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WO2010061910A1 - High-gloss multilayer plastic container - Google Patents

High-gloss multilayer plastic container Download PDF

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Publication number
WO2010061910A1
WO2010061910A1 PCT/JP2009/070007 JP2009070007W WO2010061910A1 WO 2010061910 A1 WO2010061910 A1 WO 2010061910A1 JP 2009070007 W JP2009070007 W JP 2009070007W WO 2010061910 A1 WO2010061910 A1 WO 2010061910A1
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WO
WIPO (PCT)
Prior art keywords
plastic container
resin
multilayer plastic
layer
gloss
Prior art date
Application number
PCT/JP2009/070007
Other languages
French (fr)
Japanese (ja)
Inventor
雄一郎 加藤
将 石川
Original Assignee
東洋製罐株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋製罐株式会社 filed Critical 東洋製罐株式会社
Priority to CN2009801479190A priority Critical patent/CN102227359A/en
Priority to JP2010540519A priority patent/JPWO2010061910A1/en
Publication of WO2010061910A1 publication Critical patent/WO2010061910A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles

Definitions

  • the present invention relates to a multilayer plastic container having excellent appearance, deep high surface gloss, and excellent scratch resistance.
  • Multilayer plastic bottles having a transparent plastic (particularly copolymerized PET) resin as the outermost layer are excellent in surface gloss (Patent Document 1), and are used in applications requiring high decorativeness such as for cosmetics.
  • the polyester resin is inferior in scratch resistance, and has a surface that is easily damaged during packing and transportation or at a retail store, and the appearance is easily impaired.
  • an object of the present invention is to provide a multilayer plastic container excellent in surface gloss and scratch resistance.
  • the present inventors solved the above-mentioned problems by forming inorganic particles in the outermost transparent resin layer of the multilayer plastic container to obtain an outermost layer having specific performance.
  • the present invention has been completed by finding out what can be done. That is, the present invention provides a high gloss multilayer plastic container, wherein the outermost transparent resin contains inorganic particles, the surface has a dynamic friction coefficient of 2 or less, and the 60 ° gloss is 90% or more. provide.
  • a multilayer plastic container having excellent surface gloss and scratch resistance can be obtained.
  • the high gloss multilayer plastic container of the present invention is characterized in that the outermost transparent resin contains inorganic particles, the surface dynamic friction coefficient is 2 or less, and the 60 ° gloss is 90% or more.
  • the transparent resin constituting the outermost layer of the high gloss multilayer plastic container of the present invention include polyester resins, polyamide resins, and polycarbonate resins.
  • the transparent resin is preferably a polyester resin.
  • thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene terephthalate is preferable in terms of easy molding and easy transparency.
  • a preferable polyester resin is polyethylene terephthalate (PET).
  • a copolymerized PET resin mainly composed of ethylene terephthalate units and containing other polyester units can be used.
  • the copolymer component for forming such a copolymerized PET resin 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 their alkyl ester derivatives; propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol, cyclohexane dimethanol And glycol components such as ethylene oxide adduct of bisphenol A, diethylene glycol and triethylene glycol.
  • a particularly preferable polyester-based resin includes amorphous copolymerized PET resin.
  • the polyester resin to be used is a polyester having an intrinsic viscosity [ ⁇ ] of 0.5 (dl / g) or more, particularly 0.6 (dl / g) or more from the viewpoint of mechanical properties of the container wall. Is preferred.
  • the polyester resin may be uncolored or colored as long as it is transparent. You may add a well-known additive to a polyester-type resin to such an extent that transparency is not impaired.
  • additives include thermoplastic elastomers, other thermoplastic resins, rubber resins, inorganic fillers, pigments, plasticizers, antioxidants, antistatic agents, light stabilizers, antiblocking agents, lubricants, and dyes. it can. However, it is preferable to avoid using an additive that increases the surface roughness of the polyester resin.
  • the inorganic particles contained in the outermost transparent resin layer are not particularly limited, and silica, glass particles (glass beads), talc, alumina, titanium oxide, kaolin, zeolite, aluminosilicate, calcium nitrate, nitric acid Examples include barium and calcium carbonate. Silica particles or glass particles are preferable, and silica particles are more preferable.
  • the inorganic particles are preferably transparent.
  • the content of inorganic particles in the outermost transparent resin layer is preferably 0.1 to 1.0% by weight, more preferably 0.1 to 0.3% by weight. If the content is less than the above range, the effect of reducing scratches cannot be obtained.
  • the average particle size of the inorganic particles is preferably 1 to 15 ⁇ m. In the present invention, it is more preferable to use inorganic particles having an average particle diameter of 5 to 8 ⁇ m, particularly silica particles. If the average particle size is smaller than the above range, the effect of reducing scratches cannot be obtained. On the other hand, if the average particle size exceeds the above range, the surface roughness of the container increases. When the average particle size is 5 to 8 ⁇ m, the effect of reducing scratches can be obtained in a range where the content is relatively small, and a container having good gloss can be obtained.
  • the high gloss multilayer plastic container of the present invention has a surface dynamic friction coefficient of 2 or less, preferably 1.5 or less, and most preferably 1.2 or less.
  • the dynamic friction coefficient is measured by the following method with reference to JIS K 7125. Secure two bottles horizontally on a sliding table. On top of that, 100 ml of tap water is put, and a bottle with a wire attached to the nozzle is placed on top of it. The wire is connected to the fixed load cell, and the slide table is pulled in the horizontal direction opposite to the load cell (see FIG. 1). Measure the load cell load when the bottle with water in the upper part is dragged against the lower bottle, and convert it to the coefficient of dynamic friction. The direction of the bottles is the same for all three bottles.
  • the high gloss multilayer plastic container of the present invention has a surface 60 ° gloss of 90% or more.
  • the 60 ° gloss is measured according to JIS Z 8741, for example, using VG 2000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • the high gloss multilayer plastic container of the present invention preferably has a surface roughness Ra of 0.1 to 0.2 ⁇ m. More preferably, it is 0.1 to 0.15 ⁇ m. If the surface roughness Ra is 0.2 ⁇ m or less, a sufficient glossiness is obtained, but if it is less than 0.1 ⁇ m, scratches tend to occur.
  • the surface roughness Ra is measured according to JIS B 0601 using, for example, 1400A-3DF manufactured by Tokyo Seimitsu Kogyo.
  • a blow mold having a surface roughness of the inner surface of the blow mold of about 0.2 ⁇ m ⁇ Ra ⁇ 0.8 ⁇ m is used.
  • a container with Ra ⁇ 0.2 ⁇ m can be obtained even when the surface roughness of the outer layer of the container is maximum. If the surface roughness of the inner surface of the blow mold is made smaller than the above range, an air trap may occur during molding of the plastic container, and molding defects such as partial surface irregularities may occur.
  • the high gloss multilayer plastic container of the present invention preferably has a transparent resin layer, a transparent adhesive resin layer, and a colored polyolefin resin layer in order from the outer surface side, and the colored polyolefin resin layer preferably contains a bright pigment.
