom of the bottle base A UV-blocking bottle, comprising: The present invention can be applied to a bottle made of any material, but it is preferable that the bottle base is a polyester bottle having at least a body portion biaxially stretched. In the present invention, the positional relationship between the ultraviolet ray blocking film layer and the ultraviolet ray blocking ink layer may be in any positional relationship as long as the entire surface of the body and bottom of the bottle is covered with them, but the ultraviolet ray blocking ink layer It is most preferable that both layers are provided on the bottle base in such a positional relationship that the ultraviolet ray blocking film layer overlaps the peripheral portion of the bottle base.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Action] In the present invention, a heat-shrinkable ultraviolet shielding film layer is applied to the body of the bottle base, and a peelable ultraviolet shielding ink layer is applied to the bottom of the bottle base. It is characterized by providing two types of coatings of the application-separation type, which is a coating, whereby an ultraviolet shielding layer is formed over the entire body and bottom of the bottle to improve the ultraviolet shielding properties of the bottle. As well as being able to form a UV-blocking layer smoothly over the entire body and bottom of the bottle, the appearance characteristics of the bottle can be improved without impairing the independence of the bottle, and the collection and reuse of used bottles In this case, separation from the bottle is easily performed by peeling off the ultraviolet blocking layer, and since the bottle itself is not colored, it can be mixed with other recovered transparent bottles. Next, an advantage that is also excellent in recycling of the bottle is achieved.

[0009] The container wall of the bottle is roughly divided into a body extending vertically in a cylindrical shape and a bottom extending undulating but extending horizontally as a whole. In the present invention, by providing a UV blocking ink layer by coating on the bottom, a smooth UV blocking coating can be formed in close contact with the bottom, and a heat-shrinkable coating can be formed on the body. By providing the ultraviolet ray blocking film layer by heat shrinkage (heat shrink), a smooth ultraviolet ray shielding coating can be formed on the body in a tightly adhered state. For this reason, ultraviolet transmission to the contents through the body and the bottom is completely prevented, and the contents are excellent in storage stability. Further, the formed ultraviolet shielding coating is smooth and has excellent appearance characteristics.

Further, since the ultraviolet blocking ink layer provided on the bottom of the bottle is releasable, it can be easily peeled off from the bottom of the bottle when washed with a weak alkaline liquid or the like. Since the blocking film layer is in close contact with the body due to its shrinkage force, the film layer can be easily separated from the body by making a cut or tear in the film layer, and the used bottle can be easily recycled. Will be.

FIG. 1 is a sectional view of the right half of FIG. 1 showing an example of a bottle base used in the present invention. A bottle base 10 has a body 11 and a bottom 12, and a shoulder 13 is provided on the top of the body 11. Is connected to the cervix 14 via. Bottom 12
Is provided with a corner 15 for connection to the body, a circumferential grounding portion 16, and a dome portion 17 protruding upward. Mouth and neck 14
Has a sealing opening 18 with a cap (not shown),
A screw 19 for cap tightening and a support ring 19a are provided on the lower outer periphery.

In the left half of FIG. 1 showing the outer surface of the ultraviolet shielding bottle of the present invention, the ultraviolet shielding bottle 20 is shown.
Is composed of an ultraviolet shielding ink layer 22 applied to cover the entire outer surface of the bottom portion 12 and a heat-shrinkable ultraviolet shielding film layer 21 applied to cover the entire outer surface of the body portion 11.

FIG. 2 is an enlarged view of the periphery of the ink layer 22 and the film layer 21 in the bottle. In FIG. 2, an ink layer 22 is provided at the bottom corner portion 15 so as to overlap the ink layer 22. A film layer 21 is provided. In the arrangement of the ink layer 22 and the film layer 21 shown in FIG. 2, even when there is an error in the arrangement of the ink layer and the film layer, the ultraviolet light shielding layer can be formed without forming a gap on the entire body and bottom of the bottle. And can form
Since the close contact of the film layer with the bottle body due to the heat shrinkage is performed in a manner involving the corners, there is also obtained an advantage that the film can be securely adhered and fixed to the body of the bottle.

[Bottle Substrate] The present invention can be applied to any bottle formed of plastic or glass, but is particularly advantageously applicable to a bottle made of a plastic material which is required to be recycled. As the resin constituting the bottle, any plastic material that can be stretch blow-molded can be used,
Thermoplastic polyesters, especially ethylene terephthalate-based thermoplastic polyesters, are advantageously used. Of course, polycarbonate, arylate resin or the like can also be used.

The ethylene terephthalate-based thermoplastic polyester used in the present invention contains most of the ester repeating units,
In general, the ethylene terephthalate unit accounts for 70 mol% or more, particularly 80 mol% or more, and has a glass transition point (Tg) of 50 to 90 ° C., particularly 55 to 80 ° C., and a melting point (Tm) of 200 to 275 ° C. Especially 220 to 27
Thermoplastic polyesters at 0 ° C. are preferred.

Although homopolyethylene terephthalate is preferred in terms of heat and pressure resistance, a copolymerized polyester containing a small amount of an ester unit other than the ethylene terephthalate unit may be used. Examples of dibasic acids other than terephthalic acid include: isophthalic acid, phthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; succinic acid, adipic acid, sebacic acid,
One or a combination of two or more aliphatic dicarboxylic acids such as dodecanedioic acid; diol components other than ethylene glycol include propylene glycol,
4-butanediol, diethylene glycol, 1,6-
Hexylene glycol, cyclohexane dimethanol,
One or more of ethylene oxide adducts of bisphenol A and the like can be mentioned.

