WO2017038623A1 - 加飾用樹脂組成物及び該組成物を用いて形成されたメタリック層を有する多層ダイレクトブローボトル - Google Patents
加飾用樹脂組成物及び該組成物を用いて形成されたメタリック層を有する多層ダイレクトブローボトル Download PDFInfo
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- WO2017038623A1 WO2017038623A1 PCT/JP2016/074817 JP2016074817W WO2017038623A1 WO 2017038623 A1 WO2017038623 A1 WO 2017038623A1 JP 2016074817 W JP2016074817 W JP 2016074817W WO 2017038623 A1 WO2017038623 A1 WO 2017038623A1
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B29C49/04—Extrusion blow-moulding
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- 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
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Definitions
- the present invention relates to a decorative resin composition containing a metal pigment, and more particularly to a multilayer direct blow bottle having a metallic layer formed of the resin composition.
- Direct blow bottles generally have a flexible body wall and can be easily discharged with squeeze etc., so it can be used in a variety of foods, cosmetics, hair care (shampoo, rinse, etc.) products. It is widely used as a plastic container that fills the contents.
- a means of decorating the appearance in metallic style is adopted, but decorating in metallic style is limited to high price products such as cosmetic containers.
- a coating film of a metal pigment is formed on the outer surface of the container by spray coating using a metal pigment or the like, or a metal pigment is used.
- a method of creating a shrink film by gravure printing and covering the outer surface of the container with this shrink film is adopted, but such a means is to perform coating with each container or processing with a shrink film. This is because, for example, it is substantially inapplicable to decoration of inexpensive containers for hair care products.
- Patent Document 1 proposes a master batch method for forming a bottle having a layer decorated with a metal pigment by direct blow molding.
- a master batch method can perform metallic decoration at a lower cost than the spray coating method and the shrink film method described above, but in this case, the metallic feeling is not sufficient and the metallic feeling is more enhanced. There is a need to increase it.
- the above-described shrink film method has a drawback that the shape of the container is limited to a straight body shape or a shape close thereto.
- the present applicant previously proposed a multilayer direct blow bottle characterized in that a metallic layer in which a metal pigment having an average thickness of 1 ⁇ m or less is dispersed in a resin is formed at a position that can be seen from the outer surface side.
- Japanese Patent Application No. 2014-172762 Japanese Patent Application No. 2014-172762.
- an extremely thin metal pigment having an average thickness of 1 ⁇ m or less is used as a pigment for imparting a metallic feeling, and thereby a high metallic feeling is expressed.
- the reality is that a metallic feel is required.
- an object of the present invention is to provide a decorative resin composition that can be decorated in a metallic tone by an extremely inexpensive means and can give a remarkably excellent metallic feeling.
- Another object of the present invention is to provide a multilayer direct blow bottle provided with a metallic layer formed using the decorative resin composition and a method for producing the same.
- LDPE density and low-density polyethylene
- the metal pigment is dispersed in an amount of 0.1 to 30.0 parts by mass per 100 parts by mass of the total amount of the low density polyethylene (LDPE) and the linear low density polyethylene (LLDPE).
- the metal pigment is an aluminum pigment, Is preferred.
- a multilayer direct blow bottle characterized in that the metallic layer made of the decorative resin composition is formed at a position that can be visually recognized from the outer surface side.
- This multi-layer direct blow bottle (5) When a multi-angle colorimeter is used and light is incident on the outer surface of the bottle wall at 45 degrees, the lightness L * 15 (L * a * b *) due to the reflected light in the direction of 15 degrees with respect to the regular reflected light (Color system) is 150 or more, It shows the characteristics.
- the multilayer direct blow bottle is generally (6)
- the metallic layer is formed below the outer surface layer or the outer surface transparent resin layer
- the blend used for forming the metallic layer has the following viscosity conditional expressions (1) and (2): ⁇ 6 ⁇ V 6 -2000 (1) ⁇ 30 ⁇ V 30 -2000 (2)
- ⁇ 6 and ⁇ 30 indicate the shear viscosity (Pa ⁇ s) at shear rates of 6 s ⁇ 1 and 30 s ⁇ 1 when measured at a temperature of 210 ° C., respectively. That you are satisfied, Is preferred.
- the decorative resin composition is further prepared by melt mixing in an extruder, and co-extrusion using the resin composition prepared in the extruder is used to form a layer made of the composition. Is formed into a bottle shape by forming a pipe-shaped preform formed at a position that can be viewed from the outer surface side, and blowing a blow fluid with one end of the preform closed. A method of manufacturing a blow bottle is provided.
- a metal pigment having an average thickness of 600 nm or less is dispersed in the resin, and this metal pigment exhibits a metallic appearance and is decorated.
- this metal pigment is dispersed in a blend of low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).
- LDPE is obtained by polymerizing ethylene in a high pressure (about 1000 to 4000 atmospheres) and high temperature (about 100 to 350 ° C.) using a radical initiator as a catalyst, and is called high pressure polyethylene.
- a radical initiator as a catalyst
- an ethylene chain includes a long-chain branch, and such a structure brings about a decrease in density and flexibility.
- LLDPE is obtained by copolymerizing several kinds of ⁇ -olefin (for example, 1-butene, 1-hexene, 4-methylpentene-1, 1-octene, etc.) with a small amount of ethylene as a repeating unit.
- a thin metal pigment is dispersed in a blend of LDPE and LLDPE having the structure as described above. Therefore, when such a resin composition is melt extruded, the metal pigment is extruded.
- a direct blow molded container in which the layer formed by extrusion of such a resin composition exists at a position where it can be visually recognized from the outside, there is very little irregular reflection light, and many of them are normal. It becomes reflected light and an excellent metallic feeling is developed.
- the metal pigment when a metal pigment is dispersed only in LDPE, the metal pigment can be oriented in the extrusion direction to some extent by melt extrusion, but the orientation is not sufficient, and unoriented metal pigments There will be many, and the metallic feeling is not enough. Since this LDPE contains many long branches, it is considered that stress is applied to the metal pigment in directions other than the extrusion direction during melt extrusion. However, when LLDPE is blended with LDPE, since the linearity of LLDPE is high, stress applied to the metal pigment in a direction other than the extrusion direction can be effectively relaxed during melt extrusion, and as a result, It becomes possible to orient more metal pigments in the extrusion direction, and it seems that a better metallic feeling is expressed.
- the multilayer direct blow molded container in which the layer (metallic layer) formed by the decorative resin composition of the present invention is formed at a position where it can be visually recognized from the outside exhibits an excellent metallic feeling.
- the layer (metallic layer) formed by the decorative resin composition of the present invention when a multi-angle colorimeter is used and light is incident on the outer surface of the bottle wall at 45 degrees, the reflected light in the 15-degree direction is reflected from the regular reflected light.
- the lightness L * 15 is as high as 150 or more. The higher the brightness is, the more specular light is reflected and the more excellent metallic feeling is expressed.
- the L * 15 is a L * value by the L * a * b * color system (CIE1976 color space).
- Multi-layer direct blow bottles with a metallic layer as described above exhibit high decorativeness (metallic feel) due to the metallic layer, and without any post-treatment such as spray coating or shrink film treatment. Since the feeling is expressed, it has a great advantage of being extremely inexpensive. That is, the multilayer direct blow bottle of the present invention is effectively applied not only to expensive cosmetic applications but also to packaging of low-priced products represented by hair care products such as shampoos and rinses, liquid detergents and the like.
- FIG. 1 Schematic which shows the example of the layer structure of the multilayer direct blow bottle of this invention.
- the figure which shows the form of the resin flow of resin which forms the layer (inner layer) adjacent to the resin for metallic layers and the metallic layer in the case of extrusion molding.