  • a transparent adhesive resin constituting the transparent adhesive resin layer a known resin having adhesiveness to both the transparent resin and the polyolefin resin can be used.
  • a polyester resin is used as the transparent resin, for example, ethylene / ⁇ -olefin copolymer resins and acid-modified resins thereof, olefin / acid copolymer resins, glycidyl group-containing resins and the like can be used.
  • tackifier to those resin.
  • the copolymer those produced by any bonding mode such as random, block, graft and the like can be used.
  • the acid-modified resin include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and crotonic acid; or resins that are graft-modified with these anhydrides. These resins can be used alone or as a blend resin of two or more; 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.
  • a well-known additive to a transparent adhesive resin layer.
  • 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 transparent adhesive resin layer may be uncolored or colored as long as it is transparent, and may contain a glitter pigment.
  • the adhesive resin layer is colored, for example, by adding a bright pigment to the colored polyolefin layer, the reflected light from the bright pigment is transmitted through the transparent colored adhesive layer, giving a deep and unique metallic feeling. This is preferable. In some cases, a special hue effect can be obtained by changing the color tone of the transparent adhesive layer and the polyolefin layer.
  • the colorant used for the transparent adhesive resin layer is not particularly limited as long as the transparency is not impaired.
  • an organic pigment such as an azo pigment, a phthalocyanine pigment, a condensed polycyclic pigment, or a dyed lake pigment can be used.
  • resin which comprises a colored polyolefin-type resin layer there is no restriction
  • Any polyolefin-based resins such as graft-modified polyolefin resins can be used.
  • Particularly preferred polyolefin resins include propylene-ethylene block copolymers. These polyolefin resins can be used alone or in admixture of two or more.
  • the colored polyolefin resin layer may be either a transparent colored layer or an opaque colored layer. Moreover, you may comprise not only one colored layer but 2 or more colored layers. In addition, an intermediate layer made of another resin or the like, or an inner surface resin layer made of, for example, a polyolefin resin can be provided on the inner layer side of the colored polyolefin-based resin layer.
  • colorant blended in the colored polyolefin resin layer there are no particular restrictions on the colorant blended in the colored polyolefin resin layer, and organic pigments such as azo pigments, phthalocyanine pigments, condensed polycyclic pigments and dyed lake pigments, and aluminum bright pigments such as polarized pearl pigments. Further, bright pigments such as mica-based bright pigments and glass-based bright pigments can be used. These colorants can be used alone or in combination of two or more. These colorants and extender pigments may be used in combination.
  • a bright pigment is blended in the colored polyolefin resin layer, the reflected light of the bright pigment passes through a combination of a transparent polyester resin layer and a transparent adhesive resin layer, resulting in a deep gloss.
  • a multilayer plastic container having a metallic color tone can be obtained.
  • the colored polyolefin resin layer has a multi-layer structure comprising a transparent colored resin layer adjacent to the transparent adhesive resin layer and a colored resin layer containing a bright pigment provided on the inner layer side, it is transparent to the metal ground. This is preferable because a deep and unique metallic feeling as if ink was printed is obtained.
  • FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the multilayer plastic container of the present invention.
  • This container has a transparent polyester resin layer A, a transparent adhesive resin layer B, a colored polyolefin resin layer C containing a bright pigment, and a colored polyolefin resin layer D containing no bright pigment in order from the outer surface side.
  • a container having the layer structure shown in FIG. 1 was manufactured as follows.
  • Four extruders (hereinafter, the resin extruders constituting the resin layers A, B, C, and D are referred to as extruders A, B, C, and D, respectively) were filled with the resin.
  • the parison was sandwiched between molds having cavities, and compressed air was blown into the parison to produce a rectangular tube-shaped hollow container.
  • each physical property value was measured by the method described above.
  • the surface roughness Ra of the multilayer plastic container was “1400A-3DF manufactured by Tokyo Seimitsu Kogyo”, and “VG 2000 manufactured by Nippon Denshoku Industries Co., Ltd.” was used for the 60 ° gloss. Further, the surface roughness Ra of the multilayer plastic container was measured by cutting a portion having a large surface roughness directly or directly in a size of 15 mm ⁇ 15 mm from a flat portion other than the nozzle portion of the container.
  • the vibration test was performed according to JIS Z 0232 with the following equipment and conditions.
  • Testing machine Electrodynamic testing machine manufactured by Shinken Co., Ltd.
  • Testing method Random testing method (Bottle filled with rated amount of tap water (20 ° C), put into an actual distribution carton, and place the carton on the shaking table Apply random vibration for 30 minutes in the vertical method.)
  • Extruder A having a diameter of 40 mm was filled with transparent amorphous cyclohexanedimethanol (CHDM) copolymerized polyethylene terephthalate resin (Eastman's PETG DryStar 0601).
  • Extruder B with a diameter of 40 mm is filled with a transparent and colorless LDPE resin containing styrene elastomer (Mitsubishi Chemical Modic F512A) and 0.3% by weight azo red pigment as a coloring pigment. did.
  • CHDM transparent amorphous cyclohexanedimethanol
  • Extruder B with a diameter of 40 mm is filled with a transparent and colorless LDPE resin containing styrene elastomer (Mitsubishi Chemical Modic F512A) and 0.3% by weight azo red pigment as a coloring pigment.
  • Extruder C having a diameter of 50 mm, transparent colorless ethylene / propylene block copolymer resin (EP310D manufactured by HMC), 0.5% by weight of pearl red (mica-based pigment having an average particle diameter of 21 ⁇ m) as a bright pigment, and as a colored pigment 0.5% by weight of azo red pigment was filled.
  • An extruder D having a diameter of 40 mm was filled with the ethylene / propylene block copolymer resin (EP310D manufactured by HMC). The resin filled in each extruder was plasticized and kneaded while being heated, and extruded from a multilayer head to form a multilayer parison.
  • each layer of this bottle was an outer layer A 50 ⁇ m, a transparent adhesive resin layer B 70 ⁇ m, a bright colored polyolefin resin layer C 710 ⁇ m, and a colored polyolefin resin layer D 170 ⁇ m.
  • the bottle surface roughness Ra was 0.07 ⁇ m, the dynamic friction coefficient was 4.67, and the 60 ° gloss was 102.8%. As a result of the vibration test, many noticeable scratches were generated.
  • Example 1 A master batch (Sumitomo) made by adding 5% by weight of porous silica with an average particle size of 8 ⁇ m (laser diffraction scattering method) as inorganic particles to transparent amorphous cyclohexanedimethanol (CHDM) copolymer polyethylene terephthalate resin EPM-7Y029 manufactured by Color Co., Ltd. was added in an amount of 2.5% by weight to the resin of the outer layer A (addition amount of porous silica in the outer layer A was 0.125% by weight).
  • a square cylindrical hollow bottle was obtained.
  • the bottle surface roughness Ra was 0.10 ⁇ m
  • the dynamic friction coefficient was 1.10
  • 60 ° gloss was 96.4%.
  • Example 2 A rectangular tube-shaped hollow bottle having a capacity of 500 mL was obtained in the same manner as in Example 1 except that the addition amount of the master batch was 5.0 wt% (the addition amount in the outer layer A was 0.25 wt%).