A composite material obtained by blending ethylene terephthalate-based thermoplastic polyester with about 5% to 25% of, for example, polyethylene naphthalate, polycarbonate or polyarylate having a relatively high glass transition point can be used. Material strength at high temperatures can be increased. Further, polyethylene terephthalate and the above-mentioned material having a relatively high glass transition point can be laminated and used.

The ethylene terephthalate-based thermoplastic polyester used should have at least a molecular weight sufficient to form a film, and an injection grade or an extrusion grade is used depending on the application. Its intrinsic viscosity (IV) is generally 0.6 to 1.4 dL / g,
In particular, those in the range of 0.63 to 1.3 dL / g are desirable.

The plastic bottle is usually produced by molding a preform of the above-mentioned plastic material by injection molding, and biaxially stretch-blowing the preform at a stretching temperature, generally at a temperature of 85 to 120 ° C. Since the wall of the bottle is biaxially oriented by the stretch blow molding, physical properties such as impact resistance and gas barrier properties of the bottle are improved. As for the stretching ratio, the axial stretching ratio is 2 to 5 times, particularly 2.2 to 4 times, and the circumferential stretching ratio is 2.5 to 6.6.
It is better to multiply, especially 3 to 6 times. The axial stretching ratio is determined by the axial length of the preform molded article and the stroke length of the stretching rod, while the circumferential stretching ratio is determined by the diameter of the preform and the diameter of the mold cavity. . For bottles that require heat resistance, the body or the bottom after stretch blow molding is 100 to 250
By heat setting at a temperature of ° C., heat resistance can be improved. Also, to increase the heat resistance and rigidity of the bottle mouth,
The mouth of the bottle can be heated to perform thermal crystallization of the mouth.

[Heat-shrinkable UV-blocking film layer] The UV-blocking film layer is made of a heat-shrinkable synthetic resin film. In order to impart a UV-blocking effect, a coloring agent such as a pigment or a dye, an ultraviolet absorber or the like is used. UV blocking agents and the like. (1) Film Material As the synthetic resin constituting the film, a resin generally used for a heat-shrinkable film can be used. Examples thereof include chlorine-containing resins such as polyvinyl chloride resin and polyvinylidene chloride resin; polystyrene resins; polyester resins such as polyethylene terephthalate (PET); and olefin resins such as polyethylene and polypropylene. From the viewpoint of tear strength and scratch resistance, a heat-shrinkable film made of a polyester resin is preferable. In particular, biaxially stretched polyethylene terephthalate (PE
T) Film is most preferred.

The heat-shrinkable polyester resin comprises an acid component mainly composed of an aromatic dicarboxylic acid or an ester-forming derivative thereof and an alcohol component, and is preferably terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or an ester thereof. It consists of an acid component whose main component is a formed derivative and an alcohol component whose main component is ethylene glycol. In addition, a mixture of two or more polyester resins can be used as the polyester resin.

The aromatic dicarboxylic acid constituting the heat-shrinkable polyester resin includes terephthalic acid, isophthalic acid, naphthalene-1,4- or -2,6-dicarboxylic acid and the like. These aromatic dicarboxylic acids or their ester-forming derivatives are preferably contained in an amount of at least 80 mol%, more preferably at least 85 mol%, in all the acid components of the polyester resin. This is because when the aromatic dicarboxylic acid or its ester-forming derivative is less than 80 mol%, the mechanical strength of the formed polyester film tends to decrease.

Further, for the purpose of increasing the heat shrinkage, an aliphatic dicarboxylic acid or an ester-forming derivative thereof is
You may make it contain in less than 20 mol%, preferably less than 15 mol% in all the acid components of a polyester resin. This is because when these aliphatic dicarboxylic acid components are contained in an amount of 20 mol% or more, the mechanical strength of the polyester film may be reduced. Examples of the aliphatic dicarboxylic acid that can be used include glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid, and succinic acid.

In the present invention, the alcohol component constituting the polyester resin is mainly composed of at least one selected from ethylene glycol, butanediol, cyclohexanedimethanol, and an ethylene oxide adduct of a bisphenol compound or a derivative thereof. Preferably, these diol components are contained in the total alcohol component in an amount of 80 mol% or more. Among them, those containing 50 mol% or more of ethylene glycol in all alcohol components are preferred, and more preferably 70 mol% or more. This is because if the content of ethylene glycol is less than 50 mol%, the polymerization reactivity tends to decrease when producing the resin, and a resin having the desired degree of polymerization may not be obtained. is there.

As the alcohol component, a cyclohexane dimethanol component is added to the total alcohol component in an amount of 5 to 4%.
The content of 0 mol% is preferable from the viewpoints of reduction of shrinkage unevenness, relaxation of shrinkage unevenness, low-temperature shrinkage characteristics, and the like. This is because if the proportion of the cyclohexanedimethanol component is less than 5 mol%, shrinkage unevenness is likely to occur, and a sufficient amount of shrinkage cannot be obtained. Conversely, if the proportion exceeds 40 mol%, shrinkage starts. This is because, when the temperature is lowered and shrinkage is performed at a high temperature, rapid shrinkage is caused, and uneven shrinkage is likely to occur. More preferably, 8 to
It is in the range of 30 mol%. Further, in addition to the diol component, propylene glycol, triethylene glycol, diethylene glycol, neopentyl glycol,
Other alcohol components such as polyethylene glycol and polyoxytetramethylene glycol can be used in a range that does not impair the effects of the present invention, for example, in a range of 20 mol% or less. Further, for the purpose of suppressing rapid shrinkage and further reducing shrinkage unevenness, a trivalent or higher polyvalent carboxylic acid or polyhydric alcohol can be used. Specific examples of the trivalent or higher polycarboxylic acid or polyhydric alcohol include trimellitic acid, pyromellitic acid and polyvalent carboxylic acids such as anhydrides thereof, trimethylolpropane,
Polyhydric alcohols such as trimethylolethane, glycerin, diglycerin, and pentaerythritol are exemplified.
Among them, trimethylolpropane, trimellitic acid, from the viewpoint of thermal stability during film formation and reactivity during polycondensation,
Pentaerythritol is preferred.

