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WO2018056136A1 - Sheet and packaging container - Google Patents

Sheet and packaging container Download PDF

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Publication number
WO2018056136A1
WO2018056136A1 PCT/JP2017/033000 JP2017033000W WO2018056136A1 WO 2018056136 A1 WO2018056136 A1 WO 2018056136A1 JP 2017033000 W JP2017033000 W JP 2017033000W WO 2018056136 A1 WO2018056136 A1 WO 2018056136A1
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WO
WIPO (PCT)
Prior art keywords
sheet
resin
polyolefin
acid
inorganic substance
Prior art date
Application number
PCT/JP2017/033000
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French (fr)
Japanese (ja)
Inventor
祐一郎 角
重樹 黒木
Original Assignee
株式会社Ｔｂｍ
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Filing date
Publication date
Application filed by 株式会社Ｔｂｍ filed Critical 株式会社Ｔｂｍ
Publication of WO2018056136A1 publication Critical patent/WO2018056136A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/02—Wrappers or flexible covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment

Definitions

  • the present invention relates to a sheet and a packaging container.
  • a packaging container made of a plastic sheet has many advantages such as excellent water resistance, and is used as a material to replace a paper packaging container. However, from an environmental point of view, the use of petroleum-based resources should be minimized.
  • Patent Document 1 In connection with plastic packaging containers, this is a plastic for corrugated board filled with mineral powder.
  • Patent Document 1 has the following description. That is, it is described that an iron oxide or hydroxide powder is added to a plastic material for corrugated cardboard, and that 1 to 30% by weight of a calcium compound powder may be added. Is said to improve combustibility and reduce dioxin production during incineration.
  • Patent Document 2 for example, technologies for filling mineral powders and enhancing the functions of products have been developed one after another. Of course, these are also aimed at reducing petroleum resources at the same time. ing.
  • the important thing is the physical properties of the sheet, and the material is required to be resistant to deformation due to external force.
  • the present invention has been made in view of the above circumstances, and a plastic sheet is filled with an inorganic substance to save petroleum resources and at the same time has a physical property equal to or higher than that of a petroleum-based material only sheet and The purpose is to provide a packaging container.
  • the present inventors In manufacturing a plastic sheet containing a large amount of inorganic substance particles, the present inventors have used a hydrophobic thermoplastic resin in combination with a polyolefin-based resin having a hydrophilic group, so that no inorganic substance is filled. The inventors have found a method capable of producing a sheet having physical properties comparable to those of a filled sheet, and have completed the present invention. More specifically, the present invention provides the following.
  • a sheet The sheet is composed of a resin composition that includes a thermoplastic resin and inorganic substance particles in a ratio of 85:15 to 20:80, and further includes a polyolefin-based resin having a hydrophilic group.
  • the elastic modulus of the sheet is 1,000 MPa or more. Is a sheet.
  • polyolefin resin is an acid-modified polyolefin resin having a carboxylic acid or carboxylic anhydride segment.
  • the present invention it is possible to provide a sheet and a packaging container having a physical property equivalent to or higher than that of a sheet made of only a petroleum-based material while at the same time saving an oil-based resource by filling the plastic sheet with an inorganic substance.
  • the sheet of the present invention comprises a resin composition containing a thermoplastic resin and inorganic particles in a ratio of 85:15 to 20:80, and further comprising a polyolefin-based resin having a hydrophilic group, and has an elastic modulus.
  • the sheet is 1,000 MPa or more.
  • the polyolefin-based resin having a hydrophilic group has a hydrophobic segment of the polyolefin having a hydrophilic group having an affinity for a thermoplastic resin, while the hydrophilic group segment of the polyolefin-based resin has an affinity for an inorganic substance particle.
  • a dispersion effect is expected for the inorganic particles.
  • seat of this invention has a favorable physical property in the point of an elasticity modulus and tear strength, for example.
  • the polyolefin-based resin having a hydrophilic group is used as a compatibilizing agent, but in the present invention, it has an effect of dispersing inorganic substance particles in the thermoplastic resin as described above.
  • the polyolefin resin having a hydrophilic group is a resin having a polyolefin resin in the main chain and a hydrophilic group in the side chain.
  • the main chain polyolefin-based resin include polycycloolefin, polypropylene, polyethylene, polyvinyl chloride, polymethylpentene, and polybutene. Of these, polypropylene and polyethylene are preferred.
  • the hydrophilic group in the polyolefin resin is for dispersing inorganic substance particles in the thermoplastic resin, and specific examples include hydrophilic groups such as carboxylic acid, carboxylic anhydride, amino group, and hydroxyl group.