  • the bottle surface roughness Ra was 0.15 ⁇ m
  • the dynamic friction coefficient was 0.76
  • the 60 ° gloss was 93.0%.
  • the scratches were hardly noticeable and had excellent gloss.
  • Comparative Example 2 In Comparative Example 1, only the mold was changed to obtain a rectangular tube-shaped hollow bottle having a capacity of 190 mL.
  • the bottle surface roughness Ra was 0.05 ⁇ m
  • the dynamic friction coefficient was 4.67
  • the 60 ° gloss was 100.5%.
  • Example 3 A rectangular tube-shaped hollow bottle having a capacity of 190 mL was obtained in the same manner as in Example 1 except that the mold was the same as that in Comparative Example 2.
  • the bottle surface roughness Ra was 0.10 ⁇ m
  • the dynamic friction coefficient was 1.10
  • the 60 ° gloss was 96.9%.
  • fine flaws were observed, but no major flaws were generated.
  • Example 4 A rectangular tube-shaped hollow bottle having a capacity of 190 mL was obtained in the same manner as in Example 3 except that the addition amount of the master batch was changed to 5% by weight.
  • the bottle surface roughness Ra was 0.15 ⁇ m
  • the dynamic friction coefficient was 0.76
  • the 60 ° gloss was 92.0%.
  • the scratches were hardly noticeable and had excellent gloss.
  • Example 5 A rectangular tube-shaped hollow bottle having a capacity of 500 mL was obtained in the same manner as in Comparative Example 3 except that the addition amount of the master batch was 10 wt% (the addition amount in the outer layer A was 0.5 wt%).
  • the bottle surface roughness Ra was 0.10 ⁇ m
  • the dynamic friction coefficient was 1.27
  • the 60 ° gloss was 99.0%.
  • the state of large conspicuous scratches was reduced from Comparative Example 1.

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Abstract

Provided is a multilayer plastic container having excellent surface gloss and scratch resistance.  The high-gloss multilayer plastic container is characterized in that a transparent resin in the outermost layer contains inorganic particles and that the surface dynamic friction coefficient is 2 or less and the 60° gloss is 90% or more.

Description

高光沢多層プラスチック容器High gloss multilayer plastic container
　本発明は、優れた外観と深みのある高い表面光沢を有し、耐傷性に優れた多層プラスチック容器に関する。 The present invention relates to a multilayer plastic container having excellent appearance, deep high surface gloss, and excellent scratch resistance.
　最外層に透明プラスチック（特に、共重合ＰＥＴ）樹脂を有する多層プラスチックボトルは、表面光沢に優れ（特許文献１）、化粧品向けなどの高い装飾性が求められる用途で採用されている。
　しかしながら、ポリエステル樹脂は耐傷性に劣り、梱包・輸送時あるいは小売店頭などで傷付き、外観性が損なわれ易い面がある。 Multilayer plastic bottles having a transparent plastic (particularly copolymerized PET) resin as the outermost layer are excellent in surface gloss (Patent Document 1), and are used in applications requiring high decorativeness such as for cosmetics.
However, the polyester resin is inferior in scratch resistance, and has a surface that is easily damaged during packing and transportation or at a retail store, and the appearance is easily impaired.
国際公開第２００８／０９０６５５号パンフレットInternational Publication No. 2008/090655 Pamphlet
　したがって、本発明は、表面光沢に優れ、耐傷性に優れた多層プラスチック容器を提供することを目的とする。 Therefore, an object of the present invention is to provide a multilayer plastic container excellent in surface gloss and scratch resistance.
　本発明者らは、上記課題を解決するために鋭意検討した結果、多層プラスチック容器の最外層の透明樹脂層に無機粒子を含有させて特定の性能を有する最外層とすることで上記課題を解決できることを見出し、本発明を完成した。
　すなわち、本発明は、最外層の透明樹脂が無機粒子を含有し、表面の動摩擦係数が２以下であり、かつ、６０°グロスが９０％以上であることを特徴とする高光沢多層プラスチック容器を提供する。 As a result of intensive studies to solve the above-mentioned problems, the present inventors solved the above-mentioned problems by forming inorganic particles in the outermost transparent resin layer of the multilayer plastic container to obtain an outermost layer having specific performance. The present invention has been completed by finding out what can be done.
That is, the present invention provides a high gloss multilayer plastic container, wherein the outermost transparent resin contains inorganic particles, the surface has a dynamic friction coefficient of 2 or less, and the 60 ° gloss is 90% or more. provide.
　本発明によれば、表面光沢に優れ、耐傷性に優れた多層プラスチック容器を得ることができる。 According to the present invention, a multilayer plastic container having excellent surface gloss and scratch resistance can be obtained.
動摩擦係数の測定方法の概略図である。It is the schematic of the measuring method of a dynamic friction coefficient. 本発明の高光沢多層プラスチック容器の層構成の１例を示す断面模式図である。It is a cross-sectional schematic diagram which shows an example of the layer structure of the high gloss multilayer plastic container of this invention.
　本発明の高光沢多層プラスチック容器は、最外層の透明樹脂が無機粒子を含有し、表面の動摩擦係数が２以下であり、かつ、６０°グロスが９０％以上であることを特徴とする。
　本発明の高光沢多層プラスチック容器の最外層を構成する透明樹脂としては、ポリエステル系樹脂、ポリアミド系樹脂、ポリカーボネート系樹脂などが挙げられる。透明樹脂として、好ましくはポリエステル系樹脂である。特に、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリナフタレンテレフタレート等の熱可塑性ポリエステル類を使用すると、成形が容易で、透明性を容易に得られる点で好ましい。
　好ましいポリエステル系樹脂としては、ポリエチレンテレフタレート（ＰＥＴ）が挙げられる。しかしながら、ポリエチレンテレフタレートの本質を損なわない限り、エチレンテレフタレート単位を主体とし、他のポリエステル単位を含む共重合ＰＥＴ樹脂を使用することができる。このような共重合ＰＥＴ樹脂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、ジフエノキシエタン－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、シクロへキサンジメタノール、ビスフエノール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。
　特に好ましいポリエステル系樹脂としては、非晶性の共重合ＰＥＴ樹脂が挙げられる。使用するポリエステル系樹脂は、容器壁の機械的な性質の観点からは、固有粘度［η］が０．５（ｄｌ／ｇ）以上、特に０．６（ｄｌ／ｇ）以上のポリエステルであることが好ましい。
　また、ポリエステル系樹脂は透明であれば無着色でも或いは着色してあってもよい。ポリエステル系樹脂には、透明性を損なわない程度に、公知の添加物を添加してもよい。添加物としては、例えば、熱可塑性エラストマー、他の熱可塑性樹脂、ゴム樹脂、無機フィラー、顔料、可塑剤、酸化防止剤、帯電防止剤、光安定剤、アンチブロッキング剤、滑剤、染料等を使用できる。しかしながら、ポリエステル系樹脂の表面粗度を大きくするような添加物を使用することは避けることが好ましい。 The high gloss multilayer plastic container of the present invention is characterized in that the outermost transparent resin contains inorganic particles, the surface dynamic friction coefficient is 2 or less, and the 60 ° gloss is 90% or more.