- the decorative resin composition of the present invention is obtained by dispersing a metal pigment in a base resin as a matrix.
- a base resin low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) are used. And are used.
- the metal pigment to be dispersed in the base resin is for generating a metallic feeling and exhibits a metallic luster, such as an aluminum pigment, a copper pigment, a copper zinc (brass) pigment, a copper tin (bronze) pigment, A bright pigment whose surface such as mica is coated with aluminum, iron oxide, titanium oxide, or the like can be used.
- a metallic pigment or an aluminum bright pigment is suitable from the viewpoint of metallic luster.
- a thin metal pigment having an average thickness of 600 nm or less, preferably in the range of 100 to 500 nm is used. That is, when such a metal pigment having a thin average thickness is used, the metal pigment is quickly oriented along the flow direction (extrusion direction) of the base resin at the time of melt extrusion, which will be described later. It is possible to develop a metallic tone. For example, when a metal pigment having an average thickness larger than the above range is used, the directivity of reflected light is lowered and irregularly reflected light is increased, resulting in insufficient metallic feeling. Further, if the thickness of the metal pigment is excessively thin, the strength is lowered, and therefore, the metal pigment tends to be slightly lowered due to breakage during melt extrusion.
- the average particle diameter of the metal pigment is generally preferably in the range of 1 to 50 ⁇ m, particularly 5 to 30 ⁇ m, and the aspect ratio (ratio of particle diameter to thickness: particle diameter ( ⁇ m) / thickness ( ⁇ m)) ) Is preferably in the range of 10 or more.
- a flat shape having a particle size larger than the thickness has extremely high directivity of reflected light when oriented, and is extremely advantageous for giving a metallic feeling.
- the metal pigment is preferably a metal pigment obtained by mechanically flattening metal powder into flakes using a ball mill or the like. That is, such a metal pigment is usually as thick as 100 nm or more and is not easily damaged during melt extrusion.
- the metal pigment mentioned above is mixed with base resin in the state disperse
- a dispersant those that increase the dispersibility of the metal pigment in the base resin without impairing the extrudability of the base resin are preferably used.
- hydrocarbon waxes such as polyethylene wax and polypropylene wax, Higher fatty acid waxes are preferably used.
- Such a dispersant is generally used in an amount of about 10 to 50 parts by mass per 100 parts by mass of the metal pigment.
- the above-described metal pigment is 0.1 to 30.0 parts by mass, particularly 0.5 to 10.0 parts by mass, more preferably 1.0 to 5.0 parts by mass per 100 parts by mass of the base resin described later.
- the base resin for dispersing the metal pigment while shapeable polyethylene bottle shape is used by direct blow molding, in the present invention, in particular a density of 0.910 g / cm 3 or more, 0 blends of linear low density polyethylene (LLDPE) of .930g / cm 3 less than the low density polyethylene and (LDPE) density of 0.910 ⁇ 0.925g / cm 3 is used as the base resin.
- LLDPE linear low density polyethylene
- LDPE low density polyethylene
- the LDPE and LLDPE as described above are usually mixed at a mass ratio of 1: 9 to 9: 1.
- the total amount of LDPE and LLDPE is 100. It is desirable to use LDPE in an amount of 50 to 85 parts by weight, most preferably 50 to 75 parts by weight per part by weight. That is, in order to orient the metal pigment in the extrusion direction, it is necessary to mainly use LDPE having a long branch. In order to moderately suppress the orientation of the metal pigment due to the flow of LDPE, LLDPE having high linearity is used. By using it in an amount equal to or less than LDPE, the metal pigment can be most effectively oriented and the highest metallic feeling can be expressed.
- melt flow rate (MFR at 190 ° C.). ) Is 1.0 g / 10 min or less, particularly 0.3 to 1.0 g / 10 min. That is, when a material having a large MFR is used, the orientation of the metal pigment tends to be low due to the flow during melt extrusion.
- a decorative resin composition in which a metal pigment is dispersed in the blend is used for forming a metallic layer of a direct blow bottle, and this metallic layer is usually in a position in contact with the contents. Therefore, a layer adjacent to the metallic layer exists inside the metallic layer.
- the blend of LDPE and LLDPE has a melt viscosity close to that of the resin forming the layer adjacent to the inside of the metallic layer. Preferably it is.
- the blend used for forming the metallic layer has the following viscosity conditional expressions (1) and (2): ⁇ 6 ⁇ V 6 -2000 (1) ⁇ 30 ⁇ V 30 -2000 (2)
- ⁇ 6 and ⁇ 30 indicate the shear viscosity (Pa ⁇ s) at shear rates of 6 s ⁇ 1 and 30 s ⁇ 1 when measured at a temperature of 210 ° C., respectively. Is more preferable.
- the blended product further has the following viscosity conditional expression (3): ⁇ 10 ⁇ V 10 -2000 (3)
- V 10 is the shear viscosity (Pa ⁇ s) at a shear rate of 10 s ⁇ 1 of the resin adjacent to the inner layer side of the metallic layer
- ⁇ 10 is the shear rate of polyethylene used for forming the metallic layer is 10 s ⁇ 1 Shear viscosity (Pa ⁇ s) at It is optimal to satisfy
- a blend of LDPE and LLDPE so as to satisfy such a viscosity condition, deformation of the metal pigment during extrusion molding can be effectively prevented.
- the viscosity conditions required for the blend will be described later.
- the decorative resin composition in which the metal pigment is dispersed in the base resin may contain other components as long as the orientation of the metal pigment is not impaired.
- a dispersant that uniformly disperses the metal pigment may be blended.
- the above-described decorative resin composition of the present invention is used for the production of a multilayer direct blow bottle that is molded using extrusion molding. That is, the bottle is formed by extrusion forming a pipe-shaped preform (parison) having a predetermined multilayer structure, one end of the preform is pinched off, and in this state, a blow fluid such as air is preformed. It is manufactured by blowing into the bottle and shaping it into a bottle shape.
- the decorative resin composition of the present invention is used for forming a metallic layer present at a position visually recognized from the outside, and the metal pigment is oriented in the extrusion direction at the time of extrusion molding. A metallic feeling will be developed.
- the metallic layer formed from the decorative resin composition of the present invention is 1. It is shown. That is, in the embodiment of FIG. 1A, the metallic layer 1 in which the metal pigment is dispersed is formed on the outer surface, and the inner layer 3 located on the inner surface side that is in contact with the contents adjacent to the lower side thereof. Is provided. Further, in the embodiment of FIG. 1B, a transparent resin layer 2 is formed on the outer surface, and a metallic layer 1 is formed on the lower side of the transparent resin layer 2. The inner layer 3 located on the inner surface side that comes into contact with the contents is provided.
- this transparent resin layer 2 is mix
- a pigment different from the pigment to be used may be blended and decorated. Further, as long as the visibility of the metallic layer 1 is ensured, as shown in FIG. 1C, a pigment is blended in the transparent resin between the transparent resin layer 2 and the metallic layer 1 on the outer surface.
- the decorated decorative resin layer 5 can also be formed.
- the pigment blended in the decorative resin layer 5 is also different from the pigment blended in the metallic layer 1, and may be, for example, a metal pigment (for example, a pearl pigment) having an average thickness exceeding 1 ⁇ m.
- the metallic layer 1 is formed adjacent to the inner layer 3 located on the inner surface side in contact with the contents. Thus, in any aspect, the decoration by the metallic layer 1 is made.
- the metallic layer 1 is a layer formed from the above-described decorative resin composition of the present invention, and the extrusion direction (bottle 10 in the preform molding for molding the bottle 10).
- the metal pigment is oriented along the height direction), thereby giving a good metallic feeling.