  • the polyolefin-based resin having a hydrophilic group is preferably an acid-modified polyolefin-based resin in which the polyolefin-based resin has a carboxylic acid or carboxylic anhydride segment, and the acid-modified polyolefin-based polyolefin is an acid-modified polypropylene. It is particularly preferred.
  • the content of the polyolefin-based resin having a hydrophilic group in the resin composition may be, for example, in the range of 0.1 to 20% with respect to the total mass of the thermoplastic resin composition. A range of 2 to 10% is particularly preferable.
  • the weight average molecular weight of the polyolefin-based resin having a hydrophilic group can be appropriately selected from the range of, for example, 20,000 to 70,000.
  • the weight average molecular weight of the polyolefin-type resin which has a hydrophilic group is measured by the high temperature gel permeation (GPC) method.
  • polyolefin-based resin having a hydrophilic group one having an acid value in the range of 20 to 60 (mgKOH / g) may be selected, for example.
  • the thermoplastic resin contained in the resin composition in the present invention is a resin having no hydrophilic group.
  • the thermoplastic resin can be selected from resins such as polyethylene (high density polyethylene, low density polyethylene), polypropylene, polystyrene, polyethylene terephthalate, and the like. Among these, it is preferable to use a polypropylene resin and a polyethylene resin, and it is particularly preferable to use a polypropylene resin.
  • Examples of the inorganic substance particles contained in the resin composition in the present invention include calcium carbonate, titanium oxide, silica, clay, talc, kaolin, aluminum hydroxide and the like, and calcium carbonate is particularly preferable. These may be used alone or in combination of two or more. Further, in order to improve the dispersibility or reactivity of the inorganic substance particles, the surface of the inorganic substance particles may be modified in advance according to a conventional method.
  • the blending ratio (mass ratio) between the thermoplastic resin and the inorganic particles contained in the resin composition in the present invention is not particularly limited as long as it is a ratio of 85:15 to 20:80, but 85:15 to 30: A ratio of 70 is preferred, a ratio of 85:15 to 35:65 is more preferred, and a ratio of 80:20 to 40:60 is even more preferred.
  • the average particle diameter of the inorganic substance particles is preferably from 0.1 ⁇ m to 50 ⁇ m, more preferably from 1.0 ⁇ m to 15 ⁇ m.
  • the average particle diameter of the inorganic substance particles in the present invention is a 50% particle diameter (d50) obtained from an integrated% distribution curve measured with a laser diffraction particle size distribution analyzer.
  • the sheet of the present invention has a good elastic modulus.
  • the elastic modulus is 1,000 MPa or more.
  • the elastic modulus of the sheet of the present invention is 1,500 MPa or more.
  • the elastic modulus can be increased by increasing the amount of the polyolefin resin having a hydrophilic group with respect to the inorganic substance particles.
  • the elastic modulus of the sheet of the present invention may be 4,000 MPa or less.
  • the elastic modulus and yield strength of the sheet are measured according to JIS K7161.
  • inorganic particles especially calcium carbonate is said to be effective in improving impact strength when blended with polypropylene resin.
  • it is necessary to determine the suitability of its use based on various physical properties such as tensile strength and tear strength.
  • the present inventors pay attention to the elastic modulus and yield strength of the sheet, and when the inorganic substance particles are blended with the thermoplastic resin, what effect the polyolefin resin having the hydrophilic group has? We examined whether to demonstrate.
  • the elastic modulus of the sheet is improved as the blending ratio of the inorganic substance particles increases due to the effect of the inorganic substance solids.
  • the effect of the combined use increases as the blending ratio of the thermoplastic resin decreases.
  • the elastic modulus is Of course, other physical property values are improved rather than a sheet of 100% thermoplastic resin.
  • the effect of the polyolefin-based resin acid-modified polypropylene resin having a hydrophilic group is clear.
  • thermoplastic resin in addition to the above-mentioned inorganic substance particles, thermoplastic resin, polyolefin resin having a hydrophilic group, as an auxiliary agent, a foaming agent, a colorant, a lubricant, A coupling agent, a fluidity improver, a dispersant, an antioxidant, an ultraviolet absorber, a stabilizer, an antistatic agent, and the like may be blended.
  • foaming agent For example, aliphatic hydrocarbons (propane, normal butane, isobutane, normal pentane, isopentane, hexane etc.), alicyclic hydrocarbons (cyclohexane, cyclopentane, cyclobutane etc.), halogen Hydrocarbons (trifluoromonochloroethane, difluorodichloromethane, etc.) and the like. These foaming agents may be used individually by 1 type, and may be used in combination of 2 or more type.