Examples of the transparent resin constituting the outermost layer of the high gloss multilayer plastic container of the present invention include polyester resins, polyamide resins, and polycarbonate resins. The transparent resin is preferably a polyester resin. In particular, the use of thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene terephthalate is preferable in terms of easy molding and easy transparency.
A preferable polyester resin is polyethylene terephthalate (PET). However, as long as the essence of polyethylene terephthalate is not impaired, a copolymerized PET resin mainly composed of ethylene terephthalate units and containing other polyester units can be used. Examples of the copolymer component for forming such a copolymerized PET resin include isophthalic acid, p-β-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 their alkyl ester derivatives; propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol, cyclohexane dimethanol And glycol components such as ethylene oxide adduct of bisphenol A, diethylene glycol and triethylene glycol.
A particularly preferable polyester-based resin includes amorphous copolymerized PET resin. The polyester resin to be used is a polyester having an intrinsic viscosity [η] of 0.5 (dl / g) or more, particularly 0.6 (dl / g) or more from the viewpoint of mechanical properties of the container wall. Is preferred.
The polyester resin may be uncolored or colored as long as it is transparent. You may add a well-known additive to a polyester-type resin to such an extent that transparency is not impaired. Examples of additives include thermoplastic elastomers, other thermoplastic resins, rubber resins, inorganic fillers, pigments, plasticizers, antioxidants, antistatic agents, light stabilizers, antiblocking agents, lubricants, and dyes. it can. However, it is preferable to avoid using an additive that increases the surface roughness of the polyester resin.
　最外層の透明樹脂層に含有される無機粒子としては、特に限定されるものではなく、シリカ、ガラス粒子（ガラスビーズ）、タルク、アルミナ、酸化チタン、カオリン、ゼオライト、アルミノシリケート、硝酸カルシウム、硝酸バリウム、炭酸カルシウムなどが挙げられる。好ましくはシリカ粒子又はガラス粒子であり、より好ましくはシリカ粒子である。また、無機粒子は透明であることが好ましい。
　最外層の透明樹脂層中の無機粒子の含有量は、好ましくは０．１～１．０重量％であり、より好ましくは０．１～０．３重量％である。含有量が上記範囲より少ないと傷付きを低減する効果が得られず、一方、無機粒子の粒径にもよるが、含有量が上記範囲を超えると容器の光沢感が得られない。
　無機粒子の平均粒径は、好ましくは１～１５μｍである。本発明においては、平均粒径が５～８μｍである無機粒子、特にシリカ粒子を用いるのがより好ましい。平均粒径が上記範囲より小さいと傷付きの低減効果が得られず、一方、上記範囲を超えると容器の表面粗度が大きくなる。平均粒径を５～８μｍとすれば、含有量が比較的少ない範囲で傷付き低減の効果が得られるとともに、光沢性の良好な容器が得られる。 The inorganic particles contained in the outermost transparent resin layer are not particularly limited, and silica, glass particles (glass beads), talc, alumina, titanium oxide, kaolin, zeolite, aluminosilicate, calcium nitrate, nitric acid Examples include barium and calcium carbonate. Silica particles or glass particles are preferable, and silica particles are more preferable. The inorganic particles are preferably transparent.
The content of inorganic particles in the outermost transparent resin layer is preferably 0.1 to 1.0% by weight, more preferably 0.1 to 0.3% by weight. If the content is less than the above range, the effect of reducing scratches cannot be obtained. On the other hand, depending on the particle size of the inorganic particles, the glossiness of the container cannot be obtained if the content exceeds the above range.
The average particle size of the inorganic particles is preferably 1 to 15 μm. In the present invention, it is more preferable to use inorganic particles having an average particle diameter of 5 to 8 μm, particularly silica particles. If the average particle size is smaller than the above range, the effect of reducing scratches cannot be obtained. On the other hand, if the average particle size exceeds the above range, the surface roughness of the container increases. When the average particle size is 5 to 8 μm, the effect of reducing scratches can be obtained in a range where the content is relatively small, and a container having good gloss can be obtained.
　本発明の高光沢多層プラスチック容器は、表面の動摩擦係数が２以下であり、好ましくは１．５以下であり、最も好ましくは１．２以下である。前記動摩擦係数は、ＪＩＳ　Ｋ　７１２５を参考にして、次の方法により測定される。スライド式テーブルの上に２本のボトルを横置きに固定する。その上に、１００ｍｌの水道水を入れ、かつ、ノズル部にワイヤーを取り付けたボトルを重ねて置く。固定されたロードセルに前記ワイヤーを繋ぎ、スライドテーブルをロードセルとは逆側の水平方向に引く（図１参照）。上部の水を入れたボトルが下部のボトルに対して引きずられた際のロードセル荷重を測定し、動摩擦係数に換算する。尚、ボトルの向きは３本とも同じである。 The high gloss multilayer plastic container of the present invention has a surface dynamic friction coefficient of 2 or less, preferably 1.5 or less, and most preferably 1.2 or less. The dynamic friction coefficient is measured by the following method with reference to JIS K 7125. Secure two bottles horizontally on a sliding table. On top of that, 100 ml of tap water is put, and a bottle with a wire attached to the nozzle is placed on top of it. The wire is connected to the fixed load cell, and the slide table is pulled in the horizontal direction opposite to the load cell (see FIG. 1). Measure the load cell load when the bottle with water in the upper part is dragged against the lower bottle, and convert it to the coefficient of dynamic friction. The direction of the bottles is the same for all three bottles.
　また、本発明の高光沢多層プラスチック容器は、表面の６０°グロスが９０％以上である。前記６０°グロスは、ＪＩＳ　Ｚ　８７４１に準じて、例えば日本電色工業（株）製ＶＧ　２０００を用いて測定される。 Also, the high gloss multilayer plastic container of the present invention has a surface 60 ° gloss of 90% or more. The 60 ° gloss is measured according to JIS Z 8741, for example, using VG 2000 manufactured by Nippon Denshoku Industries Co., Ltd.
　また、本発明の高光沢多層プラスチック容器は、表面粗度Ｒａが０．１～０．２μｍであることが好ましい。より好ましくは、０．１～０．１５μｍである。表面粗度Ｒａが０．２μｍ以下であれば十分な光沢感が得られるが、０．１μｍを下回ると傷付きが生じやすくなる。前記表面粗度Ｒａは、ＪＩＳ　Ｂ　０６０１に準じて、例えば東京精密工業製１４００Ａ－３ＤＦを用いて測定される。
　高光沢多層プラスチック容器の表面粗度をＲａ≦０．２μｍとなるようにするには、ブロー金型内面の表面粗度が０．２μｍ≦Ｒａ≦０．８μｍ程度のブロー金型を使用する。このような処理した金型を使用することによって、容器外層の表面粗度が最大でもＲａ≦０．２μｍの容器を得ることができる。
　ブロー金型内表面の表面粗度を上記範囲より小さくすると、プラスチック容器の成形時にエアートラップが発生し、部分的表面凹凸等の成形不良が生じることがある。 The high gloss multilayer plastic container of the present invention preferably has a surface roughness Ra of 0.1 to 0.2 μm. More preferably, it is 0.1 to 0.15 μm. If the surface roughness Ra is 0.2 μm or less, a sufficient glossiness is obtained, but if it is less than 0.1 μm, scratches tend to occur. The surface roughness Ra is measured according to JIS B 0601 using, for example, 1400A-3DF manufactured by Tokyo Seimitsu Kogyo.