The above polyester resin can be produced by a known direct polymerization method, transesterification method or the like, and the degree of polymerization is not particularly limited. / Measured at 25 ° C in a mixed solution of equal weight of tetrachloroethane)
1.2 is preferred.

(2) Ultraviolet ray blocking agent The heat-shrinkable film is blended with a coloring agent such as a pigment or a dye and an ultraviolet ray blocking agent such as an ultraviolet absorber in order to impart an ultraviolet ray blocking property. Examples of the coloring agent include pigments, dyes, decorating agents, and the like. Examples of the coloring agents include inorganic pigments such as titanium oxide, calcium carbonate, zinc oxide, talc, red iron oxide, barium sulfate, iron oxide, ultramarine, and carbon black; Organic pigments such as organic, isoindolinone-based, anthraquinone-based, perinone-based, perylene-based, quinacridone-based, phthalocyanine-based, thioindigo-based, dioxazine-based, and heterocyclic-based dyes; perinone-based, thioindigo-based dyes, metal powder, mica,
Decorating agents such as shells and phosphors are included.

Dyes and pigments are classified according to their colors as follows. Black dye pigments Carbon black, acetylene black, run black, aniline black, nigrosine black. Yellow dye / Pink zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, naphthol yellow S, hansa yellow G,
Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake. Orange color pigment Red lead graphite, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indathrene brilliant orange RK, benzidine orange G, indathrene brilliant orange GK. Red dye / pigment Bengala, Cadmium Red, Lead Tan, Mercury Cadmium, Permanent Red 4R, Risor Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B. Purple dye Manganese purple, fast violet B, methyl violet lake. Blue dye / Dark blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated phthalocyanine blue, fast sky blue, indaslen blue B
C. Green color pigment chrome green, chromium oxide, pigment green B,
Malachite Green Lake, Fanal Yellow Green G. White pigment Zinc white, titanium oxide, antimony white, zinc sulfide. Extender barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white. As these pigments, it is preferable to use flash pigments from the viewpoint of dispersibility.

Known UV absorbers can be used without limitation, and particularly preferred are salicylic acid, benzotriazole, benzophenone and cyanoacrylate UV absorbers. Specific examples are shown below. -Salicylic acid ultraviolet absorber (a) Phenyl salicylate (b) pt-butylphenyl salicylate (c) p-octylphenyl salicylate-Benzotriazole ultraviolet absorber (a) 2- (5-methyl-2-hydroxyphenyl) )
Benzotriazole (trade name: Tinuvin P: manufactured by Nippon Ciba Geigy Co., Ltd.) (b) 2- [2-hydroxy-3,5-bis (α, α
-Dimethylbenzyl) phenyl] -2H-benzotriazole (trade name: Tinuvin 234, manufactured by Nippon Ciba Geigy Co., Ltd.) (c) 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole ( Product Name: Tinuvin 3
20, manufactured by Nippon Ciba Geigy Co., Ltd.) (d) 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole (trade name: Tinuvin 326, Nippon Ciba Geigy Co., Ltd.) (E) 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (trade name: Tinuvin 327, manufactured by Nippon Ciba Geigy Co., Ltd.) (f) 2 -(3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole (trade name: Tinuvin 3
28, manufactured by Nippon Ciba Geigy Co., Ltd.) (g) 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole (trade name: Tinuvin 32)
9, manufactured by Nippon Ciba Geigy Co., Ltd.)-Benzophenone ultraviolet absorber (a) 2-hydroxy-4-methoxybenzophenone (trade name: Sumisorb 110, manufactured by Sumitomo Chemical Co., Ltd.) (b) 2-hydroxy-4 -Octyloxybenzophenone (trade name: Sumisorb 130, manufactured by Sumitomo Chemical Co., Ltd.) (c) Bis (2-hydroxy-4-methoxy) benzophenone (trade name: Ubinal D-49, BASF)
(D) 2-Hydroxybenzophenone (trade name: Ubinal 400, manufactured by BASF) (e) bis (2,4-dihydroxy) benzophenone (trade name: Ubinal D50, BASF) (F) 2,4-dihydroxybenzophenone (trade name: Chemisorb 10, manufactured by Chemipro Kasei Co., Ltd.) (g) 2-hydroxy-4-dodecyloxybenzophenone (trade name: Chemisorb 13, Chemipro Kasei Co., Ltd.) )
(H) 4-benzyloxy-2-hydroxybenzophenone (trade name: Chemisorb 15, Chemipro Kasei Co., Ltd.)
(I) 2,2'-dihydroxy-4-methoxybenzophenone (trade name: Chemisorb 111, manufactured by Chemipa Kasei Co., Ltd.)-Cyanoacrylate ultraviolet absorber (a) 2-ethylhexyl-2-cyano- 3,3'-
Diphenyl acrylate (b) Ethyl-2-cyano-3,3'-diphenyl acrylate

The preferable blending amount of the ultraviolet ray blocking agent is 1 to 50 parts by weight per 100 parts by weight of the resin constituting the film.
Parts by weight, especially 1 to 20 parts by weight.