  • lubricants examples include stearic acid, hydroxystearic acid, complex stearic acid, oleic acid and other fatty acid lubricants, fatty alcohol lubricants, stearamide, oxystearamide, oleylamide, erucylamide, ricinolamide, behenamide, methylol Amide, Methylenebisstearoamide, Methylenebisstearobehenamide, Bisamidic acid of higher fatty acid, Aliphatic amide type lubricant such as composite amide, stearic acid-n-butyl, methyl hydroxystearate, polyhydric alcohol fatty acid ester, Examples thereof include aliphatic ester lubricants such as saturated fatty acid esters and ester waxes, and fatty acid metal soap group lubricants.
  • antioxidants phosphorus antioxidants, phenol antioxidants, pentaerythritol antioxidants can be used.
  • Phosphorus antioxidants such as phosphorous esters, more specifically phosphorous esters and phosphate esters, are preferably used.
  • Examples of phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, etc. Triester, diester, monoester of phosphorous acid, etc. Is mentioned.
  • phosphate ester examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate, and the like. These phosphorus antioxidants may be used alone or in combination of two or more.
  • phenolic antioxidants include ⁇ -tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2- tert-Butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethyl) Aminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, and tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane Etc., and these can be used alone or in combination of two or more. wear.
  • the use of the sheet of the present invention is not particularly limited, and for example, it can be used for various uses such as packaging, cardboard, wallpaper, etc., but since the tear strength and elastic modulus are good, these physical properties are required, For example, it is suitable for use as packaging and cardboard.
  • the sheet composed of the resin composition of the present invention can be produced according to a conventional method.
  • it can be produced by kneading and melting the above-mentioned thermoplastic resin, inorganic substance particles, and a polyolefin-based resin having a hydrophilic group, and forming the sheet into a sheet shape by an extruder.
  • the present invention includes a packaging container formed by the above-described sheet.
  • polypropylene resin polypropylene homopolymer (manufactured by Nippon Polypro Co., Ltd .: EA9) (abbreviation PP1), as surface-treated calcium carbonate, Ryton S-4 (Bihoku Flour & Chemical Co., Ltd. average particle size 2.2 ⁇ m) ( Abbreviation CC1), magnesium stearate (abbreviation MS1) as a lubricant, and acid-modified polyolefin resin (Umelix 1001, manufactured by Sanyo Chemical Co., Ltd., acid value: 26 (mgKOH / g)) (abbreviation CA1) as an additive. did.
  • PP1 and PP1 + CA1 resin were introduced from the uppermost stream with a heavy-weight vibration feeder, and from the middle of the cylinder CC1 and MS1 were charged by a gravimetric biaxial screw feeder, and after extruding the strand, cooled and cut to be pelletized.
  • the cylinder temperature of the PP1, PP1 + CA1 resin charging portion was set to 150 ° C.
  • the cylinder temperature of the CC1 and MS1 charging portions was set to 190 to 200 ° C.
  • the pellets thus produced were extruded at 220 ° C.
  • the tensile test of the extruded sheet was performed according to JISK7127 using a Toyo Seiki Seisakusho Strograph Tensile Tester E3-L.
  • the elastic modulus of the sheet was 1846 MPa, and the yield point strength was 26.1 MPa.
  • the elastic modulus of the sheet was 1515 MPa, and the yield point strength was 36.4 MPa.
  • the elastic modulus of the sheet was 1943 MPa, and the yield point strength was 19.7 MPa.
  • Example 1 As described above, as can be seen from the comparison between Example 1 and Comparative Example 1 and Example 2 and Comparative Example 2, the modulus of elasticity and the yield strength were increased by adding CA1 (acid-modified polyolefin resin). Further, as can be seen from the comparison between Example 2 and Comparative Example 3, compared to Comparative Example 3 in which only the petroleum-based material (PP only) is used, Example 2 includes not only the elastic modulus but also the yield point in spite of containing calcium carbonate. It was found that the strength was also good.
  • CA1 acid-modified polyolefin resin
  • Example 2 The sheet according to Example 2 and the sheet according to Comparative Example 2 were observed with a microscope.
  • the microscope used was TM3000 manufactured by Hitachi High-Technologies Corporation. The observation results are shown in FIG. In FIG. 1, (a) is an image of a sheet according to Example 2, and (b) is an image of a sheet according to Comparative Example 2.