- the thickness of the body portion of the metallic layer 1 varies depending on the size of the bottle, but it is desirable to have an appropriate thickness, for example, 10 ⁇ m or more. That is, if the thickness of the metallic layer 1 is too thin, the flow of the base resin during extrusion molding tends to be turbulent, and as a result, the orientation of the metal pigment becomes insufficient and the metallic feeling may be reduced. It is.
- Transparent resin layer 2 In the present invention, as shown in FIG. 1 (b), when the metallic layer 1 is formed on the lower side of the transparent resin layer 2 on the outer surface, the lower metallic layer 1 is used as the transparent resin.
- Various thermoplastic resins that can be used for the molding of direct blow bottles can be used on condition that they have transparency as long as the metallic feeling shown is not impaired.
- Such a thermoplastic resin is not particularly limited, but in general, an extrusion-grade olefin resin or polyester resin is preferably used.
- olefin resins examples include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), linear ultra-low density polyethylene (LVLDPE), etc.
- Examples thereof include copolymers and ion-crosslinked olefin copolymers (ionomers).
- An amorphous or low crystalline copolymer (COC) of an acyclic olefin and a cyclic olefin can also be used as a transparent resin for forming the transparent resin layer 2.
- polyester resin examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), or amorphous polyester resin in which a small amount of a copolyester unit is introduced into an ethylene terephthalate unit. be able to.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene naphthalate
- amorphous polyester resin in which a small amount of a copolyester unit is introduced into an ethylene terephthalate unit. be able to.
- copolymer component for forming the copolyester examples include isophthalic acid, p- ⁇ -oxyethoxybenzoic acid, naphthalene-2,6-dicarboxylic acid, diphenoxyethane-4,4′-dicarboxylic acid, 5- Dicarboxylic acid components such as sodium sulfoisophthalic acid, adipic acid, sebacic acid or alkyl ester derivatives of these dicarboxylic acids; propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol, cyclohexanedimethanol, Examples include glycol components such as ethylene oxide adducts of bisphenol A, diethylene glycol, and triethylene glycol.
- an olefin resin and an amorphous polyester resin are particularly preferable from the viewpoint of scratch resistance, flexibility, glossiness, and the like.
- the thickness of the body portion of the transparent resin layer 2 can be set in an appropriate range depending on the size of the direct blow bottle 10 and the required flexibility, squeeze property, etc.
- the thickness is set to about 10 to 200 ⁇ m.
- the adhesiveness between the transparent resin layer 2 and the metallic layer 1 is poor.
- an adhesive resin layer may be appropriately interposed therebetween.
- Adhesive resins used for forming such an adhesive resin layer are known per se, such as ethylene- ⁇ -olefin copolymer resins and their acid-modified resins, olefin-acid copolymer resins, glycidyl groups, and the like. Containing resin can be used. Moreover, in order to improve adhesiveness, you may add a well-known tackifier to those resin.
- any resin produced in any bonding mode such as random, block, or graft can be used.
- the acid-modified resin for example, an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, or a resin graft-modified with these anhydrides is used.
- These resins can be used alone, as a blend resin of two or more kinds, or as a blend resin with other resins.
- the tackifier include rosin resin, terpene resin, and petroleum resin. These resins can be used alone or in admixture of two or more.
- additives that can be used include thermoplastic elastomers, other thermoplastic resins, rubber resins, inorganic fillers, pigments, plasticizers, antioxidants, antistatic agents, light stabilizers, and antiblocking agents.
- a resin obtained by adding a tackifier to a polyolefin resin (particularly a polyethylene resin) is preferable.
- the thermoplastic elastomer is preferably a styrene-based elastomer in order to reduce unevenness at the layer interface.
- the metallic pigment mentioned in the section of the metallic layer can be blended in the adhesive resin layer to further improve the metallic feeling.
- the thickness of the adhesive resin layer may be such that an appropriate adhesive force can be obtained, and is generally about 10 to 200 ⁇ m.
- the inner layer facing the inner surface may be a known thermoplastic resin used for molding this type of direct blow bottle, such as the olefin resin described above. Or polyester resin.
- the inner layer facing the inner surface is desirably formed of high density polyethylene (HDPE) having a density of 0.930 g / cm 3 or more.
- the thickness of the inner layer formed by such HDPE is usually about 50 to 200 ⁇ m.
- the inner layer may have a multilayer structure including a plurality of resin layers.
- a regrind layer obtained by mixing scraps such as virgin resin can be provided as an intermediate layer.
- a gas barrier resin layer can be provided as an intermediate layer not facing the inner surface.
- a gas barrier resin layer is formed of, for example, a resin having an oxygen permeability coefficient of 5.5 ⁇ 10 ⁇ 12 cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg or less at 37 ° C.-0% RH,
- ethylene-vinyl alcohol copolymer and polyamide are representative, and ethylene-vinyl alcohol copolymer is particularly preferable.
- an ethylene-vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer), specifically, an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol%, particularly 25 to 50 mol%.
- a copolymer saponified product obtained by saponifying the polymer so that the degree of saponification is 96% or more, particularly 99 mol% or more is preferably used.
- the ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as EVOH) should have a molecular weight sufficient to form a film.
- EVOH ethylene-vinyl alcohol copolymer
- It has an intrinsic viscosity of 0.01 dl / g or more, particularly 0.05 dl / g or more, measured at 30 ° C.
- the above gas barrier resin layer may be blended with another thermoplastic resin in the oxygen barrier resin as long as the excellent oxygen barrier property is not impaired.
- a known oxygen-absorbing resin layer may be included as an intermediate layer not facing the inner surface.
- This oxygen-absorbing resin layer supplements oxygen barrier properties, and is a layer containing an oxidizing polymer and a transition metal catalyst, as described in JP-A-2002-240813, etc.
- the oxidizing polymer is oxidized by oxygen by the action of the system catalyst, thereby absorbing oxygen and blocking the permeation of oxygen.
- Such an oxidizable polymer and a transition metal catalyst are described in detail in the above Japanese Patent Application Laid-Open No.
- oxidizable polymer examples include Olefin resins having tertiary carbon atoms (such as polypropylene and polybutene-1, or copolymers thereof), thermoplastic polyesters or aliphatic polyamides; xylylene group-containing polyamide resins; ethylenically unsaturated group-containing polymers ( For example, polymers derived from polyenes such as butadiene).
- Olefin resins having tertiary carbon atoms such as polypropylene and polybutene-1, or copolymers thereof
- thermoplastic polyesters or aliphatic polyamides such as polypropylene and polybutene-1, or copolymers thereof
- xylylene group-containing polyamide resins examples include polymers derived from polyenes such as butadiene.
- ethylenically unsaturated group-containing polymers For example, polymers derived from polyenes such as butadiene.
- transition metal catalyst the inorganic
- the gas barrier resin layer and the oxygen-absorbing resin layer used as the intermediate layer as described above are set to such a thickness that the oxygen barrier property required according to the size of the bottle 10 and the type of contents is developed. Further, both the gas barrier resin layer and the oxygen-absorbing resin layer can be provided as intermediate layers.
- the inner layer 3 has a multilayer structure as described above, when the adhesion between adjacent layers is poor, or when the adhesion between the inner layer 3 and the metallic layer 1 is poor, the above-described adhesion is performed.
- An agent resin layer may be interposed.
- the total thickness of the inner layer 3 as described above is such that the characteristics required for the bottle 10 are developed according to the layer structure, the type of resin used, and the size (internal volume) of the bottle 10. It only has to be set.
- Decorative resin layer 5 In the present invention, as shown in FIG. 1 (c), the decorative resin layer 5 appropriately formed between the transparent resin layer 2 and the metallic layer 1 on the outer surface is blended with a pigment in the transparent resin.