(3) Production method of heat-shrinkable film The synthetic resin film is given heat-shrinkability by, for example, the following method. First, the synthetic resin material is dried, melted, melt-extruded from a die, and a raw film is formed by a casting method, a calendar method, or the like. Next, the raw film is heated at 3 ° C. from the glass transition temperature (Tg) of the synthetic resin.
At a temperature higher than 5 ° C., preferably 1.5 to 5.0 times, preferably 1.0 to 5.0 times in the vertical or horizontal direction.
It is stretched 4.8 times to give a high shrinkage to the film.
Further, if necessary, the direction perpendicular to the stretching direction may be 1.0
The film is stretched up to 1.8 times, preferably 1.0 to 1.5 times.
This is effective for improving the tensile strength of the film and preventing the shrinkage in the stretching direction from being unnecessarily shrunk.

The stretching of the film is performed by a method such as simultaneous biaxial stretching, sequential biaxial stretching, or uniaxial stretching. Either longitudinal stretching or transverse stretching may be performed first. The stretched heat-shrinkable film can be used as a product as it is, but from the viewpoint of dimensional stability and the like, it is 50 to 1 mm.
The heat treatment may be performed at a temperature of 50 ° C. for several seconds to several tens of seconds. By performing such a heat treatment, favorable properties such as adjustment of the shrinkage in the shrinking direction of the film, reduction of shrinkage with time during storage of the unshrinkable film, and reduction of shrinkage spots can be exhibited. Although the thickness of the heat-shrinkable film is not particularly limited, it is 1 to 600 μm, particularly 10 to 3 μm.
Those having a size of 00 μm, particularly 20 to 70 μm, are practically used.

(4) Other Film Processing and Additives In order to further impart specific performance, conventionally known various processing and appropriate additives can be blended. Examples of processing include irradiation of ultraviolet rays, α-rays, β-rays, γ-rays, or electron beams, corona treatment, plasma irradiation treatment, flame treatment, and the like, vinylidene chloride, polyvinyl alcohol, polyamide, polyolefin, and the like. Resin coating, laminating
Or metal deposition. Examples of additives include resins such as polyamide, polyolefin, polymethyl methacrylate, and polycarbonate, inorganic particles such as kaolin, and release agents.

[Releasable UV-blocking ink layer] The UV-blocking ink layer is formed by applying a liquid ink composition to the bottom of a bottle, curing and drying. The ink layer is not particularly limited as long as it has an ultraviolet shielding property and can be peeled off from the bottom of the bottle in a predetermined peeling treatment.
If the ink layer is removed in a liquid form or dissolved in a processing liquid, it can be removed in a short time, but it is necessary to remove the newly generated organic matter in the processing liquid. Therefore, it is preferable to remove the film by removing it in a film form.

The ink layer can be peeled off by heating and foaming the ink layer to peel off the ink layer from the bottle substrate.
A method in which the ink layer is swollen with a treatment liquid and peeled off from the bottle substrate in a film form, a hot melt adhesive is applied in advance to the outer surface of the bottle, the ink layer is applied on the adhesive, and the adhesive is dissolved by heating. A known peeling method such as a method of removing an ink layer can be applied. In the present invention, a method of swelling the ink layer with a treatment liquid and peeling it from the bottle substrate in a film form is most preferable because the ink layer coating step and the ink layer peeling step are relatively easy. As a method of swelling the ink layer, for example, a method of chemically modifying a compound constituting the ink layer by introducing a specific functional group, and immersing the ink layer in a treatment liquid having a high affinity for the functional group. Examples can be given. in this way,
It is important to cure the ink layer to form a three-dimensional crosslinked structure. That is, if the crosslinked structure is not sufficiently formed, the ink layer is dissolved in the treatment liquid, and it is difficult to peel off the ink layer.

(1) Ink composition The ink composition used to form the ink layer contains, of course, an ultraviolet ray blocking agent such as a coloring agent or an ultraviolet ray absorbing agent for imparting an ultraviolet ray blocking effect. In the present invention, it is preferable that a release-imparting agent is added to impart releasability.

UV-blocking agent: As the UV-blocking agent, those exemplified for the heat-shrinkable film in the body of the bottle can be used for the ink layer.

Release agent: The release agent is, for example,
It is blended to form a space between the ink layer and the bottle base by foaming, or to introduce a specific functional group into the ink layer to swell in a specific processing solution. In the case of peeling by foaming, known fine particles of a foaming agent can be used.
In order to improve the applicability of the ink composition, the particle size of the foaming agent is preferably 1 to 50 μm. In order to cause the ink layer to swell and peel off in a film form, it is also important that the releasability-imparting agent has a polymerizable functional group. When the ink layer is cured, the release agent is chemically bonded to the three-dimensional crosslinked structure, and the treatment liquid easily enters the crosslinked structure and swells.
The ink layer can be peeled into a film.