  • Example 2 As shown in FIG. 1, in Comparative Example 2 that does not contain CA1 (acid-modified polyolefin resin), there is a space around the calcium carbonate particles, or the boundary with the resin is clear. In Example 2 including a resin, it was found that the calcium carbonate particles were covered with CA1 (acid-modified polyolefin resin).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Wrappers (AREA)

Abstract

Provided are a sheet and a packaging container that economize petroleum resources by filling a plastic sheet with an inorganic substance, and that have physical properties of a similar extent to or better than those of a sheet comprising only petroleum raw materials. This sheet is configured by a resin composition containing a thermoplastic resin and particles of an inorganic substance at a ratio of 85:15 to 20:80, and further containing a polyolefin resin having a hydrophilic group, and the elastic modulus of the sheet is at least 1000 MPa. It is preferable that the polyolefin resin having a hydrophilic group be an acid-modified polyolefin resin having a carboxylic acid or an anhydrous carboxylic acid segment.

Description

シート及び包装容器Sheets and packaging containers
　本発明は、シート及び包装容器に関する。 The present invention relates to a sheet and a packaging container.
　プラスチック製のシートからなる包装容器は、耐水性に優れる等利点が多いことから、紙製の包装容器に代わる材料として使用される。しかし、環境の観点からは、石油系資源の利用はできる限り抑える必要がある。 A packaging container made of a plastic sheet has many advantages such as excellent water resistance, and is used as a material to replace a paper packaging container. However, from an environmental point of view, the use of petroleum-based resources should be minimized.
　プラスチック製の包装容器に関連して、鉱物質粉末を充填した段ボール用プラスチックで、特許文献１に次のような記載がある。すなわち、段ボール用プラスチック材料に鉄の酸化物又は水酸化物の粉末を添加することが記され、さらにカルシウムの化合物の粉末を１～３０重量％添加してもよいと記載されて、これらの方法は焼却時に、燃焼性の改善とダイオキシンの生成量の低減をもたらすとされている。 In connection with plastic packaging containers, this is a plastic for corrugated board filled with mineral powder. Patent Document 1 has the following description. That is, it is described that an iron oxide or hydroxide powder is added to a plastic material for corrugated cardboard, and that 1 to 30% by weight of a calcium compound powder may be added. Is said to improve combustibility and reduce dioxin production during incineration.
　また、例えば特許文献２に記載されているように、鉱物質粉末を充填して、製品の機能を強化する技術も次々と開発されており、当然ながらこれらは同時に石油系資源の低減を目的にしている。 In addition, as described in Patent Document 2, for example, technologies for filling mineral powders and enhancing the functions of products have been developed one after another. Of course, these are also aimed at reducing petroleum resources at the same time. ing.
特開２０００－２９６５７１号公報JP 2000-296571 A 特開２０００－８６７９１号公報JP 2000-86791 A
　例えば、包装用として使用する場合、重要なことはシートの物性で、素材として外力に対し変形しにくい性質が求められる。 For example, when used for packaging, the important thing is the physical properties of the sheet, and the material is required to be resistant to deformation due to external force.
　本発明は以上の実情に鑑みてなされたものであり、プラスチックシートについて、無機物質を充填させて石油系資源を節減すると同時に石油系素材のみのシートと同程度もしくはそれ以上の物性をもつシート及び包装容器を提供することを目的とする。 The present invention has been made in view of the above circumstances, and a plastic sheet is filled with an inorganic substance to save petroleum resources and at the same time has a physical property equal to or higher than that of a petroleum-based material only sheet and The purpose is to provide a packaging container.
　本発明者らは、無機物質粒子を多く含むプラスチック製のシートの製造にあたって、疎水性の熱可塑性樹脂と、親水性基を有するポリオレフィン系樹脂を併用することにより、無機物質を充填しても無充填のシートと比較して遜色のない物性値をもつシートを作成できる方法を見出し、本発明を完成するに至った。より具体的には、本発明は以下のようなものを提供する。 In manufacturing a plastic sheet containing a large amount of inorganic substance particles, the present inventors have used a hydrophobic thermoplastic resin in combination with a polyolefin-based resin having a hydrophilic group, so that no inorganic substance is filled. The inventors have found a method capable of producing a sheet having physical properties comparable to those of a filled sheet, and have completed the present invention. More specifically, the present invention provides the following.