- the base transparent resin include various resins exemplified for the metallic layer 1 and the transparent resin layer 2 described above, and adhesive resins exemplified for the adhesive resin layer.
- blended for decorating should just be a different pigment from the metal pigment mix
- each layer constituting the layer is blended with a lubricant, various modifiers, an ultraviolet absorber and the like as long as the metallic feeling is not impaired. Also good.
- the multi-layer direct blow bottle 10 described above forms a pipe-shaped multi-layer preform (parison) by co-extrusion using the number of extruders corresponding to the number of layers, pinches off one end of the preform, It is manufactured by blowing a blow fluid such as compressed air into a bottle shape.
- the metal pigment and the base resin are desirably mixed in a state where the base resin is plasticized. Specifically, the base resin is introduced into the kneading part of the extruder, and with the base resin melted, the metal pigment (specifically, the metal pigment dispersed in the aforementioned dispersant) is introduced. In this state, the mixture is extruded from an extruder to form the metallic layer 1 in the multilayer preform.
- the shearing force applied to the metal pigment by the screw of the extruder is effectively relieved, and damage and deformation of the metal pigment during extrusion molding are effectively prevented.
- the metal pigment is extruded. Since the alignment is aligned along the direction and this alignment state is maintained as it is after the blow, a good metallic feeling is stably expressed. For example, if a metal pigment is introduced before the base resin is plasticized, the shearing force applied to the metal pigment by the extrusion screw increases, so that the metal pigment is easily damaged or deformed, and the metallic feeling is likely to vary. Because there is a fear.
- the extrusion molding as described above is performed by attaching a multilayer die to the tip of the extruder and melt-extruding the resin (or resin composition) corresponding to each layer in the annular space in the die.
- the resin or resin composition
- FIG. 2 when the metallic layer 1 is provided adjacent to the inner layer 3, the resin flow of the inner layer 3 is extruded while maintaining a straight cylindrical shape, next to the multilayer die. From the annular space, the resin flow of the metallic layer 1 adjacent to the inner layer 3 (the resin flow of the resin composition for decoration of the present invention) is compressed inward and extruded to join the resin flow of the inner layer 3.
- the joined resin flow is pushed downward while maintaining a straight cylindrical shape with a layered structure of the resin flow of the inner layer 3 and the resin flow of the metallic layer 1.
- the junction area of the resin flow of the inner layer 3 and the resin flow of the metallic layer 1 is indicated by X.
- the flow rate of the melted resin is the fastest. Therefore, the resin flow in the metallic layer 1 is subjected to the largest shearing force in the junction region X.
- the resin located on the outer surface of the metallic layer 1 is omitted in FIG. 2, but the extruded resin flow is extruded so as to reduce the diameter from the outer surface side in the lower part where the combined resin flow becomes a stable laminar flow, Designed to merge.
- the resin in the layer located on the outer surface side of the metallic layer 1 is a time when the resin flow of the decorative resin composition forming the metallic layer 1 becomes a stable laminar flow.
- the resin flow of the inner layer 3 adjacent to the inner side of the metallic layer 1 is almost equal to that of the metallic layer 1 in the joining area X.
- the resin flow of the decorative resin composition ).
- the shear viscosity of the resin flow of the decorative resin composition (that is, the shear viscosity of the blended product) is too small as compared with the shear viscosity of the resin flow of the inner layer 3, the inner layer in the junction region X The resin flow of 3 and the resin flow of the metallic layer 1 are disturbed, the thickness of the metallic layer 1 is uneven, which may cause shark skin, and this resin flow (decorating resin composition) This may cause deformation of the metal pigment contained in the glass and reduce the metallic feeling. This is because the metal pigment is thin and easily deforms due to a shearing force due to a difference in viscosity.
- a blend of LDPE and LLDPE used for forming the decorative resin composition is expressed by the following formulas (1) and (2): ⁇ 6 ⁇ V 6 -2000 (1) ⁇ 30 ⁇ V 30 -2000 (2)
- V 6 and V 30 are the shear viscosities (Pa ⁇ s) of the resin forming the layer adjacent to the inner layer side of the metallic layer 1 at a shear rate of 6 s ⁇ 1 and 30 s ⁇ 1 when measured at a temperature of 210 ° C., respectively.
- the layer adjacent to the inner layer side of the metallic layer 1 means the inner layer 3 facing the inner surface of the bottle (for example, a layer formed of polyethylene such as HDPE).
- the metallic layer 1 When itself has a multilayer structure, it is a regrind layer, a gas barrier layer, an oxygen absorption layer or an adhesive layer adjacent to the metallic layer 1 according to the layer structure, and these resin layers are formed.
- the blend used for the formation of the metallic layer 1 is prepared so as to satisfy the conditions of the above formulas (1) and (2).
- the melt extrusion temperature is roughly 150 to 230 ° C., and is a temperature in the vicinity of 210 ° C., and the shear rate in the die head (particularly the above-mentioned confluence).
- the shear rate in the region X is approximately in the range of 6-30 s ⁇ 1 .
- the above viscosity condition is that the viscosity of the resin adjacent to the inner layer side of the metallic layer 1 is used for forming the metallic layer in the die head of the extruder, particularly in the merging portion region X. This means that it is not excessively large compared to the viscosity of polyethylene.
- the blend used for forming the metallic layer 1 satisfies the conditional expressions (1) and (2), the stress generated in the resin flow of the metallic layer 1 in the joining region X is effectively relaxed. As described above, deformation of the metallic pigment is effectively prevented, and in combination with the orientation of the metal pigment described above, a more excellent metallic feeling can be expressed, and further, uneven thickness of the metallic layer 1 and generation of shark skin Is more effectively suppressed.
- the vertical axis y is the shear viscosity (Pa ⁇ s)
- Viscosity conditional expressions (1) and (2) are set so that the shear viscosity at shear rates of 6 s ⁇ 1 and 30 s ⁇ 1 is within a predetermined range.
- It is a value (2000 Pa ⁇ s) corresponding to (V 6 - ⁇ 6 ) in 1)
- ⁇ is a value (2000 Pa ⁇ s) corresponding to (V 30 - ⁇ 30 ) in the formula (2).
- the above-described blend used for forming the metallic layer 1 further includes the following viscosity conditional expression (3): ⁇ 10 ⁇ V 10 -2000 (3)
- V 10 is a shear rate of 10 s ⁇ 1 of the resin adjacent to the inner layer side of the metallic layer 1.
- Shear viscosity (Pa ⁇ s) at ⁇ 10 is the shear viscosity (Pa ⁇ s) of the blend used in forming the metallic layer 1 at a shear rate of 10 s ⁇ 1 . It is desirable to satisfy
- the shear viscosity curve is shown as a substantially straight line, but depending on the blend used, this curve may be a convex curve upward in the region at shear rates of 6 s ⁇ 1 to 30 s ⁇ 1. Or it may be a downwardly convex curve. Therefore, even if the shear viscosity at the shear rate of 6 s ⁇ 1 and the shear viscosity at the shear rate of 30 s ⁇ 1 satisfy the conditions of the equations (1) and (2), the shear rate 6 s ⁇ 1 and the shear rate shear rate of blend in the intermediate region of the 30s -1 it is sometimes the shear rate of the resin layer adjacent to the inner layer falls below significantly.
- the shear viscosity of the blend for the metallic layer 1 is close to the shear viscosity of the resin of the adjacent layer even when the shear rate is 10 s ⁇ 1.