In order to make the surface roughness of the high gloss multilayer plastic container Ra ≦ 0.2 μm, a blow mold having a surface roughness of the inner surface of the blow mold of about 0.2 μm ≦ Ra ≦ 0.8 μm is used. By using such a treated mold, a container with Ra ≦ 0.2 μm can be obtained even when the surface roughness of the outer layer of the container is maximum.
If the surface roughness of the inner surface of the blow mold is made smaller than the above range, an air trap may occur during molding of the plastic container, and molding defects such as partial surface irregularities may occur.
　また、本発明の高光沢多層プラスチック容器は、外面側から順に透明樹脂層、透明接着樹脂層及び着色ポリオレフィン系樹脂層を有し、着色ポリオレフィン系樹脂層が光輝顔料を含むことが好ましい。
　透明接着樹脂層を構成する透明接着樹脂としては、透明樹脂とポリオレフィン樹脂の両者に接着性のある公知の樹脂を使用できる。前記透明樹脂としてポリエステル樹脂を用いた場合は、例えば、エチレン・α－オレフィン共重合樹脂及びそれらの酸変性樹脂、オレフィンと酸の共重合樹脂、グリシジル基含有樹脂等が使用できる。また、接着性を向上させるために、それらの樹脂に公知の粘着付与剤を添加してもよい。
　共重合体としては、ランダム、ブロック、グラフト等、どのような結合様式で製造されたものでも使用できる。酸変性樹脂としては、例えば、アクリル酸、メタクリル酸、マレイン酸、フマール酸、イタコン酸、クロトン酸等の不飽和カルボン酸；又はこれらの無水物でグラフト変性した樹脂が用いられる。これらの樹脂は、単独で、又は２種以上のブレンド樹脂として；あるいは他樹脂とのブレンド樹脂として使用できる。粘着付与剤としては、例えば、ロジン系樹脂、テルペン系樹脂、石油樹脂などがあげられる。これらの樹脂は、単独で、又は２種以上を混合して使用することができる。 The high gloss multilayer plastic container of the present invention preferably has a transparent resin layer, a transparent adhesive resin layer, and a colored polyolefin resin layer in order from the outer surface side, and the colored polyolefin resin layer preferably contains a bright pigment.
As the transparent adhesive resin constituting the transparent adhesive resin layer, a known resin having adhesiveness to both the transparent resin and the polyolefin resin can be used. When a polyester resin is used as the transparent resin, for example, ethylene / α-olefin copolymer resins and acid-modified resins thereof, olefin / acid copolymer resins, glycidyl group-containing resins and the like can be used. Moreover, in order to improve adhesiveness, you may add a well-known tackifier to those resin.
As the copolymer, those produced by any bonding mode such as random, block, graft and the like can be used. Examples of the acid-modified resin include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and crotonic acid; or resins that are graft-modified with these anhydrides. These resins can be used alone or as a blend resin of two or more; or as a blend resin with other resins. Examples of the tackifier include rosin resin, terpene resin, and petroleum resin. These resins can be used alone or in admixture of two or more.
　また、透明接着樹脂層には、公知の添加物を添加してもよい。添加物としては、例えば、熱可塑性エラストマー、他の熱可塑性樹脂、ゴム樹脂、無機フィラー、顔料、可塑剤、酸化防止剤、帯電防止剤、光安定剤、アンチブロッキング剤などを使用できる。特に、ポリオレフィン樹脂（特にポリエチレン系樹脂）に粘着付与剤を添加した樹脂が好ましい。また、熱可塑性エラストマーは、層界面の凹凸の低減のため、スチレン系のエラストマーを使用することが好ましい。
　また、透明接着樹脂層は、透明であれば無着色でも或いは着色してあってもよく、光輝性顔料を含有させてもよい。接着樹脂層を着色した場合には、例えば、着色ポリオレフィン層に光輝性顔料を含有させることにより、光輝性顔料による反射光が透明着色接着層を透過して、深みのある独特のメタリック感が得られるので好ましい。また、透明接着層とポリオレフィン層の色調を変えることによって、特殊な色相効果が得られ好ましい場合もある。透明接着樹脂層に使用する着色料としては、透明性を損なわない限り特に制限はない。このような着色料としては、例えば、アゾ系顔料、フタロシアニン系顔料、縮合多環系顔料、染色レーキ系顔料等の有機顔料を使用することができる。 Moreover, you may add a well-known additive to a transparent adhesive resin layer. Examples of 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. In particular, 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 transparent adhesive resin layer may be uncolored or colored as long as it is transparent, and may contain a glitter pigment. When the adhesive resin layer is colored, for example, by adding a bright pigment to the colored polyolefin layer, the reflected light from the bright pigment is transmitted through the transparent colored adhesive layer, giving a deep and unique metallic feeling. This is preferable. In some cases, a special hue effect can be obtained by changing the color tone of the transparent adhesive layer and the polyolefin layer. The colorant used for the transparent adhesive resin layer is not particularly limited as long as the transparency is not impaired. As such a colorant, for example, an organic pigment such as an azo pigment, a phthalocyanine pigment, a condensed polycyclic pigment, or a dyed lake pigment can be used.
　着色ポリオレフィン系樹脂層を構成する樹脂としては特に制限はない。例えば、公知の低密度ポリエチレン、線状低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、プロピレン－エチレン共重合体、エチレン－酢酸ビニル共重合体、エチレン系不飽和カルボン酸乃至その無水物でグラフト変性されたポリオレフィン樹脂等のポリオレフィン系樹脂類はいずれも使用することができる。特に好ましいポリオレフィン系樹脂としては、プロピレン－エチレンブロック共重合体が挙げられる。これらのポリオレフィン系樹脂は単独で、又は２種以上を混合して用いることができる。また、容器の成形時等に発生するリプロ（回収材料）を混合して使用してもよい。
　着色ポリオレフィン系樹脂層は、透明着色層或いは不透明着色層のいずれでもよい。また、１層の着色層のみならず２層以上の着色層として構成してもよい。また、着色ポリオレフィン系樹脂層の内層側に、さらに他の樹脂等からなる中間層や、容器の内面を構成する、例えばポリオレフィン系樹脂からなる内面樹脂層を設けることもできる。
　着色ポリオレフィン系樹脂層に配合する着色料としては特に制限はなく、アゾ系顔料、フタロシアニン系顔料、縮合多環系顔料及び染色レーキ系顔料等の有機顔料や、偏光パール顔料等のアルミ系光輝顔料、マイカ系光輝顔料、ガラス系光輝顔料等の光輝顔料等を使用することができる。これらの着色料は１種又は２種以上を組合せて使用することができる。また、これらの着色料と体質顔料等を組合せて用いてもよい。
　着色ポリオレフィン系樹脂層中に光輝顔料を配合した場合には、光輝顔料の反射光が、透明ポリエステル系樹脂層及び透明接着樹脂層を組合わせた層を通過することによって、深みのある光沢感を有するメタリック色調の多層プラスチック容器を得ることができる。
　特に、着色ポリオレフィン系樹脂層を透明接着樹脂層に隣接する透明着色樹脂層と、その内層側に設けた光輝顔料を含有する着色樹脂層からなる複層構成とした場合には、金属地に透明インキを印刷したような、深みのある独特のメタリック感が得られるので好ましい。 There is no restriction | limiting in particular as resin which comprises a colored polyolefin-type resin layer. For example, known low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylenically unsaturated carboxylic acid or its anhydride. Any polyolefin-based resins such as graft-modified polyolefin resins can be used. Particularly preferred polyolefin resins include propylene-ethylene block copolymers. These polyolefin resins can be used alone or in admixture of two or more. Moreover, you may mix and use the repro (collection material) generated at the time of shaping | molding of a container.