　（１）　シートであって、
　熱可塑性樹脂と、無機物質粒子とを８５：１５～２０：８０の比率で含み、さらに、親水性基を有するポリオレフィン系樹脂を含む樹脂組成物によって構成され、シートの弾性率が１，０００ＭＰａ以上であるシート。 (1) A sheet,
The sheet is composed of a resin composition that includes a thermoplastic resin and inorganic substance particles in a ratio of 85:15 to 20:80, and further includes a polyolefin-based resin having a hydrophilic group. The elastic modulus of the sheet is 1,000 MPa or more. Is a sheet.
　（２）　包装用である、（１）に記載のシート。 (2) The sheet according to (1), which is for packaging.
　（３）　段ボールに用いられる、（１）又は（２）に記載のシート。 (3) The sheet according to (1) or (2), which is used for cardboard.
　（４）　前記ポリオレフィン系樹脂がカルボン酸又は無水カルボン酸のセグメントを有する酸変性ポリオレフィン系樹脂である、（１）から（３）のいずれかに記載のシート。 (4) The sheet according to any one of (1) to (3), wherein the polyolefin resin is an acid-modified polyolefin resin having a carboxylic acid or carboxylic anhydride segment.
　（５）　酸変性ポリオレフィン系ポリオレフィンが酸変性ポリプロピレンである、（４）に記載のシート。 (5) The sheet according to (4), wherein the acid-modified polyolefin-based polyolefin is acid-modified polypropylene.
　（６）　前記樹脂組成物が、前記ポリオレフィン系樹脂を前記樹脂組成物の全体の質量に対して０．２～１０％含有する、（１）から（５）のいずれかに記載のシート。 (6) The sheet according to any one of (1) to (5), wherein the resin composition contains 0.2 to 10% of the polyolefin resin with respect to the total mass of the resin composition.
　（７）　前記無機物質粒子が炭酸カルシウム粒子を含む、（１）から（６）のいずれかに記載のシート。 (7) The sheet according to any one of (1) to (6), wherein the inorganic substance particles include calcium carbonate particles.
　（８）　（１）から（７）のいずれかに記載のシートにより形成された包装容器。 (8) A packaging container formed by the sheet according to any one of (1) to (7).
　本発明によると、プラスチックシートについて、無機物質を充填させて石油系資源を節減すると同時に石油系素材のみのシートと同程度もしくはそれ以上の物性をもつシート及び包装容器を提供することができる。 According to the present invention, it is possible to provide a sheet and a packaging container having a physical property equivalent to or higher than that of a sheet made of only a petroleum-based material while at the same time saving an oil-based resource by filling the plastic sheet with an inorganic substance.
実施例２に係るシート、比較例２に係るシートについての顕微鏡観察による画像である。It is the image by microscope observation about the sheet | seat which concerns on Example 2, and the sheet | seat which concerns on the comparative example 2. FIG.
　以下、本発明の実施形態について説明するが、本発明は特にこれに限定されず、適宜変更可能である。 Hereinafter, embodiments of the present invention will be described, but the present invention is not particularly limited thereto and can be appropriately changed.
　＜シート＞
　本発明のシートは、熱可塑性樹脂と、無機物質粒子とを８５：１５～２０：８０の比率で含み、さらに、親水性基を有するポリオレフィン系樹脂を含む樹脂組成物によって構成され、弾性率が１，０００ＭＰａ以上であるシートである。 <Sheet>
The sheet of the present invention comprises a resin composition containing a thermoplastic resin and inorganic particles in a ratio of 85:15 to 20:80, and further comprising a polyolefin-based resin having a hydrophilic group, and has an elastic modulus. The sheet is 1,000 MPa or more.
　親水性基を有するポリオレフィン系樹脂は、親水性基を有するポリオレフィンの疎水性のセグメントが熱可塑性樹脂と親和性をもち、一方でポリオレフィン系樹脂の親水性基のセグメントが無機物質粒子と親和性があって、無機物質粒子に対し分散効果が見込まれている。これにより、本発明のシートは、例えば、弾性率、引き裂き強度の点において、良好な物性を有する。なお、上記親水性基を有するポリオレフィン系樹脂は相溶化剤として使われているものであるが、本発明においては、上記のように無機物質粒子を熱可塑性樹脂中に分散させる効果を有する。 The polyolefin-based resin having a hydrophilic group has a hydrophobic segment of the polyolefin having a hydrophilic group having an affinity for a thermoplastic resin, while the hydrophilic group segment of the polyolefin-based resin has an affinity for an inorganic substance particle. Thus, a dispersion effect is expected for the inorganic particles. Thereby, the sheet | seat of this invention has a favorable physical property in the point of an elasticity modulus and tear strength, for example. The polyolefin-based resin having a hydrophilic group is used as a compatibilizing agent, but in the present invention, it has an effect of dispersing inorganic substance particles in the thermoplastic resin as described above.