- the shear viscosity of the blend is contiguous throughout the region at shear rates of 6 s -1 to 30 s -1 (corresponding to the shear rate of the resin in the die head). It is close to the shear viscosity of the resin of the layer. That is, the shear viscosity of the blend for the metallic layer 1 and the resin of the layer adjacent to the inner layer side of the metallic layer 1 is approximated in the merging portion region X where the shear rate is not uniform.
- ⁇ is a value (2000 Pa ⁇ s) corresponding to (V 10 ⁇ 10 ) in the formula (3).
- the shear viscosity of a blend of LDPE and LLDPE prepared in advance will be described later.
- the blend of LDPE and LLDPE is changed or blended within the aforementioned range. What is necessary is just to change suitably the kind of LDPE or LLDPE used for this.
- the metallic layer 1 for decorating in a metallic tone is obtained at the same time as molding, and does not require coating after molding or treatment with a decorated shrink film, And since it can manufacture using the existing extrusion molding machine, the increase in the cost for metallic decoration can be avoided effectively, and also the form of a bottle (like a shrink film decorated with metallic) In particular, there is no restriction on the form of the body). Furthermore, despite the formation of the metallic layer 1 in which the metallic pigment is dispersed by extrusion molding, the metallic pigment is effectively prevented from being damaged or deformed, so that a good metallic feeling is stably provided. .
- the metal pigment in the metallic layer 1 is effectively oriented in the extrusion direction, a multi-angle colorimeter is used, and light is incident on the outer surface of the bottle wall at 45 degrees.
- the lightness L * 15 by the reflected light in the direction of 15 degrees with respect to the regular reflected light is 150 or more, and the highest is 160 or more.
- the flip-flop (FF) value represented by the following formula also shows a high value of 15 or more.
- L * 15 is the brightness of the reflected light in the direction of 15 degrees with respect to the regular reflected light when light is incident on the outer surface of the bottle wall at 45 degrees.
- L * 110 is the brightness of the reflected light in the direction of 110 degrees with respect to the regular reflected light
- L * 45 is in the direction of 45 degrees with respect to the regular reflection light (90 degrees with respect to the reflection surface). Is the brightness of the reflected light. That is, a high lightness L * 15 and a high FF value indicate that a very excellent metallic feeling is expressed.
- the L * value indicating the brightness of each reflected light described above are all L * value by the L * a * b * color system (CIE1976 color space).
- the multilayer direct blow bottle 10 described above may have various layer configurations shown in FIG. 1, but the most commonly employed layer configurations are as follows.
- Adhesive layer Adhesive resin thickness 20-200 ⁇ m
- Metallic layer Metal pigment (especially flaky aluminum pigment)
- Regrind layer Burr and HDPE during bottle molding Thickness 500-1000 ⁇ m
- Inner layer HDPE Thickness 50-200 ⁇ m
- the multilayer direct blow bottle provided with the metallic layer made of the decorative resin composition of the present invention effectively avoids the increase in cost due to the metallic decoration, so that not only high-priced products such as cosmetics, but also shampoo and It can also be used as a packaging bottle for low-priced products such as rinses, liquid detergents, and softeners, and the product value can be improved by metallic decoration.
- the shear viscosity of the used resin was measured as follows. ⁇ Measurement of shear viscosity> This was performed in accordance with JIS K7199: 1999 using CAPILOGRAPH manufactured by Toyo Seiki Seisakusho. The measurement conditions were as follows: a capillary die having a capillary length of 10 mm and a capillary diameter of 1.0 mm was used, the test temperature was 210 ° C., the preheating time was 5 minutes, the residence time was 15 minutes, and the shear rate was sequentially decreased.
- Layer structure 5 layers, 5 types (outside) PET / AD / metallic layer (base resin + aluminum pigment) / HDPE / HDPE (inside) (Outside) 5/7/10/68/10 (Unit: wt%)
- Inside material Polyethylene terephthalate resin (PET): Eastman Easter GN001
- LDPE-B Nippon Polyethylene Corporation Novatec LB420M Density: 0.922 g / cm 3 MFR (190 ° C.): 0.7 g / 10 min
- Table 1 shows the type and blend ratio of the base resin of the metallic layer used in each example and comparative example, and the type and content of the aluminum pigment.
- the lightness L * 15 , flip-flop (FF) value, and metallic feeling of the produced multilayer bottle were evaluated. The results are shown in Table 1.
- the evaluation method is described below.
- the average thickness of the aluminum pigment is the average value of 50 randomly selected aluminum pigments measured with a scanning electron microscope, and the average particle size is the volume cumulative particle size distribution curve measured with a laser diffraction particle size distribution analyzer.
- the particle size is represented by D 50 which is a particle size having a cumulative degree of 50%.
- the central part of the body part of the produced multilayer bottle was cut at four points at intervals of 90 ° to obtain test pieces.
- the test surface is irradiated with light having a wavelength range of 400 to 700 nm at an incident angle of 45 ° with the vertical direction of the test surface of the test piece as a plane being 0 ° as a reference.
- the brightness of reflected light (L * a * b * L * value of the color system) when the offset angle from the regular reflection direction to the incident light side is 15 °, 45 °, and 110 ° is set to L * 15 , L * 45 , measured as L * 110 .
- the degree of change in the L * value between the offset angle of 15 ° and 110 ° is calculated as the FF value shown below.
- FF value 2.69 * (L * 15- L * 110 ) 1.11 / L * 45 0.86 (Comprehensive evaluation)
- Table 1 shows the comprehensive evaluation results of the presence of visual metallic feeling and the appearance defects (die line, Miguel). Evaluation is shown by relative evaluation based on Comparative Example 1, where ++ is very excellent, ++ is excellent, + is good, and ⁇ is equivalent to the standard.
- the shear viscosity ⁇ (Pa ⁇ s) at shear rates of 6 s ⁇ 1 , 30 s ⁇ 1 and 10 s ⁇ 1 of the blends used for forming the metallic layer in Examples 2 and 3 measured at a temperature of 210 ° C. It was as follows.
- Example 2 6804 Pa ⁇ s (6 s ⁇ 1 ) 4053 Pa ⁇ s (30 s ⁇ 1 ) 5400 Pa ⁇ s (10 s ⁇ 1 )
- Example 3 7451 Pa ⁇ s (6 s ⁇ 1 ) 3944 Pa ⁇ s (30 s ⁇ 1 ) 5456 Pa ⁇ s (10 s ⁇ 1 )
- the relationship between the shear viscosity of the blend used for forming the metallic layer and the shear viscosity of HDPE used for forming the adjacent inner layer satisfies the viscosity conditional expressions (1), (2), and (3).
