WO2013073579A1 - Feuille de résine multicouche et récipient moulé - Google Patents

Feuille de résine multicouche et récipient moulé Download PDF

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Publication number
WO2013073579A1
WO2013073579A1 PCT/JP2012/079523 JP2012079523W WO2013073579A1 WO 2013073579 A1 WO2013073579 A1 WO 2013073579A1 JP 2012079523 W JP2012079523 W JP 2012079523W WO 2013073579 A1 WO2013073579 A1 WO 2013073579A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
resin sheet
styrene
ultraviolet absorber
absorber
Prior art date
Application number
PCT/JP2012/079523
Other languages
English (en)
Japanese (ja)
Inventor
洪太 永岡
中里　利勝
小茂田　含
Original Assignee
電気化学工業株式会社
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 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to JP2013544297A priority Critical patent/JP6091425B2/ja
Priority to CN201280055646.9A priority patent/CN103930276A/zh
Publication of WO2013073579A1 publication Critical patent/WO2013073579A1/fr

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Classifications

    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • 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
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • 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
    • B32B2439/70—Food packaging
    • 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
    • B32B2439/80—Medical packaging

Definitions

  • the present invention generally relates to a multilayer resin sheet, and more particularly to a thermoplastic resin sheet suitable for use in packaging materials in which deterioration of contents due to ultraviolet rays is a problem.
  • the present invention also relates to a molded container formed by molding such a resin sheet.
  • Patent Document 1 proposes a food packaging material containing an unsaturated fatty acid in its contents, to which an inorganic ultraviolet absorbent mainly composed of titanium oxide is added.
  • an inorganic ultraviolet absorbent mainly composed of titanium oxide
  • an organic ultraviolet absorber capable of cutting ultraviolet rays having a wavelength of 380 to 400 nm as the ultraviolet absorber.
  • Patent Document 2 even when an organic ultraviolet absorber is used, there is a problem in health and safety due to precipitation and elution of the ultraviolet absorber into the contents due to migration or the like. Furthermore, when an organic ultraviolet absorber is used, a problem arises in that the mold and the like are contaminated by precipitates of the components during heat molding, and productivity is impaired.
  • the present invention has been made in view of the above circumstances, and a main object of the present invention is to provide a multilayer resin sheet suitable for use as a packaging material in applications where deterioration of contents due to ultraviolet rays is a problem.
  • the present invention uses an organic ultraviolet absorber, it is possible to reliably suppress the alteration, discoloration, deterioration, etc. of the contents, and the transparency is not significantly reduced, and the organic ultraviolet absorber
  • An object of the present invention is to provide a multilayer resin sheet that eliminates the conventional problems caused by the precipitation of slag.
  • Another object of the present invention is to provide a molded container that can be obtained by molding the multilayer resin sheet.
  • an outer layer made of a styrene resin not containing an organic ultraviolet absorber is laminated on both sides of an inner layer made of a styrene resin containing an organic ultraviolet absorber.
  • a multilayer resin sheet is provided.
  • the organic ultraviolet absorbent that can be used for the purpose of the present invention is not limited to a specific one. However, in one embodiment, it can be used for packaging materials such as foods, and ultraviolet light having a wavelength of 380 to 400 nm. Therefore, a benzophenone-based or benzotriazole-based ultraviolet absorber is preferably selected.
  • the addition amount of the organic ultraviolet absorber is preferably 0.1 to 1.0 parts by mass (that is, 0.1 to 1.0 parts by mass with respect to 100 parts by mass of all resin components including the inner layer and the outer layer). To 1.0 PHR), more preferably 0.1 to 0.8 parts by mass (that is, 0.1 to 0.8 PHR).
  • the thickness of the outer layer containing no organic ultraviolet absorber is at least 25 ⁇ m or more, preferably 30 ⁇ m or more, more preferably 35 ⁇ m or more.
  • the multilayer resin sheet has excellent transparency, and its total light transmittance is 60% or more, preferably 70% or more, more preferably 80% or more.
  • a molded container formed by molding the multilayer resin sheet is provided.
  • the molded container is a molded container for packaging contents that may be altered, discolored, deteriorated or the like due to ultraviolet rays, and is preferably required to be transparent so that the contents are visible. is there.
  • the multilayer resin sheet of the present invention contains an organic ultraviolet absorber, it is possible to cut ultraviolet rays having a wavelength of 380 nm to 400 nm, and there is no possibility of poor dispersion or a decrease in transparency.
  • the outer layer does not contain an organic UV absorber, the organic UV absorber does not precipitate and does not contaminate the mold even if a heat molding process is performed using a mold or the like. There is no contamination of the contents due to the precipitation.
  • the multilayer resin sheet includes an inner layer and an outer layer formed on both surfaces of the inner layer.
  • the outer layer is divided into a notch forming side outer layer on which a notch is to be formed and a notch non-forming outer layer on the opposite side, both of which may be formed of the same resin or different resins. May be.