　親水性基を有するポリオレフィン系樹脂は、主鎖にポリオレフィン系樹脂を有し、側鎖に親水性基を有する樹脂である。主鎖のポリオレフィン系樹脂の部分は、ポリシクロオレフィン、ポリプロピレン、ポリエチレン、ポリ塩化ビニル、ポリメチルペンテン、ポリブテン等が挙げられる。これらのうち、ポリプロピレン、ポリエチレンが好ましい。 The polyolefin resin having a hydrophilic group is a resin having a polyolefin resin in the main chain and a hydrophilic group in the side chain. Examples of the main chain polyolefin-based resin include polycycloolefin, polypropylene, polyethylene, polyvinyl chloride, polymethylpentene, and polybutene. Of these, polypropylene and polyethylene are preferred.
　ポリオレフィン系樹脂における親水性基は、無機物質粒子を熱可塑性樹脂中に分散させるものであり、具体的には、カルボン酸、無水カルボン酸、アミノ基、水酸基等の親水性基が挙げられる。これらのうち、親水性基を有するポリオレフィン系樹脂は、ポリオレフィン系樹脂がカルボン酸又は無水カルボン酸のセグメントを有する酸変性ポリオレフィン系樹脂であることが好ましく、酸変性ポリオレフィン系ポリオレフィンが酸変性ポリプロピレンであることが特に好ましい。 The hydrophilic group in the polyolefin resin is for dispersing inorganic substance particles in the thermoplastic resin, and specific examples include hydrophilic groups such as carboxylic acid, carboxylic anhydride, amino group, and hydroxyl group. Among these, the polyolefin-based resin having a hydrophilic group is preferably an acid-modified polyolefin-based resin in which the polyolefin-based resin has a carboxylic acid or carboxylic anhydride segment, and the acid-modified polyolefin-based polyolefin is an acid-modified polypropylene. It is particularly preferred.
　樹脂組成物における、親水性基を有するポリオレフィン系樹脂の含有量は、例えば、熱可塑性樹脂組成物の全体の質量に対して、０．１～２０％の範囲内であってよいが、０．２～１０％の範囲内であることが特に好ましい。 The content of the polyolefin-based resin having a hydrophilic group in the resin composition may be, for example, in the range of 0.1 to 20% with respect to the total mass of the thermoplastic resin composition. A range of 2 to 10% is particularly preferable.
　親水性基を有するポリオレフィン系樹脂の重量平均分子量は、例えば、２０，０００～７０，０００の範囲内から適宜選択することができる。なお、親水性基を有するポリオレフィン系樹脂の重量平均分子量は、高温ゲルパーミエーション（ＧＰＣ）法により測定する。 The weight average molecular weight of the polyolefin-based resin having a hydrophilic group can be appropriately selected from the range of, for example, 20,000 to 70,000. In addition, the weight average molecular weight of the polyolefin-type resin which has a hydrophilic group is measured by the high temperature gel permeation (GPC) method.
　親水性基を有するポリオレフィン系樹脂は、例えば、酸価度が２０～６０（ｍｇＫＯＨ／ｇ）の範囲内のものを選択してもよい。 As the polyolefin-based resin having a hydrophilic group, one having an acid value in the range of 20 to 60 (mgKOH / g) may be selected, for example.
　本発明における樹脂組成物に含まれる熱可塑性樹脂は、親水性基を有さない樹脂である。熱可塑性樹脂としては、例えば、ポリエチレン（高密度ポリエチレン、低密度ポリエチレン）、ポリプロピレン、ポリスチレン、ポリエチレンテレフタレート等の樹脂等の中から選択することができる。これらのうち、ポリプロピレン樹脂、ポリエチレン樹脂を用いることが好ましく、ポリプロピレン樹脂を用いることが特に好ましい。 The thermoplastic resin contained in the resin composition in the present invention is a resin having no hydrophilic group. The thermoplastic resin can be selected from resins such as polyethylene (high density polyethylene, low density polyethylene), polypropylene, polystyrene, polyethylene terephthalate, and the like. Among these, it is preferable to use a polypropylene resin and a polyethylene resin, and it is particularly preferable to use a polypropylene resin.