The colored polyolefin resin layer may be either a transparent colored layer or an opaque colored layer. Moreover, you may comprise not only one colored layer but 2 or more colored layers. In addition, an intermediate layer made of another resin or the like, or an inner surface resin layer made of, for example, a polyolefin resin can be provided on the inner layer side of the colored polyolefin-based resin layer.
There are no particular restrictions on the colorant blended in the colored polyolefin resin layer, and organic pigments such as azo pigments, phthalocyanine pigments, condensed polycyclic pigments and dyed lake pigments, and aluminum bright pigments such as polarized pearl pigments. Further, bright pigments such as mica-based bright pigments and glass-based bright pigments can be used. These colorants can be used alone or in combination of two or more. These colorants and extender pigments may be used in combination.
When a bright pigment is blended in the colored polyolefin resin layer, the reflected light of the bright pigment passes through a combination of a transparent polyester resin layer and a transparent adhesive resin layer, resulting in a deep gloss. A multilayer plastic container having a metallic color tone can be obtained.
In particular, when the colored polyolefin resin layer has a multi-layer structure comprising a transparent colored resin layer adjacent to the transparent adhesive resin layer and a colored resin layer containing a bright pigment provided on the inner layer side, it is transparent to the metal ground. This is preferable because a deep and unique metallic feeling as if ink was printed is obtained.
　次に、本発明の高光沢多層プラスチック容器を実施例によりさらに説明するが、以下の具体例は本発明を限定するものではない。
　図２は、本発明の多層プラスチック容器の層構成の１例を示す断面模式図である。この容器は、外面側から順に透明ポリエステル系樹脂層Ａ、透明接着樹脂層Ｂ、光輝顔料を含む着色ポリオレフィン系樹脂層Ｃ、及び光輝顔料を含まない着色ポリオレフィン系樹脂層Ｄを有する。 Next, although the high gloss multilayer plastic container of this invention is further demonstrated by an Example, the following specific examples do not limit this invention.
FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the multilayer plastic container of the present invention. This container has a transparent polyester resin layer A, a transparent adhesive resin layer B, a colored polyolefin resin layer C containing a bright pigment, and a colored polyolefin resin layer D containing no bright pigment in order from the outer surface side.
　以下の例では、図１に示す層構成を有する容器を次のようにして製造した。４つの押出し機（以下、各樹脂層Ａ，Ｂ，Ｃ，Ｄを構成する樹脂の押出し機を、それぞれ押出し機Ａ、Ｂ、Ｃ、Ｄと言う。）にそれぞれ樹脂を充填した。各樹脂を加熱しながら可塑化及び混練して押出し、多層ヘッドを用いて、外面側から順に、透明ポリエステル系樹脂層Ａ、透明接着樹脂層Ｂ、光輝顔料を含む着色ポリオレフィン系樹脂層Ｃ、及びポリオレフィン系樹脂層Ｄからなる多層パリソンを形成した。ついで、キャビティーを有する金型でパリソンを挟み、パリソンに圧縮空気を吹き込んで、角筒型の中空容器を製造した。使用した金型の内表面粗度は、Ｒａ＝０．６μｍであった。 In the following example, a container having the layer structure shown in FIG. 1 was manufactured as follows. Four extruders (hereinafter, the resin extruders constituting the resin layers A, B, C, and D are referred to as extruders A, B, C, and D, respectively) were filled with the resin. Plasticizing, kneading and extruding each resin while heating, using a multilayer head, in order from the outer surface side, transparent polyester resin layer A, transparent adhesive resin layer B, colored polyolefin resin layer C containing a bright pigment, and A multilayer parison composed of the polyolefin resin layer D was formed. Next, the parison was sandwiched between molds having cavities, and compressed air was blown into the parison to produce a rectangular tube-shaped hollow container. The inner surface roughness of the mold used was Ra = 0.6 μm.
　以下の例では、各物性値は既に記載した方法により測定した。各物性値の測定にあたり、多層プラスチック容器の表面粗度Ｒａは「東京精密工業製１４００Ａ－３ＤＦ」を、６０°グロスは「日本電色工業（株）製ＶＧ　２０００」をそれぞれ使用した。
　また、多層プラスチック容器の表面粗度Ｒａは、容器のノズル部以外の平坦な部分から、表面粗度の大きい部分を直接、或いは１５ｍｍ×１５ｍｍの大きさで切り出し、測定に供した。 In the following examples, each physical property value was measured by the method described above. In measuring each physical property value, the surface roughness Ra of the multilayer plastic container was “1400A-3DF manufactured by Tokyo Seimitsu Kogyo”, and “VG 2000 manufactured by Nippon Denshoku Industries Co., Ltd.” was used for the 60 ° gloss.
Further, the surface roughness Ra of the multilayer plastic container was measured by cutting a portion having a large surface roughness directly or directly in a size of 15 mm × 15 mm from a flat portion other than the nozzle portion of the container.
（振動試験）
　振動試験はＪＩＳ　Ｚ　０２３２に準じて、次の機器及び条件で行った。
試験機　：（株）振研製動電型試験機
試験方法：ランダム試験方法（ボトルに定格量の水道水（２０℃）を充填し、実際の流通カートンに入れ、カートンを振動台の上に置き、垂直方法に３０分間、ランダム振動をかける。）
　実際の流通カートンは次のとおりである。
　５００ｍｌボトル用：３列×４＝１２本入り（仕切板あり）、材質：通常の紙段ボール　１９０ｍｌボトル用：２列×３＝６本入り（仕切板無し）、材質：通常の紙段ボール
　試験後、目視により傷付きの程度を評価した。目安として、長さ３cmを越える大きな傷が多数発生した場合を不良（×）、３ｃｍ以上の傷が少数見られた場合を可（△）、１～３ｃｍ程度の細かな傷の場合を良（○）、１ｃｍに満たない小さな傷のみの場合を優（◎）とした。 (Vibration test)
The vibration test was performed according to JIS Z 0232 with the following equipment and conditions.