  • the inner layer may be a single layer of a specific resin, but is preferably formed in a plurality of layers using a plurality of different resins. In the case of multiple layers, there are no restrictions on the number of layers, the thickness of each layer, etc., the resin structure is changed between the notch formation side and the notch non-formation side, or one or more types of central layers with different functionality are interposed between them. Can be provided.
  • the resin for the inner layer contains an organic ultraviolet absorber, while the resin for the outer layer does not contain an organic ultraviolet absorber.
  • an organic ultraviolet absorber is contained in at least one of the resins, and preferably, an organic ultraviolet absorber is contained in all the inner layers.
  • the organic ultraviolet absorber is not contained in any outer layer in the resin of the outer layer.
  • a styrene resin is used because of its excellent thermoformability and rigidity.
  • the styrene resin has a normal meaning understood by those skilled in the art, and in addition to the homopolymer of the styrene monomer, a monomer copolymerizable with the styrene monomer is polymerized. Also included are modified resins such as copolymers and rubber-modified styrene resins.
  • styrene monomer examples include styrene, ⁇ -methyl styrene, p-methyl styrene, dimethyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene, and the like, and can be copolymerized with the styrene monomer.
  • Examples of the monomer include acrylic acid, ethyl acrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, methacrylic acid, ethyl methacrylate, methyl methacrylate, butyl methacrylate, 2-methacrylic acid 2- Examples include ethylhexyl, acrylonitrile, maleic anhydride, N-phenylmaleimide, ethylene, propylene and the like.
  • polystyrene for example, general-purpose polystyrene resin (GPPS), which can be mentioned first as the styrene resin, is the most versatile styrene resin in consideration of transparency and cost.
  • GPPS general-purpose polystyrene resin
  • styrene-based resins include styrene-methyl methacrylate copolymers, styrene-methyl acrylate copolymers, styrene-methacrylic acid copolymers, styrene-acrylic acid copolymers, and styrene-acrylonitrile copolymers.
  • AS resin styrene-N-phenylmaleimide copolymer, and the like.
  • the amount of the styrene monomer in the copolymer is preferably 4 to 95 parts by mass, more preferably 10 to 94 parts by mass, and particularly preferably 20 to 90 parts by mass.
  • the content is high, the bending cracking property when formed into a molded product tends to be inferior, and the splitting property of the molded product due to perforation or the like tends to decrease, and when it is low, the transparency tends to decrease.
  • a rubber-modified styrenic resin can be used as the styrenic resin.
  • This is a polymer in which a rubbery polymer is dispersed in the form of a matrix composed of a normal unmodified styrenic resin.
  • a graft copolymer obtained by polymerizing an aromatic vinyl monomer by a conventional method in the presence of a rubber-like polymer.
  • Examples of the rubbery polymer include diene rubber, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, butadiene-acrylonitrile copolymer, isobutylene-isoprene copolymer, acrylic rubber, ethylene- ⁇ - Examples include olefin-polyene copolymers, urethane rubber, silicone rubber, butyl rubber, and hydrogenated diene rubber. Such rubber-modified styrenic resins are used to improve impact resistance and buffering properties.
  • styrene resin polystyrene (GPPS), styrene-acrylonitrile copolymer (AS resin), styrene-methyl methacrylate copolymer, acrylonitrile-styrene-methyl methacrylate copolymer, styrene-maleic anhydride Copolymer, high impact polystyrene (HIPS), styrene-acrylonitrile-butadiene copolymer (ABS resin), ⁇ -methylstyrene modified ABS resin, imide modified ABS resin, styrene-methyl methacrylate-butadiene copolymer (MBS) Resin), a resin obtained by graft polymerization of acrylonitrile and styrene on the rubber component, and the like are preferably used.
  • GPPS polystyrene
  • AS resin styrene-acrylonitrile copolymer
  • AS resin styrene-
  • GPPS general-purpose polystyrene resin
  • HIPS impact-resistant polystyrene
  • GPPS General polystyrene resin
  • GPPS is mainly composed of styrene as mentioned above, but o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene as trace components.
  • ⁇ -methylstyrene, vinylnaphthalene, vinylanthracene, 1,1-diphenylethylene and other aromatic vinyl compounds may be used, and commercially available resins may be used.
  • the impact-resistant polystyrene resin specifically refers to a polystyrene resin containing fine-grained graft rubber grafted with a styrenic monomer.
  • rubber components in the graft rubber include 1,3. -Butadiene (butadiene), 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2-methylpentadiene, etc.
  • Those using diene rubber as a monomer are preferably used.
  • thermoplastic elastomer of a styrene-conjugated diene block copolymer having a diene component of 50% by mass or more can also be used.
  • polybutadiene and styrene-butadiene block copolymers are preferred.
  • the amount is 96 to 5 parts by mass, preferably 90 to 6 parts by mass, particularly preferably 80 to 10 parts by mass.
  • the average particle diameter of rubber particles of impact-resistant polystyrene (HIPS) is 1.0 ⁇ m or less, preferably 0.8 ⁇ m or less, more preferably 0.5 ⁇ m or less, and the lower limit is 0.01 ⁇ m.
  • HIPS impact-resistant polystyrene
  • the organic ultraviolet absorber used in the present invention is not limited to a specific one as long as it can be used for packaging materials such as food and can cut ultraviolet rays having a wavelength of 380 to 400 nm.
  • a benzophenone-based or benzotriazole-based ultraviolet absorber is preferably selected.
  • a specific thing can also be used for these ultraviolet absorbers individually, and multiple types can also be used together.
  • benzophenone ultraviolet absorber examples include, for example, 2,4-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4- ( ⁇ -hydroxyethoxy) -benzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane and the like. Of these, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane is particularly preferable because of its good heat resistance.