　本発明における樹脂組成物に含まれる無機物質粒子としては、例えば、炭酸カルシウム、酸化チタン、シリカ、クレー、タルク、カオリン、水酸化アルミニウム等が挙げられ、特に炭酸カルシウムが好ましい。これらは単独で使用しても、２種類以上併用してもよい。また、無機物質粒子の分散性又は反応性を高めるために、無機物質粒子の表面を予め常法に従い改質しておいてもよい。 Examples of the inorganic substance particles contained in the resin composition in the present invention include calcium carbonate, titanium oxide, silica, clay, talc, kaolin, aluminum hydroxide and the like, and calcium carbonate is particularly preferable. These may be used alone or in combination of two or more. Further, in order to improve the dispersibility or reactivity of the inorganic substance particles, the surface of the inorganic substance particles may be modified in advance according to a conventional method.
　本発明における樹脂組成物に含まれる熱可塑性樹脂と、無機物質粒子との配合比（質量比）は、８５：１５～２０：８０の比率であれば特に限定されないが、８５：１５～３０：７０の比率であることが好ましく、８５：１５～３５：６５の比率であることがより好ましく、８０：２０～４０：６０の比率であることがより一層好ましい。 The blending ratio (mass ratio) between the thermoplastic resin and the inorganic particles contained in the resin composition in the present invention is not particularly limited as long as it is a ratio of 85:15 to 20:80, but 85:15 to 30: A ratio of 70 is preferred, a ratio of 85:15 to 35:65 is more preferred, and a ratio of 80:20 to 40:60 is even more preferred.
　無機物質粒子の平均粒子径は、０．１μｍ以上５０μｍ以下が好ましく、１．０μ以上１５μｍ以下がより好ましい。本発明における無機物質粒子の平均粒子径は、レーザー回折式粒度分布測定装置で測定した、積算％の分布曲線から得られる５０％粒子径（ｄ５０）である。 The average particle diameter of the inorganic substance particles is preferably from 0.1 μm to 50 μm, more preferably from 1.0 μm to 15 μm. The average particle diameter of the inorganic substance particles in the present invention is a 50% particle diameter (d50) obtained from an integrated% distribution curve measured with a laser diffraction particle size distribution analyzer.
　本発明のシートは、弾性率が良好であり、具体的には、弾性率が、１，０００ＭＰａ以上である。好ましくは、本発明のシートの弾性率は、１，５００ＭＰａ以上であることが好ましい。弾性率は、無機物質粒子に対する親水性基を有するポリオレフィン系樹脂の量を増やすことで、高くすることができる。また、本発明のシートの弾性率は、４，０００ＭＰａ以下であってもよい。本発明において、シートの弾性率および降伏強度は、ＪＩＳ　Ｋ７１６１に準じて測定する。 The sheet of the present invention has a good elastic modulus. Specifically, the elastic modulus is 1,000 MPa or more. Preferably, the elastic modulus of the sheet of the present invention is 1,500 MPa or more. The elastic modulus can be increased by increasing the amount of the polyolefin resin having a hydrophilic group with respect to the inorganic substance particles. Further, the elastic modulus of the sheet of the present invention may be 4,000 MPa or less. In the present invention, the elastic modulus and yield strength of the sheet are measured according to JIS K7161.
　無機物質粒子のなかでも特に炭酸カルシウムは、ポリプロピレン樹脂に配合すると衝撃強度の向上に効果があるとされている。しかし、プラスチックシートの場合には、引張強度、引裂き強度等いろいろな物性値でその使用の適否を判断する必要がある。 Among inorganic particles, especially calcium carbonate is said to be effective in improving impact strength when blended with polypropylene resin. However, in the case of a plastic sheet, it is necessary to determine the suitability of its use based on various physical properties such as tensile strength and tear strength.
　以上の観点から、本発明者らは、シートの弾性率と降伏点強度に着目して、熱可塑性樹脂に無機物質粒子を配合した場合に、上記親水性基を有するポリオレフィン樹脂がどのような効果を発揮するか検討した。 From the above viewpoints, the present inventors pay attention to the elastic modulus and yield strength of the sheet, and when the inorganic substance particles are blended with the thermoplastic resin, what effect the polyolefin resin having the hydrophilic group has? We examined whether to demonstrate.
　無機物質粒子を熱可塑性樹脂に配合した場合（特に、炭酸カルシウムを配合した場合）、シートの弾性率は、無機物質固体の効果で、無機物質粒子の配合率の増加に従い向上する。 When the inorganic substance particles are blended with the thermoplastic resin (particularly when calcium carbonate is blended), the elastic modulus of the sheet is improved as the blending ratio of the inorganic substance particles increases due to the effect of the inorganic substance solids.