In order to make the ink layer peelable with an aqueous alkali solution, an alkali swelling component is incorporated into the ink composition as a release agent. When the ink layer contains an alkali swelling component, film-like peeling becomes possible by a short-time treatment with an alkaline solution. That is, the ink layer formed on the bottom of the bottle is peeled off in a film form in an extremely short alkali treatment step after the collection of the bottle, and the bottle can be collected in a clean state as a plastic raw material.

Examples of the alkali swelling component include radiation curable hydrophilic organic compounds containing one or more amide groups or amino groups in the molecule and having one or more unsaturated double bonds. it can. Such alkali swelling components include, for example, (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, dimethylaminopropane (meth)
Acrylamide, N-vinylpyrrolidone, N-vinylformamide, acryloylmorpholine, N-methylol (meth) acrylamide, N-methoxymethyl (meth)
(Meth) acrylic acid derivatives such as acrylamide, N-ethoxymethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, (meth) acryloyloxyethyltrimethylammonium chloride and (meth) acrylamidopropyltrimethylammonium chloride Can be mentioned. Among these, particularly useful are dimethylacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, and N-vinylpyrrolidone in view of their molecular structures. Further, prepolymers and oligomers derived from the above-mentioned alkali swelling component can also be used.

Since the ink layer has a function of rapidly swelling and penetrating the deepened part of the cured film without being hydrolyzed with the aqueous alkali solution,
Even a thick print-cured film formed by multi-color superposition has a feature that swelling and infiltration with an alkaline aqueous solution can be completed in an extremely short time. Therefore, the coated cured film is quickly exfoliated in a short time by treatment with an alkaline aqueous solution, and the exfoliated film can be easily filtered off in a short time, so that organic substances diffuse into the treated alkaline aqueous solution. Can be suppressed very effectively. This means that the plastic material as a raw material to be recycled is prevented from being deteriorated by the alkaline aqueous solution, and the alkaline aqueous solution also has a very low treatment contamination degree, and can be repeatedly used.

Vehicle: The ink composition comprises a vehicle as a basic component, similar to a normal ink composition, and the above-mentioned ultraviolet ray blocking agent, release agent and, if necessary, other additives dispersed therein. It is. Oil,
Resins, solvents, plasticizers and the like are used. As oils,
Linseed oil which is a drying oil, boiled linseed oil, soybean oil which is a semi-dry oil, castor oil which is a non-drying oil and the like are used alone or in combination, and these oils are also used for denaturing the resin described below. used. As the resin, rosin, modified rosin, natural resins such as Gilsonite, and the following synthetic resins, for example, phenol resin, alkyd resin, xylene resin, urea resin, melamine resin, polyamide resin, acrylic resin, epoxy resin, ketone resin, Benzoguanamine resin, petroleum resin, vinyl chloride resin, vinyl acetate resin,
Chlorinated polypropylene, chlorinated rubber, cyclized rubber, cellulose derivatives and the like are used alone or in combination of two or more. As the solvent, polyhydric alcohol derivatives, polyhydric alcohols, alcohols, toluene, methyl ethyl ketone (MEK), solvent naphtha and the like are used. As the plasticizer, a phthalate-based, adipic-ester-based, citrate-based, or polyester-based plasticizer is used.

Other components: Other additives include natural or synthetic waxes, desiccants, dispersants, wetting agents, crosslinking agents, gelling agents, thickeners, anti-skinning agents, stabilizers, and gloss. Erasers, defoamers, photopolymerization initiators and the like are used.

The ink vehicle used may be heat-curable or ultraviolet-curable. As the heat-curable type, an ink using an alkyd type or polyester type vehicle is preferable. Vehicles of the alkyd or polyester type are (i) polyhydric alcohols, for example
Glycerin, pentaerythritol, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, sorbitol, mannitol,
At least one trimethylolpropane and (ii) a polybasic acid such as phthalic anhydride, isophthalic acid, maleic acid, fumaric acid, sebacic acid, adipic acid, citric acid, tartaric acid, malic acid, diphenic acid, 1,8 -Naphthalylic acid,
Terpene oil, at least one of rosin, and polycondensation,
If necessary, this may be (iii) a fatty oil or fatty acid, such as linseed oil, soybean oil, perilla oil, fish oil, tung oil, sunflower oil, walnut oil, deer oil, castor oil, dehydrated castor oil, distilled fatty acid, cottonseed oil, coconut oil Or a resin modified with these fatty acids or monoglycerides of fatty acids, and this resin is further modified with rosin, modified with non-drying fatty acid, modified with urea melamine resin, modified with drying oil fatty acid, modified with carbonic acid resin, modified with maleic resin, and modified with ester rosin. It is also used in the form of denaturation and other modifications of natural resins. An acid catalyst known per se, for example, toluenesulfonic acid, benzenesulfonic acid or the like can be used for curing the alkyd type or polyester type vehicle. These acid catalysts can be added in an amount of 0.5 to 1% by weight based on the resin. As the curing agent, metal soaps of various metals such as lead, cobalt, zinc, and manganese, dryers such as naphthenate, amino resins, and the like are used.