  • benzotriazole ultraviolet absorber examples include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [3,5-bis (2,2-dimethylpropyl) -2-hydroxyphenyl].
  • Benzotriazole 2- (3-tertiarybutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-ditertiarybutyl-2-hydroxyphenyl) -5-chlorobenzotriazole 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like.
  • 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethyl) Butyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred because of its good heat resistance.
  • the styrene-based resin includes mineral oil, rosin esters, terpene resins, higher fatty acids, higher fatty acid salts, higher fatty acid amides, antioxidants, antistatic agents, antibacterial agents and the like as long as the effects of the present invention are not impaired. These additives can also be contained.
  • the total thickness of the resin sheet of the present invention is not particularly limited, but may be any thickness that can be used for normal thermoforming such as vacuum forming and vacuum / pressure forming, for example, a thickness of 0.2 to 2.5 mm. it can.
  • the thickness of each outer layer must have a sufficient thickness so that the UV absorber in the inner layer does not precipitate out of the sheet during heat processing, and the notch forming side and the notch forming side In any case, it is at least 25 ⁇ m or more, preferably 30 ⁇ m or more, more preferably 35 ⁇ m or more.
  • the upper limit of the thickness of each outer layer is not particularly limited as long as the total thickness of the resin sheet and the amount of the organic ultraviolet absorber contained are appropriate, and are, for example, 50 ⁇ m or less.
  • the resin sheet of the present invention is formed of a styrene resin as described above, the resin component can be adjusted to have excellent transparency.
  • the total light transmittance of the sheet is 60% or more. , Preferably 70% or more, more preferably 80% or more.
  • the total light transmittance can be measured by a method described in, for example, JIS K-7361-1, K-7105 and the like.
  • the method for producing the multilayer resin sheet of the present invention is not particularly limited, and a general method can be used.
  • the multilayer resin sheet of the present invention is excellent in thermoformability, rigidity, and transparency, so that transparency is required or preferred, and further, for packaging contents that may be altered, discolored, deteriorated, etc. by ultraviolet rays. It is suitably used for forming a molding container.
  • the method of thermoforming the resin sheet of the present invention includes general vacuum forming, pressure forming, and as an application thereof, a plug assist method in which a plug is brought into contact with one side of the sheet, and a pair of both sides of the sheet.
  • a method called so-called match mold molding, which performs molding by bringing the male and female molds forming the contact into contact, is not limited thereto.
  • a known sheet heating method such as radiation heating with an infrared heater or the like which is non-contact heating can be applied.
  • HIPS resin “Toyostyrene H850” (manufactured by Toyo Styrene Co., Ltd., butadiene content: 9.0% by mass)
  • GPPS resin “Toyostyrene G200C” (manufactured by Toyo Styrene Co., Ltd.)
  • Organic ultraviolet absorber A benzotriazole ultraviolet absorber ("Tinuvin P" manufactured by Ciba Specialty Chemicals) was used.
  • Example 1> Using three 40 mm single-screw extruders, the outer layer (organic UV absorber-free styrene resin layer) 35 ⁇ m / inner layer (organic UV absorber-containing styrene resin layer) 680 ⁇ m / A three-layer resin sheet having a thickness of 750 ⁇ m and a layer structure of 35 ⁇ m was manufactured as an outer layer (an organic ultraviolet absorber-free styrene resin layer).
  • HIPS / GPS a mixture of HIPS resin and GPPS resin at a mass ratio of 65/35
  • HIPS / GPS a mass ratio of HIPS resin and GPPS resin
  • the organic ultraviolet absorber was added to the resin mixed with GPPS) so as to have a ratio of 0.3 PHR to 100 parts by mass of all resin components including the inner layer and the outer layer.
  • the ultraviolet transmittance at a wavelength of 380 to 400 mm was measured using a spectrophotometer, and the ultraviolet shielding rate was determined to be 95%.
  • the total light transmittance measured by the method described in JIS K-7105 was 68%.
  • Example 2 Except that the amount of organic ultraviolet absorber added was 0.2 PHR (Example 2), 0.9 PHR (Example 3) and 0.1 PHR (Example 4), the same conditions as in Example 1 were obtained. A three-layer resin sheet was produced, and performance was evaluated for the same characteristics as in Example 1. As for Example 3, although the total light transmittance and film-forming property were slightly inferior, both levels had no practical problems. there were. In Example 4, the ultraviolet shielding rate was inferior, but it was a level with no practical problem.
  • Examples 5 and 6 Three-layer resin sheet under the same conditions as in Example 1 except that the ratio of the two types of styrene resins (HIPS resin and GPPS resin) used for the outer layer and inner layer was changed as described in Table 1. When performance was evaluated for the same characteristics as in Example 1, satisfactory results were obtained.
  • HIPS resin and GPPS resin styrene resins
  • Examples 7 and 8> Except for changing the total thickness as described in Table 1, a three-layer resin sheet was produced under exactly the same conditions as in Example 1, and the performance was evaluated for the same characteristics as in Example 1. Satisfactory results were obtained.
  • Table 1 summarizes the results of Examples 1 to 8 and Comparative Example.
  • surface is as follows.
  • X The occurrence of fumes is observed to some extent in practical use.