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Abstract
Description
即ち、プラスチック容器の外観をメタリック調に加飾するためには、金属顔料などを用いてのスプレー塗装により、容器の外表面に金属顔料の塗膜を形成したり、或いは金属顔料を用いてのグラビア印刷によりシュリンクフィルムを作成し、このシュリンクフィルムにより容器の外表面を覆うという手段が採用されているが、このような手段は、容器毎に塗装を行ったり、或いはシュリンクフィルムによる処理を行うことが必要であり、著しく高コストになってしまうため、例えばヘアケア商品用の安価な容器の加飾には実質的に適用できないからである。
さらに、前述したシュリンクフィルム方式は、容器の形状が直胴形状或いはそれに近い形状に限定されてしまうという欠点もある。
また、本出願人は、先に、平均厚みが1μm以下の金属顔料が樹脂に分散されたメタリック層が、外面側から視認できる位置に形成されていることを特徴とする多層ダイレクトブローボトルを提案した(特願2014-172762号)。かかる多層ダイレクトブローボトルでは、メタリック感を付与するための顔料として平均厚みが1μm以下と極めて薄い金属顔料が使用されており、これにより、高いメタリック感が発現するというものであるが、より一層のメタリック感が求められているのが実情である。
本発明の他の目的は、上記の加飾用樹脂組成物を用いて形成されたメタリック層を備えた多層ダイレクトブローボトル及びその製造方法を提供することにある。
(1)前記低密度ポリエチレン(LDPE)と直鎖状低密度ポリエチレン(LLDPE)とが、LDPE:LLDPE=1:9~9:1の質量比でブレンドされていること、
(2)前記低密度ポリエチレン(LDPE)及び直鎖状低密度ポリエチレン(LLDPE)は、何れも1.0g/10min以下のメルトフローレート(190℃)を有していること、
(3)前記金属顔料が、前記低密度ポリエチレン(LDPE)と直鎖状低密度ポリエチレン(LLDPE)との合計量100質量部当り0.1~30.0質量部の量で分散されていること、
(4)前記金属顔料がアルミ顔料であること、
が好適である。
この多層ダイレクトブローボトルは、
(5)多角度測色計を使用し、ボトル壁の外面に45度で光を入射したとき、正反射光に対して15度方向の反射光による明度L* 15(L*a*b*表色系)が150以上であること、
という特性を示す。
また、該多層ダイレクトブローボトルは、一般に、
(6)前記メタリック層が、外表面層または外表面透明樹脂層の下側に形成されていること、
という構造を有しており、さらに、
(7)前記メタリック層に対して内層側に隣接する層を形成している樹脂について、210℃の温度で測定したときの剪断速度6s-1及び30s-1での剪断粘度(Pa・s)をそれぞれV6、V30とした時、前記メタリック層の形成に使用されている前記ブレンド物は、下記粘度条件式(1)及び(2):
η6≧V6-2000 (1)
η30≧V30-2000 (2)
上記式(1)及び(2)中、
η6及びη30は、それぞれ、210℃の温度で測定したときの剪断速度
6s-1及び30s-1での剪断粘度(Pa・s)を示す、
を満足していること、
が好適である。
本発明では、上記のような構造を有するLDPEとLLDPEとのブレンド物中に、厚みの薄い金属顔料が分散されているため、このような樹脂組成物が溶融押出されたとき、金属顔料が押出方向に速やかに配向し、この結果として、このような樹脂組成物の押出により形成される層が外部から視認される位置に存在するダイレクトブロー成形容器では、乱反射光が極めて少なく、その多くが正反射光となり、優れたメタリック感が発現するのである。
尚、LLDPEのみに金属顔料を分散させた場合には、流動性が悪いため、シャークスキンや周方向の厚みムラによるダイラインが生じるようになるばかりか、金属顔料の配向も不十分となってしまう。LLDPEは、分子の直線性が高いため、その流動により金属顔料を配向させることが困難になるためではないかと思われる。
尚、このL* 15は、L*a*b*表色系(CIE1976色空間)によるL*値である。
即ち、本発明の多層ダイレクトブローボトルは、高価な化粧品用途に限らず、シャンプー、リンスなどのヘアケア製品、液体洗剤などに代表される低価格商品の包装に有効に適用される。
本発明の加飾用樹脂組成物は、金属顔料を、マトリックスとなるベース樹脂中に分散させたものであり、ベース樹脂としては、低密度ポリエチレン(LDPE)と直鎖状低密度ポリエチレン(LLDPE)とが使用される。
このような分散剤は、一般に、金属顔料100質量部当り10~50質量部程度の量で使用される。
本発明では、上記のような位置にメタリック層が形成されるという観点から、上記LDPEとLLDPEとのブレンド物は、メタリック層の内側に隣接する層を形成する樹脂に近い溶融粘度を有していることが好ましい。具体的には、前記メタリック層に対して内層側に隣接する層を形成している樹脂について、210℃の温度で測定したときの剪断速度6s-1及び30s-1での剪断粘度(Pa・s)をそれぞれV6、V30とした時、該メタリック層の形成に使用されている前記ブレンド物は、下記粘度条件式(1)及び(2):
η6≧V6-2000 (1)
η30≧V30-2000 (2)
上記式(1)及び(2)中、
η6及びη30は、それぞれ、210℃の温度で測定したときの剪断速度
6s-1及び30s-1での剪断粘度(Pa・s)を示す、
を満足していることがより好ましい。
また、上記のブレンド物は、さらに、下記粘度条件式(3):
η10≧V10-2000 (3)
上記式中、
V10はメタリック層の内層側に隣接する樹脂の剪断速度10s-1での
剪断粘度(Pa・s)であり、
η10はメタリック層の形成に用いるポリエチレンの剪断速度10s-1
での剪断粘度(Pa・s)である、
を満足していることが最適である。
このような粘度条件を満足するように、LDPEとLLDPEとのブレンド物が調製されていることにより、押出成形に際しての金属顔料の変形を有効に防止することができる。
尚、ブレンド物に要求される粘度条件については後述する。
上述した本発明の加飾用樹脂組成物は、押出成形を利用して成形される多層ダイレクトブローボトルの製造に使用される。即ち、このボトルは、押出成形により所定の多層構造を有するパイプ形状のプリフォーム(パリソン)を成形し、このプリフォームの一方側端部をピンチオフし、この状態で空気等のブロー流体をプリフォーム内に吹き込んでボトル形状に賦形することにより製造される。かかるボトルにおいて、本発明の加飾用樹脂組成物は、外部から視認される位置に存在するメタリック層の形成に使用されるものであり、押出成形時に金属顔料が押出方向に配向し、優れたメタリック感が発現することとなる。
即ち、図1(a)の態様では、外表面に金属顔料が分散されたメタリック層1が形成されており、その下側に隣接して、内容物と接触する内表面側に位置する内層3が設けられている。
また、図1(b)の態様では、外表面には透明樹脂層2が形成されており、この透明樹脂層2の下側にメタリック層1が形成されており、この態様でも、隣接して、内容物と接触する内表面側に位置する内層3が設けられている。このようなメタリック層1は、外面から視認される位置に形成されていればよいので、この透明樹脂層2には、メタリック層1の視認性が確保される限りにおいて、メタリック層1に配合される顔料とは異なる顔料が配合されて加飾されていてもよい。
さらに、メタリック層1の視認性が確保される限りにおいて、図1(c)に示されているように、外表面の透明樹脂層2とメタリック層1との間に、透明樹脂に顔料が配合された加飾樹脂層5を形成することもできる。この加飾樹脂層5に配合される顔料も、メタリック層1に配合される顔料とは異なるものであり、例えば、平均厚みが1μmを超える金属顔料(例えばパール顔料など)であってよい。何れの層構造においても、メタリック層1は、内容物と接触する内表面側に位置する内層3に隣接して形成される。
このように、何れの態様においても、メタリック層1による加飾がなされている。