As another example of the heat-curable type, a resin obtained by dissolving a resin such as an amino resin or an acrylic resin in a reactive diluent such as a polyfunctional acrylic monomer can be suitably used. These vehicle compositions are used, if necessary, in combination with a thermal polymerization initiator. The polyfunctional acrylic monomer is a (meth) acrylate of an alkylene oxide-modified polyhydric alcohol having two or more, particularly three or more (meth) acryloyl groups in the molecule, and is represented by the following general formula (1). What is performed is suitable. In the formula, Z is a residue of a polyhydric alcohol, and R is a group having 2 carbon atoms.
R ₁ is a hydrogen atom or a methyl group, n is a number of 1 or more, m is a number of 2 or more, particularly 3 or more, and p is a number of 1 or less including zero. It is. Examples of polyhydric alcohols from which the (meth) acrylate of the above formula (1) is derived include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, glycerin, diglycerin, trimethylolethane, ditrimethylolethane, erythritol, Examples include xylitol, mannitol, and sorbitol, but are not limited thereto. As the alkylene oxide used for denaturation of the polyhydric alcohol,
Ethylene oxide is preferred, but other alkylene oxides such as propylene oxide can of course be used.

As the thermal polymerization initiator, an organic peroxide or an azo compound can be used. Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and 2,5-dimethyl-2,5. -Bis (t-butylperoxy) hexyne-
3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy)
Balalate, benzoyl-peroxide, t-butylperoxybenzoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide and 2, 4-dichlorobenzoyl peroxide, m-toluyl peroxide and the like. Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile.

The ultraviolet-curing type may be any of an ultraviolet radical polymerization type and an ultraviolet cationic polymerization type. As the ultraviolet radical polymerization type, a combination of an acrylic monomer or prepolymer and a photoradical polymerization catalyst is used. As the acrylic monomer or prepolymer, a monomer or prepolymer having a plurality of (meth) acryloyl groups in a molecule or a mixture thereof is used. Representative photoradical polymerization catalysts include benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, xanthones, and the like. As the ultraviolet cationic polymerization type, for example, a combination of an ultraviolet curable epoxy resin and a photo cationic polymerization catalyst is used. The ultraviolet-curable epoxy resin includes an epoxy resin component having an alicyclic group in a molecule and an adjacent carbon atom of the alicyclic group forming an oxirane ring. An epoxy compound having two epoxycycloalkane groups, for example, an epoxycyclohexane ring, an epoxycyclopentane ring, or the like is used alone or in combination. Suitable examples thereof include, but are not limited to, vinylcyclohexene diepoxide, vinylcyclohexene monoepoxide,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2- (3,4
-Epoxycyclohexyl-5,5-spiro-3,4-
Epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate, limonenedioxide and the like. The cationic ultraviolet polymerization initiator used in combination with the epoxy resin is one that is decomposed by ultraviolet light to release a Lewis acid, and the Lewis acid has an action of polymerizing an epoxy group, and examples thereof include aromatic iodonium. Salts, aromatic sulfonium salts, aromatic selenium salts, aromatic diazonium salts and the like.

The viscosity of the ink composition is generally set at a shear rate of 1
It is desirable that the value be in the range of 2 to 500 poise (p, 20 ° C.) in sec ⁻¹ . The ink layer has an average particle size of 0.01
The addition of transparent fine particles having a particle size of from 1 μm to 1 μm is preferred in terms of suppressing aggregation of the pigment and improving its dispersibility. The transparent fine particles may be made of resin or inorganic transparent fine particles such as amorphous silica. In the former case, the fine particles may be spherical particles having a particle diameter of 0.01 to 1 μm produced by an emulsion polymerization method or an emulsifier-free emulsion polymerization method. It is manufactured by emulsion polymerization so as to be in the range of 0.01 to 1 μm.

Examples of the monomer include generally lipophilic and radically polymerizable monomers, such as vinyl aromatic monomers, acrylic monomers, and vinyl ether monomers. As the vinyl aromatic monomer,
For example, styrene, α-chlorostyrene, o, m, p-chlorostyrene, p-ethylenestyrene, divinylbenzene and the like can be mentioned. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-hydroxyethyl acrylate,
-Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and the like. Examples of the vinyl ether-based monomer include vinyl-n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like. The above-mentioned monomer is a non-polar monomer, but can be used by copolymerizing with a cationic monomer or an anionic monomer as required for controlling the dispersibility of fine particles, or a cross-linkable monomer for preventing dissolution. And can be used after being copolymerized. As the cationic monomer, a monomer containing a cationic group such as a basic nitrogen atom, for example, dimethylaminoacrylate, dimethylaminoethylacrylate, diethylaminopropylacrylate, N-aminoethylaminopropylacrylate, dimethylaminomethacrylate, dimethylamino Ethyl methacrylate, diethylaminopropyl methacrylate, N-aminoethylaminopropyl methacrylate, vinylpyridine, 2-vinylimidazole, 2-hydroxy-3-acryloxypropylmethylammonium chloride,
Monomers containing primary, secondary or tertiary amino groups or quaternary ammonium groups such as acrylonitrile are used. As the anionic monomer, a monomer having an anionic property such as sulfonic acid, carboxylic acid, phosphonic acid or a salt thereof, preferably a monomer having a group of sulfonic acid or a salt thereof, for example, styrene sulfonic acid, vinyl sulfonic acid, Acrylic sulfonic acid, acrylamidomethylpropane sulfonic acid, acryl sulfonic acid, methacryl sulfonic acid, acryl-2-ethyl sulfonic acid, methacryl-2-ethyl sulfonic acid, and the like, and salts thereof such as sodium, potassium, calcium, and the like.
As a crosslinkable monomer, divinylbenzene (DV
B), diallyl phthalate (DAP), triallyl isocyanurate and the like.

In addition to the above monomers, radiation curable prepolymers and oligomers can be blended. Specifically, polyester acrylate, urethane acrylate, epoxy acrylate and the like. The prepolymer, oligomer and monomer are desirably selected in consideration of adhesion to a plastic product and curability as an ink composition.