Testing machine: Electrodynamic testing machine manufactured by Shinken Co., Ltd. Testing method: Random testing method (Bottle filled with rated amount of tap water (20 ° C), put into an actual distribution carton, and place the carton on the shaking table Apply random vibration for 30 minutes in the vertical method.)
The actual distribution cartons are as follows.
For 500 ml bottles: 3 rows x 4 = 12 bottles (with dividers), material: normal paper cardboard For 190 ml bottles: 2 rows x 3 = 6 bottles (without dividers), material: normal paper cardboards After testing The degree of scratching was visually evaluated. As a guideline, if a large number of large scratches exceeding 3 cm in length have occurred, it is defective (×), if a small number of scratches of 3 cm or more are observed (△), fine scratches of about 1 to 3 cm are good ( ○) The case of only small scratches less than 1 cm was judged as excellent (優).
（比較例１）
　口径４０ｍｍの押出し機Ａに、透明非晶性シクロヘキサンジメタノール（ＣＨＤＭ）系共重合ポリエチレンテレフタレート樹脂（イーストマン製ＰＥＴＧ　ＤｒｙＳｔａｒ　０６０１）を充填した。口径４０ｍｍの押出し機Ｂに、粘着付与剤添加タイプでスチレン系エラストマーを含有した透明無色のＬＤＰＥ系樹脂（三菱化学製モディックＦ５１２Ａ）、及び着色顔料として０．３重量％のアゾ系赤色顔料を充填した。口径５０ｍｍの押出し機Ｃに、透明無色のエチレン・プロピレンブロック共重合樹脂（ＨＭＣ製ＥＰ３１０Ｄ）、及び光輝顔料として０．５重量％のパールレッド（平均粒径２１μｍの雲母系顔料）、着色顔料として０．５重量％のアゾ系赤色顔料を充填した。口径４０ｍｍの押出し機Ｄに前記エチレン・プロピレンブロック共重合樹脂（ＨＭＣ製ＥＰ３１０Ｄ）を充填した。各押出し機に充填した樹脂を加熱しながら可塑化及び混練して、多層ヘッドから押出して多層パリソンを形成した。ついで、キャビティーを有する金型でパリソンを挟み、パリソンに圧縮空気を吹き込んで容量５００ｍＬの角筒型の中空ボトルを得た。
　このボトルの各層の厚みは、外層Ａ５０μｍ、透明接着樹脂層Ｂ７０μｍ、光輝着色ポリオレフィン系樹脂層Ｃ７１０μｍ、着色ポリオレフィン系樹脂層Ｄ１７０μｍであった。また、ボトル表面の粗度Ｒａは０．０７μｍ、動摩擦係数は４．６７及び６０°グロスは１０２．８％であった。
　振動試験の結果、大きく目立つ傷が多数発生した。 (Comparative Example 1)
Extruder A having a diameter of 40 mm was filled with transparent amorphous cyclohexanedimethanol (CHDM) copolymerized polyethylene terephthalate resin (Eastman's PETG DryStar 0601). Extruder B with a diameter of 40 mm is filled with a transparent and colorless LDPE resin containing styrene elastomer (Mitsubishi Chemical Modic F512A) and 0.3% by weight azo red pigment as a coloring pigment. did. Extruder C having a diameter of 50 mm, transparent colorless ethylene / propylene block copolymer resin (EP310D manufactured by HMC), 0.5% by weight of pearl red (mica-based pigment having an average particle diameter of 21 μm) as a bright pigment, and as a colored pigment 0.5% by weight of azo red pigment was filled. An extruder D having a diameter of 40 mm was filled with the ethylene / propylene block copolymer resin (EP310D manufactured by HMC). The resin filled in each extruder was plasticized and kneaded while being heated, and extruded from a multilayer head to form a multilayer parison. Subsequently, the parison was sandwiched between molds having cavities, and compressed air was blown into the parison to obtain a square-tube hollow bottle having a capacity of 500 mL.
The thickness of each layer of this bottle was an outer layer A 50 μm, a transparent adhesive resin layer B 70 μm, a bright colored polyolefin resin layer C 710 μm, and a colored polyolefin resin layer D 170 μm. The bottle surface roughness Ra was 0.07 μm, the dynamic friction coefficient was 4.67, and the 60 ° gloss was 102.8%.
As a result of the vibration test, many noticeable scratches were generated.
（実施例１）
　無機粒子として平均粒径８μｍ（レーザー回折散乱法）の多孔質シリカを、透明非晶性シクロヘキサンジメタノール（ＣＨＤＭ）系共重合ポリエチレンテレフタレート樹脂に５重量％添加して作成されたマスターバッチ（住化カラー製ＥＰＭ－７Ｙ０２９）を、外層Ａの樹脂に２．５重量％添加（外層Ａ中の多孔質シリカの添加量０．１２５重量％）した他は比較例１と同様にして、容量５００ｍＬの角筒型の中空ボトルを得た。
　ボトル表面の粗度Ｒａは０．１０μｍ、動摩擦係数は１．１０、６０°グロスは９６．４％であった。
　振動試験の結果、細かい傷は見られるものの、大きな傷は生じなかった。 (Example 1)
A master batch (Sumitomo) made by adding 5% by weight of porous silica with an average particle size of 8μm (laser diffraction scattering method) as inorganic particles to transparent amorphous cyclohexanedimethanol (CHDM) copolymer polyethylene terephthalate resin EPM-7Y029 manufactured by Color Co., Ltd. was added in an amount of 2.5% by weight to the resin of the outer layer A (addition amount of porous silica in the outer layer A was 0.125% by weight). A square cylindrical hollow bottle was obtained.
The bottle surface roughness Ra was 0.10 μm, the dynamic friction coefficient was 1.10, and the 60 ° gloss was 96.4%.
As a result of the vibration test, fine flaws were observed, but no major flaws were generated.
（実施例２）
　マスターバッチの添加量を５．０重量％（外層Ａ中の添加量０．２５重量％）にした他は実施例１と同様にして、容量５００ｍＬの角筒型の中空ボトルを得た。
　ボトル表面の粗度Ｒａは０．１５μｍ、動摩擦係数は０．７６、６０°グロスは９３．０％であった。
　振動試験の結果、傷はほとんど目立たず、優れた光沢を有していた。 (Example 2)
A rectangular tube-shaped hollow bottle having a capacity of 500 mL was obtained in the same manner as in Example 1 except that the addition amount of the master batch was 5.0 wt% (the addition amount in the outer layer A was 0.25 wt%).
The bottle surface roughness Ra was 0.15 μm, the dynamic friction coefficient was 0.76, and the 60 ° gloss was 93.0%.
As a result of the vibration test, the scratches were hardly noticeable and had excellent gloss.
（比較例２）
　比較例１を金型のみ変更して、容量１９０ｍＬの角筒型の中空ボトルを得た。
　ボトル表面の粗度Ｒａは０．０５μｍ、動摩擦係数は４．６７、６０°グロスは１００．５％であった。
　振動試験の結果、大きく目立つ傷が多数発生した。 (Comparative Example 2)
In Comparative Example 1, only the mold was changed to obtain a rectangular tube-shaped hollow bottle having a capacity of 190 mL.