Landscapes

  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne une feuille de résine multicouche obtenue par stratification d'une couche extérieure de résine à base de styrène sans absorbeur d'UV organique sur les deux faces d'une couche intérieure de résine à base de styrène contenant un absorbeur d'UV organique. L'absorbeur d'UV organique est un absorbeur soit de benzophénone, soit de benzotriazole. Utilisée comme matériau d'emballage, la feuille de résine multicouche permet de réduire efficacement la dénaturation du contenu, la décoloration, la détérioration, notamment. Pour un matériau d'emballage transparent en particulier, il est possible d'obtenir une feuille de résine multicouche ne présentant pas de perte de transparence. Un récipient moulé peut être obtenu par moulage de la feuille de résine multicouche.
PCT/JP2012/079523 2011-11-14 2012-11-14 Feuille de résine multicouche et récipient moulé WO2013073579A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2013544297A JP6091425B2 (ja) 2011-11-14 2012-11-14 多層樹脂シート及び成形容器
CN201280055646.9A CN103930276A (zh) 2011-11-14 2012-11-14 多层树脂片及成型容器

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-248460 2011-11-14
JP2011248460 2011-11-14

Publications (1)

Publication Number Publication Date
WO2013073579A1 true WO2013073579A1 (fr) 2013-05-23

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Family Applications (1)

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PCT/JP2012/079523 WO2013073579A1 (fr) 2011-11-14 2012-11-14 Feuille de résine multicouche et récipient moulé

Country Status (3)

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JP (1) JP6091425B2 (fr)
CN (1) CN103930276A (fr)
WO (1) WO2013073579A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015199311A (ja) * 2014-04-10 2015-11-12 電気化学工業株式会社 積層シートおよびこれを用いた容器

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JP2000066603A (ja) * 1998-08-20 2000-03-03 Fuji Seal Inc ポリスチレン系フロスト調熱収縮ラベル
JP2002326324A (ja) * 2001-05-08 2002-11-12 C I Kasei Co Ltd 紫外線吸収ポリスチレン系樹脂熱収縮性フイルム
JP2008036849A (ja) * 2006-08-02 2008-02-21 Asahi Kasei Chemicals Corp 熱可塑性樹脂複合シート

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Publication number Priority date Publication date Assignee Title
JP2000066603A (ja) * 1998-08-20 2000-03-03 Fuji Seal Inc ポリスチレン系フロスト調熱収縮ラベル
JP2002326324A (ja) * 2001-05-08 2002-11-12 C I Kasei Co Ltd 紫外線吸収ポリスチレン系樹脂熱収縮性フイルム
JP2008036849A (ja) * 2006-08-02 2008-02-21 Asahi Kasei Chemicals Corp 熱可塑性樹脂複合シート

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015199311A (ja) * 2014-04-10 2015-11-12 電気化学工業株式会社 積層シートおよびこれを用いた容器

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JP6091425B2 (ja) 2017-03-08
CN103930276A (zh) 2014-07-16
JPWO2013073579A1 (ja) 2015-04-02

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