Preparation of Ink Composition: The preparation of the ink composition is carried out by mixing a vehicle with an ultraviolet ray blocking agent, a release-imparting agent, and other additives, and kneading them well using a dispersing machine such as a roll mill. The ink composition preferably contains 1 to 50 parts by weight of an ultraviolet ray blocking agent and 1 to 20 parts by weight of a release agent for 100 parts by weight of a vehicle. Also,
The ink composition contains 0.1 to 10 parts by weight of a photopolymerization initiator capable of generating a reactive active site of any of a radical activated by ultraviolet rays, a cation, and an anion, if necessary.
0.1 to 10 parts by weight of a photosensitizer which is activated by ultraviolet rays and promotes generation of a reactive site of a photopolymerization initiator can be added. Can be added in an appropriate amount.

[Method of Manufacturing Ultraviolet-Shielding Bottle] The ultraviolet-shielding bottle of the present invention has a heat-shrinkable ultraviolet-shielding film layer coated on the outer surface of the body of the bottle base.
On the outer surface of the bottom portion of the bottle base, a releasable ultraviolet ray blocking ink layer is applied. In the present invention, the film layer and the ink layer may be separately applied to the bottle substrate, or the film layer and the ink layer may be provided so as to overlap at the boundary between the bottle body and the bottom. In particular, it is preferable that both layers are provided on the bottle base in a positional relationship in which the ultraviolet ray blocking film layer overlaps the peripheral portion of the ink layer.

The film layer can be provided by winding the above-described heat-shrinkable film around the bottle body, or covering the bottle body with a film formed into a cylindrical shape, and heating to the heat shrink temperature. The heat shrink temperature is usually 5
0 to 200 ° C, but in the case of plastic bottles,
Shrink by adjusting the temperature and time so that the bottle does not soften. On the other hand, the ink layer can be applied by applying the above-described ink composition to the outer surface of the bottom and curing or drying. The curing or drying temperature is usually 50 to 150.
In this case, the temperature and time are adjusted so that the bottle does not soften. In the present invention, since the ink layer is applied only to the outer surface of the bottom, there is an advantage that a very simple application method of, for example, immersing the bottle base in a shallow ink reservoir can be employed. Moreover, since the application area is only the outer surface of the bottom portion, it is narrow, and the subsequent curing or drying step can be performed in a short time.

When the film layer and the ink layer are provided so as to overlap each other at the boundary between the bottle body and the bottom, the bottle body and the bottom can be covered with the ultraviolet blocking layer without any gap. That is, there is an advantage that when one of the film layer and the ink layer is peeled off, the other can be peeled off integrally. In order to integrally peel the film layer and the ink layer, the adhesive force between the film layer and the ink layer is important. As a method of improving the adhesive force between the film layer and the ink layer, for example,
(A) a method in which an adhesive is applied to an overlapping portion between a film layer and an ink layer; and (b) a resin component of the same kind as the resin material of the film layer is blended into the ink composition, and the phase of the film layer and the ink layer is adjusted. And (c) a method of forming a crosslinked structure between the film surface and the ink composition during curing or drying of the ink composition.

Among the above-mentioned methods, since a desired adhesive strength can be obtained without using an adhesive, (c) a crosslinked structure is formed between the film surface and the ink composition during curing or drying of the ink composition. Is preferably adopted. In order to form a crosslinked structure, at least one of the film material and the ink composition may be blended with the above-described crosslinkable monomer, oligomer, prepolymer, or the like.
Further, the film layer may be subjected to a surface treatment so that the adhesive strength is improved. This surface treatment includes flame treatment,
Examples include polar flame treatment, chemical treatment, primer treatment, corona discharge treatment, ozone treatment, ultraviolet irradiation, and plasma processing. Examples of suitable combinations of a film material and an ink composition for improving the adhesiveness include the following. Film material Ink composition Surface treatment by flame treatment Divinylbenzene blended

A clear coating film can be applied on the ink layer if desired. As the clear coating film, what is generally called a finishing varnish in the field of can printing is used, and among the resins described with respect to the ink composition, those having excellent transparency are used. And ultraviolet curable ones.

The thickness of the clear coating film is not particularly limited as long as the protection of the ink layer is sufficient, but is preferably in the range of generally 3 to 10 μm, particularly preferably 4 to 6 μm.

[Method of peeling off UV-blocking coating (recycling method of bottle)] The film layer can be easily peeled by making a cut or tear. Alternatively, the film layer and the bottle base material can be easily separated by previously providing a weakening line on the heat-shrinkable film and tearing the film along the weakening line. on the other hand,
The ink layer can be peeled off from the bottom by subjecting the ink layer to a peeling treatment such as heating, immersion in a treatment liquid, or the like.

When the ink composition contains the alkali swelling component, the ink layer can be peeled into a film by immersing the ink layer in an alkaline aqueous solution. For example, the ink layer at the bottom of the bottle is immersed in a 1 to 3% aqueous solution of caustic soda heated to 80 to 90 ° C.
It is preferable to perform a stirring treatment for 30 minutes. After detaching the ink layer, the bottle can be washed with water and dried to obtain a recyclable bottle.

When the film layer and the ink layer are integrally separated from the bottle substrate, the ink layer is subjected to a peeling treatment so that the film layer can be peeled off. Then, when the film layer is torn along the line of weakness, the film layer is gripped. The ink layer as part can also be separated from the bottle substrate.