メタリック層1は、上記で述べたように、前述した本発明の加飾用樹脂組成物から形成されている層であり、該ボトル10を成形するためのプリフォーム成形時の押出方向(ボトル10の高さ方向)に沿って、金属顔料が配向しており、これにより、良好なメタリック感が付与されている。
本発明において、図1(b)に示されているように、外表面の透明樹脂層2の下側にメタリック層1が形成されている場合、かかる透明樹脂としては、下層のメタリック層1が示すメタリック感が損なわれない限りの透明性を有していることを条件として、ダイレクトブローボトルの成形に使用し得る種々の熱可塑性樹脂を用いることができる。
このような熱可塑性樹脂としては、特に制限されないが、一般的には、押出成形用グレードのオレフィン系樹脂やポリエステル樹脂が好適に使用される。
尚、上記のコポリエステル形成用の共重合成分としては、イソフタル酸、p-β-オキシエトキシ安息香酸、ナフタレン-2,6-ジカルボン酸、ジフェノキシエタン-4,4’-ジカルボン酸、5-ナトリウムスルホイソフタル酸、アジピン酸、セバシン酸またはこれらジカルボン酸のアルキルエステル誘導体などのジカルボン酸成分;プロピレングリコール、1,4-ブタンジオール、ネオペンチルグリコール、1,6-ヘキシレングリコール、シクロヘキサンジメタノール、ビスフェノールAのエチレンオキサイド付加物、ジエチレングリコール、トリエチレングリコールなどのグリコール成分を挙げることができる。
さらに、接着樹脂層にメタリック層の項で挙げた金属顔料を配合して、更にメタリック感を向上させることもできる。
図1(a)及び図1(b)の層構造において、内表面に面する内層としては、この種のダイレクトブローボトルの成形に使用される公知の熱可塑性樹脂、例えば、前述したオレフィン系樹脂やポリエステル樹脂が使用される。特に、内表面に面する内層は、密度が0.930g/cm3以上の高密度ポリエチレン(HDPE)により形成することが望ましい。このようなHDPEにより形成される内層の厚みは、通常、50~200μm程度である。
このようなガスバリア性樹脂層は、形成するガスバリア性樹脂としては、例えば37℃-0%RHにおける酸素透過係数が5.5×10-12cc・cm/cm2・sec・cmHg以下の樹脂、例えば、エチレン-ビニルアルコール共重合体やポリアミドが代表的であり、特にエチレン-ビニルアルコール共重合体が好適である。
かかるエチレン-ビニルアルコール共重合体(エチレン-酢酸ビニル共重合体ケン化物)としては、具体的には、エチレン含有量が20乃至60モル%、特に25乃至50モル%のエチレン-酢酸ビニル共重合体を、ケン化度が96%以上、特に99モル%以上となるようにケン化して得られる共重合体ケン化物が好適に使用される。このエチレン-ビニルアルコール共重合体(以下EVOHと呼ぶことがある)は、フィルムを形成し得るに足る分子量を有するべきであり、一般に、フェノール/水の重量比が85/15の混合溶媒中、30℃で測定して0.01dl/g以上、特に0.05dl/g以上の固有粘度を有している。
上記のガスバリア性樹脂層は、その優れた酸素バリア性が損なわれない限りにおいて、酸素バリア性樹脂に他の熱可塑性樹脂がブレンドされていてもよい。
本発明において、図1(c)で示されているように、外表面の透明樹脂層2とメタリック層1との間に適宜形成される加飾樹脂層5は、透明樹脂に顔料が配合されたものであり、ベースの透明樹脂としては、前述したメタリック層1や透明樹脂層2について例示した各種の樹脂、或いは接着樹脂層で例示した接着樹脂などを挙げることができる。
また、加飾のために配合する顔料は、メタリック層1の視認性が損なわれない限りにおいて、メタリック層1に配合される金属顔料とは異なる顔料であればよく、例えば、種々の無機或いは有機顔料に加え、メタリック層1で用いる金属顔料として例示されたもののうち、平均厚みが1μmを超えるものや、天然の雲母に酸化チタンや酸化鉄をコートしたパール顔料などが使用される。
上述した多層ダイレクトブローボトル10は、層の数に応じた数の押出機を用いての共押出によりパイプ状の多層プリフォーム(パリソン)を成形し、このプリフォームの一端部をピンチオフし、内部に圧縮エアなどのブロー流体を吹き込んでボトル形状に賦形することにより、製造される。
このような手段を採用することにより、押出機のスクリューにより金属顔料に加わる剪断力が有効に緩和され、押出成形時の金属顔料の破損や変形が有効に防止され、この状態で金属顔料が押出方向に沿って揃って配向し、この配向状態がブロー後もそのまま保持されるため、良好なメタリック感が安定して発現することとなる。
例えば、ベース樹脂が可塑化する前の段階で金属顔料を投入すると、押出スクリューにより金属顔料に加わる剪断力が大きくなるため、金属顔料の破損や変形が生じ易く、メタリック感にバラつきを生じ易くなるおそれがあるからである。
また、メタリック層1の外面に位置する樹脂は、図2では省略されているが、合流した樹脂流が安定した層流となった下方部分で、外面側から縮径するように押し出されて、合流するように設計されている。
η6≧V6-2000 (1)
η30≧V30-2000 (2)
式(1)及び(2)中、
V6及びV30は、それぞれ、210℃の温度で測定したときの剪断速度
6s-1及び30s-1でのメタリック層1の内層側に隣接する層を形成す
る樹脂の剪断粘度(Pa・s)を示し、
η6及びη30は、それぞれ、210℃の温度で測定したときの剪断速度
6s-1及び30s-1での上記ブレンド物の剪断粘度(Pa・s)を示す、
で規定される剪断粘度条件を満足するように調製することにより、上記のようなメタリック層1に隣接する内層との粘度差による不都合を抑制することができる。
尚、図2の例では、メタリック層1の内層側に隣接する層は、ボトル内面に面している内層3(例えばHDPE等のポリエチレンにより形成されている層)を意味するが、この内層3自体が多層構造を有する場合には、その層構造に応じて、メタリック層1に隣接しているリグラインド層、ガスバリア層、酸素吸収層或いは接着剤層であり、これらの樹脂層を形成している樹脂に対して、メタリック層1の形成に使用されているブレンド物が上記式(1)及び(2)の条件を満足するように調製される。
メタリック層1の形成に用いるブレンド物が上記条件式(1)及び(2)を満足していることにより、上記合流部領域Xでメタリック層1の樹脂流に生じる応力が有効に緩和され、結果として、メタリック顔料の変形が有効に防止され、前述した金属顔料の配向性と相俟って、より優れたメタリック感を発現させることができ、さらにはメタリック層1の厚みムラやシャークスキンの生成もより有効に抑制されるのである。
η10≧V10-2000 (3)
上記式中、
V10は、メタリック層1の内層側に隣接する樹脂の剪断速度10s-1
での剪断粘度(Pa・s)であり、
η10は、メタリック層1の形成に使用されているブレンド物の剪断速度
10s-1での剪断粘度(Pa・s)である、
を満足していることが望ましい。
尚、図3中、γが式(3)中の(V10-η10)に相当する値(2000Pa・s)である。
また、このような高い明度L* 15に伴い、下記式で示されるフリップフロップ(FF)値も15以上と高い値を示す。
FF=(L* 15-L* 110)/L* 45
式中、
L* 15は、ボトル壁の外面に45度で光を入射したとき、正反射光に
対して15度方向の反射光による明度であり、
L* 110は、上記正反射光に対して110度方向の反射光の明度で
あり、
L* 45は、上記正反射光に対して45度方向(反射面に対して90度)
の反射光の明度である。
即ち、明度L* 15及びFF値が高いことは、非常に優れたメタリック感が発現していることを示す。
尚、上述した各反射光の明度を示すL*値は、何れもL*a*b*表色系(CIE1976色空間)によるL*値である。
最外層(透明層):
非晶性ポリエステル樹脂層
厚み10~200μm、特に25~100μm
接着剤層:
接着剤樹脂
厚み20~200μm
メタリック層:
金属顔料(特にフレーク状アルミ顔料)
LDPE:LLDPE=15:85~85:15(質量比)
厚み10~200μm、特に30~100μm
リグラインド層:
ボトル成形時のバリ及びHDPE
厚み500~1000μm
最内層:
HDPE
厚み50~200μm
<剪断粘度の測定>
(株)東洋精機製作所製CAPILOGRAPHを用い、JIS K7199:1999に準拠して行った。測定条件は、キャピラリー長10mm、キャピラリ-径1.0mmのキャピラリ-ダイを使用し、試験温度は210℃、予熱時間5分、滞留時間15分、剪断速度を順次減少させて試験を行った。
下記ダイレクトブロー成形機、押出し機を用いて500ml多層ボトル(50g)を成形した。
成形機:タハラ社製シャトル型成形機
押出し機:第1層φ30-FF L/D=22
第2層φ30-FF L/D=22
第3層φ30-FF L/D=22
第4層φ55-FF L/D=28
第5層φ40-FF L/D=28
層構成:5種5層
(外側)PET/AD/メタリック層(ベース樹脂+アルミ顔料)
/HDPE/HDPE(内側)
(外側)5/7/10/68/10(単位:wt%)(内側)
材料:
ポリエチレンテレフタレート樹脂(PET):
イーストマン社イースターGN001
接着剤樹脂(AD):三菱化学社モディックF573
メタリック層ベース樹脂
低密度ポリエチレン(LDPE)
LDPE-A:住友化学社スミカセンF108-2
密度:0.921g/cm3
MFR(190℃):0.4g/10min
LDPE-B:日本ポリエチレン社ノバテックLB420M
密度:0.922g/cm3
MFR(190℃):0.7g/10min
直鎖状低密度ポリエチレン(LLDPE):
日本ポリエチレン社ノバテックUF230
密度:0.921g/cm3
MFR(190℃):1.0g/10min
メタリック層アルミ顔料
アルミ顔料A:
平均厚み300nm、平均粒径11μm、アスペクト比37
アルミ顔料B:
平均厚み200nm、平均粒径 7μm、アスペクト比35
アルミ顔料C:
平均厚み400nm、平均粒径15μm、アスペクト比38
アルミ顔料D:
平均厚み700nm、平均粒径50μm、アスペクト比71
アルミ顔料E:
平均厚み 30nm、平均粒径 8μm、アスペクト比270
(アルミ顔料は分散剤としてポリエチレンワックスを含むペレットとして使用した。)
高密度ポリエチレン(HDPE):
プライムポリマー社ハイゼックス6700B
剪断粘度:6196Pa・s(6s-1)
2593Pa・s(30s-1)
4555Pa・s(10s-1)
作成した多層ボトルの明度L* 15、フリップフロップ(FF)値、メタリック感を評価した。結果を表1に示す。
以下に評価方法を記載する。
(アルミ顔料の平均厚み及び平均粒径)
アルミ顔料の平均厚みは、不作為に選択した50個のアルミ顔料を走査型電子顕微鏡で測定した平均値であり、平均粒径はレーザー回折式粒度分布測定器で測定した際の体積累積粒度分布曲線において累積度50%の粒子径であるD50で表した。
作製した多層ボトルの胴部の中央部分を90°間隔で4箇所を切り開いて試験片とした。X―Rite社製MA94JP多角度分光測色計を用いて、波長範囲400~700nmの光を、平面とした試験片の試験面の垂直方向を0°基準として入射角45°で試験面に照射し、正反射方向から入射光側へのオフセット角が15°、45°、110°方向の反射光の明度(L*a*b*表色系のL*値)をそれぞれL* 15、L* 45、L* 110として測定する。
測定したL*値(L* 15、L* 45、L* 110)を用い、オフセット角15°から110°間のL*値の変化の度合いを下記に示すFF値として算出する。
FF値=2.69*(L* 15-L* 110)1.11/L* 45 0.86
(総合評価)
目視によるメタリック感及び外観不良(ダイライン、ミゲル)の有無を合わせた総合評価結果を表1に示す。評価は比較例1を基準とした相対評価で示し、+++は非常に優れている、++は優れている、+は良好である、±は基準と同等を表している。
実施例2:6804Pa・s(6s-1)
4053Pa・s(30s-1)
5400Pa・s(10s-1)
実施例3:7451Pa・s(6s-1)
3943Pa・s(30s-1)
5456Pa・s(10s-1)
メタリック層の形成に用いたブレンド物の剪断粘度と、隣接する内層の形成に用いたHDPEの剪断粘度の関係は粘度条件式(1)(2)(3)を満足するものである。
2:透明樹脂層
3:内層
5:加飾樹脂層
10:多層ダイレクトブローボトル
Claims (10)
- 密度が0.910g/cm3以上、0.930g/cm3未満の低密度ポリエチレン(LDPE)と密度が0.910~0.925g/cm3の直鎖状低密度ポリエチレン(LLDPE)とのブレンド物に、平均厚みが600nm以下の金属顔料が分散されていることを特徴とする加飾用樹脂組成物。
- 前記低密度ポリエチレン(LDPE)と直鎖状低密度ポリエチレン(LLDPE)とが、LDPE:LLDPE=1:9~9:1の質量比でブレンドされている請求項1に記載の加飾用樹脂組成物。
- 前記低密度ポリエチレン(LDPE)及び直鎖状低密度ポリエチレン(LLDPE)は、何れも1.0g/10min以下のメルトフローレート(190℃)を有している請求項1に記載の加飾用樹脂組成物。
- 前記金属顔料が、前記低密度ポリエチレン(LDPE)と直鎖状低密度ポリエチレン(LLDPE)との合計量100質量部当り0.1~30.0質量部の量で分散されている請求項1に記載の加飾用樹脂組成物。
- 前記金属顔料がアルミ顔料である請求項1に記載の加飾用樹脂組成物。
- 請求項1に記載の加飾用樹脂組成物によるメタリック層が、外面側から視認できる位置に形成されていることを特徴とする多層ダイレクトブローボトル。
- 多角度測色計を使用し、ボトル壁の外面に45度で光を入射したとき、正反射光に対して15度方向の反射光による明度L* 15(L*a*b*表色系)が150以上である請求項6に記載の多層ダイレクトブローボトル。
- 前記メタリック層が、外表面層または外表面透明樹脂層の下側に形成されている請求項6に記載の多層ダイレクトブローボトル。
- 前記メタリック層に対して内層側に隣接する層を形成している樹脂について、210℃の温度で測定したときの剪断速度6s-1及び30s-1での剪断粘度(Pa・s)をそれぞれV6、V30とした時、前記メタリック層の形成に使用されている前記ブレンド物は、下記粘度条件式(1)及び(2):
η6≧V6-2000 (1)
η30≧V30-2000 (2)
上記式(1)及び(2)中、
η6及びη30は、それぞれ、210℃の温度で測定したときの剪断速度
6s-1及び30s-1での剪断粘度(Pa・s)を示す、
を満足している請求項6に記載の多層ダイレクトブローボトル。 - 請求項1に記載の加飾用樹脂組成物を、押出機内での溶融混合により調製し、該押出機内で調製された樹脂組成物を用いての共押出により、該組成物による層が外面側から視認される位置に形成されたパイプ形状のプリフォームを成形し、該プリフォームの一端部を閉じた状態でブロー流体を吹き込んでボトル形状に賦形することを特徴とする多層ダイレクトブローボトルの製造方法。
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WO2018221190A1 (ja) * | 2017-05-29 | 2018-12-06 | 東洋製罐株式会社 | 加飾多層押出ブローボトル |
JP2020138783A (ja) * | 2019-02-28 | 2020-09-03 | 株式会社吉野工業所 | 押出しブロー容器、及び押出しブロー容器の製造方法 |
JP2020138785A (ja) * | 2019-02-28 | 2020-09-03 | 株式会社吉野工業所 | 押出しブロー容器 |
JP2020138784A (ja) * | 2019-02-28 | 2020-09-03 | 株式会社吉野工業所 | 押出しブロー容器 |
JP2020196491A (ja) * | 2019-05-31 | 2020-12-10 | 株式会社吉野工業所 | 押出しブロー容器 |
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