The bottle surface roughness Ra was 0.05 μm, the dynamic friction coefficient was 4.67, and the 60 ° gloss was 100.5%.
As a result of the vibration test, many noticeable scratches were generated.
（実施例３）
　金型を比較例２と同じものにした他は実施例１と同様にして、容量１９０ｍＬの角筒型の中空ボトルを得た。
　ボトル表面の粗度Ｒａは０．１０μｍ、動摩擦係数は１．１０、６０°グロスは９６．９％であった。
　振動試験の結果、細かい傷は見られるものの、大きな傷は生じなかった。 Example 3
A rectangular tube-shaped hollow bottle having a capacity of 190 mL was obtained in the same manner as in Example 1 except that the mold was the same as that in Comparative Example 2.
The bottle surface roughness Ra was 0.10 μm, the dynamic friction coefficient was 1.10, and the 60 ° gloss was 96.9%.
As a result of the vibration test, fine flaws were observed, but no major flaws were generated.
（実施例４）
　マスターバッチの添加量を５重量％とした他は実施例３と同様にして、容量１９０ｍＬの角筒型の中空ボトルを得た。
　ボトル表面の粗度Ｒａは０．１５μｍ、動摩擦係数は０．７６、６０°グロスは９２．０％であった。
　振動試験の結果、傷はほとんど目立たず、優れた光沢を有していた。 (Example 4)
A rectangular tube-shaped hollow bottle having a capacity of 190 mL was obtained in the same manner as in Example 3 except that the addition amount of the master batch was changed to 5% by weight.
The bottle surface roughness Ra was 0.15 μm, the dynamic friction coefficient was 0.76, and the 60 ° gloss was 92.0%.
As a result of the vibration test, the scratches were hardly noticeable and had excellent gloss.
（比較例３）
　無機粒子として平均粒径４μｍ（レーザー回折散乱法）の多孔質シリカを、透明非晶性シクロヘキサンジメタノール（ＣＨＤＭ）系共重合ポリエチレンテレフタレート樹脂に５重量％添加して作成されたマスターバッチ（住化カラー製ＥＰＭ－７Ｙ０１７）を、外層Ａの樹脂に５重量％添加（外層Ａ中の添加量０．２５重量％）した他は比較例１と同様にして、容量５００ｍＬの角筒型の中空ボトルを得た。
　ボトル表面の粗度Ｒａは０．０６μｍ、動摩擦係数は２．４１、６０°グロスは１０１．０％であった。
　振動試験の結果、大きく目立つ傷が多数発生した。 (Comparative Example 3)
Masterbatch (Sumitomo Chemical) created by adding 5% by weight of porous silica with an average particle size of 4μm (laser diffraction scattering method) as inorganic particles to transparent amorphous cyclohexanedimethanol (CHDM) copolymer polyethylene terephthalate resin Colored EPM-7Y017) was added to the resin of the outer layer A in an amount of 5% by weight (the amount added in the outer layer A was 0.25% by weight). Got.
The bottle surface roughness Ra was 0.06 μm, the dynamic friction coefficient was 2.41, and the 60 ° gloss was 101.0%.
As a result of the vibration test, many noticeable scratches were generated.
（実施例５）
　マスターバッチの添加量を１０重量％（外層Ａ中の添加量０．５重量％）にした他は比較例３と同様にして、容量５００ｍＬの角筒型の中空ボトルを得た。
　ボトル表面の粗度Ｒａは０．１０μｍ、動摩擦係数は１．２７、６０°グロスは９９．０％であった。
　振動試験の結果、大きな目立つ傷の状態は比較例１より軽減された。 (Example 5)
A rectangular tube-shaped hollow bottle having a capacity of 500 mL was obtained in the same manner as in Comparative Example 3 except that the addition amount of the master batch was 10 wt% (the addition amount in the outer layer A was 0.5 wt%).
The bottle surface roughness Ra was 0.10 μm, the dynamic friction coefficient was 1.27, and the 60 ° gloss was 99.0%.
As a result of the vibration test, the state of large conspicuous scratches was reduced from Comparative Example 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Ａ　　　　透明樹脂外層
Ｂ　　　　透明接着樹脂層
Ｃ　　　　光輝顔料を含む着色ポリオレフィン系樹脂層
Ｄ　　　　ポリオレフィン系樹脂層 A Transparent resin outer layer B Transparent adhesive resin layer C Colored polyolefin resin layer D containing bright pigment D Polyolefin resin layer

Claims (8)

  1. 　最外層の透明樹脂が無機粒子を含有し、表面の動摩擦係数が２以下であり、かつ、６０°グロスが９０％以上であることを特徴とする高光沢多層プラスチック容器。 A high gloss multi-layer plastic container characterized in that the outermost transparent resin contains inorganic particles, has a surface dynamic friction coefficient of 2 or less, and 60 ° gloss is 90% or more.
  2. 　最外層の透明樹脂がポリエステル系樹脂である請求項１記載の高光沢性多層プラスチック容器。 The high gloss multilayer plastic container according to claim 1, wherein the outermost transparent resin is a polyester resin.
  3. 　ポリエステル系樹脂が共重合ＰＥＴ樹脂である請求項２の高光沢性多層プラスチック容器。 The high gloss multilayer plastic container according to claim 2, wherein the polyester resin is a copolymerized PET resin.
  4. 　無機粒子がシリカである請求項１乃至３のいずれかに記載の高光沢性多層プラスチック容器。 The high gloss multilayer plastic container according to any one of claims 1 to 3, wherein the inorganic particles are silica.
  5. 　無機粒子を０．１～０．３重量％含有する請求項１乃至４のいずれかに記載の高光沢性多層プラスチック容器。 The high gloss multilayer plastic container according to any one of claims 1 to 4, comprising 0.1 to 0.3% by weight of inorganic particles.
  6. 　無機粒子の平均粒径が５～８μｍである、請求項１乃至５のいずれかに記載の高光沢多層プラスチック容器。 6. The high gloss multilayer plastic container according to claim 1, wherein the average particle diameter of the inorganic particles is 5 to 8 μm.
  7. 　最外層の表面粗度Ｒａが０．１～０．２μｍである、請求項１乃至６のいずれかに記載の高光沢多層プラスチック容器。 The high gloss multilayer plastic container according to any one of claims 1 to 6, wherein the outermost layer has a surface roughness Ra of 0.1 to 0.2 µm.
  8. 　多層プラスチック容器が外面側から順に透明樹脂層、透明接着樹脂層及び着色ポリオレフィン系樹脂層を有し、着色ポリオレフィン系樹脂層が光輝顔料を含む、請求項１乃至７のいずれかに記載の高光沢多層プラスチック容器。 The high gloss according to any one of claims 1 to 7, wherein the multilayer plastic container has a transparent resin layer, a transparent adhesive resin layer, and a colored polyolefin resin layer in order from the outer surface side, and the colored polyolefin resin layer contains a bright pigment. Multi-layer plastic container.
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