[0061]

According to the present invention, it is an object of the present invention to provide a bottle which can easily remove the ultraviolet ray blocking layer on the outer surface from the bottle, and has excellent strength, appearance and recyclability as well as ultraviolet ray blocking performance. According to the present invention, since the entire surface of the bottle can be covered with the ultraviolet ray blocking layer without any gap, the contents that are easily deteriorated by ultraviolet rays can be stored for a long period of time. In the present invention, both the heat-shrinkable film layer on the outer surface of the bottle body and the ink layer on the outer surface of the bottom of the bottle are easily separated from the bottle base, and the recyclability is improved. Also,
If the two layers are partially adhered in a positional relationship where the film layer and the ink layer overlap, the two layers can be integrally separated from the bottle base, further improving the recyclability.

[0062]

[Example] (Measurement of transmittance in the ultraviolet and visible light regions) A measuring portion of a bottle was cut out and a spectrophotometer UV-3 manufactured by Shimadzu Corporation was used.
It measured using 100PC. (Coating of UV blocking ink) Daieichiro SR-C600 green manufactured by Dainichi Seika Kogyo Co., Ltd. 1
After diluting with a solvent and dip coating a PET bottle, it was dried. The diluted ink is preliminarily made of ultraviolet-shielding ultrafine zinc oxide (average particle size 0.06 μm) in a solid content of 4% by weight.
Was mixed in. (Attachment of Shrink Label) A cylindrical label was put on the erect bottle, and the bottle was shrunk and adhered by passing it through an infrared oven (about 85 ° C.).

[Example 1] Transparent PE having a content of 500 ml
An infrared blocking ink was applied to the bottom outer surface of a T bottle (weight 32 g, bottle for hot pack filling: shape is shown in FIG. 1). The coating position was the entire bottom surface up to a height of 5 mm of the bottle. Average ink thickness after coating is about 40μ
m. UV-blocking shrink label (average particle size 0.06 μm, ultrafine zinc oxide 4 wt% blended polystyrene film 40 μm thick) on the coated and dried bottle
The top of the bottle was applied from below the neck, and the bottom of the bottle was applied except for the bottom. The label was applied to a position overlapping with the coated portion by about 2 mm, so that the bottle was covered with no gap below the neck.
Ultraviolet and visible light transmission of the shrink label-coated PET bottle body (at a height of 9 cm from the bottom) and ultraviolet and visible light transmission of the ink-coated PET bottle bottom (center) were measured. The results are shown in FIG. 3B and FIG. 4D. In addition, since the shrink label was easily peeled off from the PET bottle section, the end was fixed with Cellotape (registered trademark), and the measurement was performed within the range where the influence of Cellotape was not exerted. Since the label had a cut, it could be easily peeled off. After peeling off the label,
The bottle was crushed. When the flakes obtained by the pulverization were immersed in a 3% aqueous solution of caustic soda heated to 90 ° C. and stirred for 30 minutes, all of the applied ink was detached and transparent flakes were obtained.

[Comparative Example 1] The measurement of the PET bottle (without shrink label coating and without ink coating) described in the example was carried out in the same manner as in the example, and the transmission of ultraviolet light and visible light was measured. The results are shown in FIG. 3A and FIG. 4C.

[Comparative Example 2] An attempt was made to apply a shrink label to the PET bottle described in the example on the entire surface including the bottom except the neck, but it was impossible to cover the center of the bottom. Moreover, since the center of the bottom is concave, the label does not adhere to the bottom and the bottle lacks upright stability.

[Brief description of the drawings]

FIG. 1 is a side sectional view showing one example of an ultraviolet ray blocking bottle of the present invention.

FIG. 2 is an enlarged cross-sectional view showing an enlarged connection portion between an ink layer and a film layer in the ultraviolet ray blocking bottle of the present invention.

FIG. 3 is a graph showing light transmittance of bottle body portions of Example 1 and Comparative Example 1.

FIG. 4 is a graph showing the light transmittance at the bottom of the bottle of Example 1 and Comparative Example 1.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) B65D 81/30 BRF B65D 81/30 BRFD 4F100 C08J 5/00 C08J 5/00 7/04 CFD 7/04 CFDZ // B65D 1/09 C08L 67:00 C08L 67:00 B65D 1/00 BF term (reference) 3E033 AA02 BA01 BA13 BA17 BA18 BA26 BB01 BB08 CA20 DA03 DB01 DC03 DD05 FA03 GA02 3E062 AA09 AB02 AC02 JA04 JA05 JA08 JB05 JB23 JC02 JD05 3E CA13 EE34 GD10 4F006 AA35 AB13 AB16 AB18 AB35 BA03 CA07 4F071 AA43 AH05 BB08 4F100 AK01B AK12 AK41A AL05 AS00B AT00A BA02 DA06 EJ38A GB16 JD09B JL09 JL16

Claims (3)

[Claims] 1. A bottle base having a mouth, a body, and a bottom, a heat-shrinkable ultraviolet shielding film layer coated on an outer surface of a body of the bottle base, and an outer surface of a bottom of the bottle base. A UV-blocking ink layer comprising a releasable UV-blocking ink layer. 2. The bottle according to claim 1, wherein the bottle base is at least a biaxially stretched polyester bottle. 3. The bottle according to claim 1, wherein the two layers are provided on the bottle base in a positional relationship in which the ultraviolet ray blocking film layer overlaps the peripheral portion of the ultraviolet ray blocking ink layer.