　さらに親水性基を有するポリオレフィン系樹脂を併用すると、熱可塑性樹脂の配合率の減少にともない併用の効果が大きくなり、特に、熱可塑性樹脂の配合率が８０％の成形シートの場合、弾性率は勿論、他の物性値も熱可塑性樹脂１００％のシートよりむしろ向上する。さらに親水性基を有するポリオレフィン系樹脂酸変性ポリプロピレン樹脂の効果は明確である。 Furthermore, when a polyolefin-based resin having a hydrophilic group is used in combination, the effect of the combined use increases as the blending ratio of the thermoplastic resin decreases. In particular, in the case of a molded sheet having a blending ratio of the thermoplastic resin of 80%, the elastic modulus is Of course, other physical property values are improved rather than a sheet of 100% thermoplastic resin. Furthermore, the effect of the polyolefin-based resin acid-modified polypropylene resin having a hydrophilic group is clear.
　なお、上述した本発明のシートと構成する樹脂組成物においては、上述した無機物質粒子、熱可塑性樹脂、親水性基を有するポリオレフィン樹脂以外にも、補助剤として、発泡剤、色剤、滑剤、カップリング剤、流動性改良材、分散剤、酸化防止剤、紫外線吸収剤、安定剤、帯電防止剤等を配合してもよい。 In addition, in the resin composition constituting the sheet of the present invention described above, in addition to the above-mentioned inorganic substance particles, thermoplastic resin, polyolefin resin having a hydrophilic group, as an auxiliary agent, a foaming agent, a colorant, a lubricant, A coupling agent, a fluidity improver, a dispersant, an antioxidant, an ultraviolet absorber, a stabilizer, an antistatic agent, and the like may be blended.
　発泡剤としては、特に限定されないが、例えば、脂肪族炭化水素類（プロパン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、ヘキサン等）、脂環族炭化水素（シクロヘキサン、シクロペンタン、シクロブタン等）、ハロゲン化炭化水素（トリフロロモノクロロエタン、ジフロロジクロロメタン等）等が挙げられる。これら発泡剤は１種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Although it does not specifically limit as a foaming agent, For example, aliphatic hydrocarbons (propane, normal butane, isobutane, normal pentane, isopentane, hexane etc.), alicyclic hydrocarbons (cyclohexane, cyclopentane, cyclobutane etc.), halogen Hydrocarbons (trifluoromonochloroethane, difluorodichloromethane, etc.) and the like. These foaming agents may be used individually by 1 type, and may be used in combination of 2 or more type.
　滑剤としては、例えば、ステアリン酸、ヒドロキシステアリン酸、複合型ステアリン酸、オレイン酸等の脂肪酸系滑剤、脂肪族アルコール系滑剤、ステアロアミド、オキシステアロアミド、オレイルアミド、エルシルアミド、リシノールアミド、ベヘンアミド、メチロールアミド、メチレンビスステアロアミド、メチレンビスステアロベヘンアミド、高級脂肪酸のビスアミド酸、複合型アミド等の脂肪族アマイド系滑剤、ステアリン酸－ｎ－ブチル、ヒドロキシステアリン酸メチル、多価アルコール脂肪酸エステル、飽和脂肪酸エステル、エステル系ワックス等の脂肪族エステル系滑剤、脂肪酸金属石鹸系族滑剤等を挙げることができる。 Examples of lubricants include stearic acid, hydroxystearic acid, complex stearic acid, oleic acid and other fatty acid lubricants, fatty alcohol lubricants, stearamide, oxystearamide, oleylamide, erucylamide, ricinolamide, behenamide, methylol Amide, Methylenebisstearoamide, Methylenebisstearobehenamide, Bisamidic acid of higher fatty acid, Aliphatic amide type lubricant such as composite amide, stearic acid-n-butyl, methyl hydroxystearate, polyhydric alcohol fatty acid ester, Examples thereof include aliphatic ester lubricants such as saturated fatty acid esters and ester waxes, and fatty acid metal soap group lubricants.
　酸化防止剤としては、リン系酸化防止剤、フェノール系酸化防止剤、ペンタエリスリトール系酸化防止剤が使用できる。リン系、より具体的には亜リン酸エステル、リン酸エステル等のリン系酸化防止安定剤が好ましく用いられる。亜リン酸エステルとしては、例えば、トリフェニルホスファイト、トリスノニルフェニルホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、等の亜リン酸のトリエステル、ジエステル、モノエステル等が挙げられる。 As the antioxidant, phosphorus antioxidants, phenol antioxidants, pentaerythritol antioxidants can be used. Phosphorus antioxidants, such as phosphorous esters, more specifically phosphorous esters and phosphate esters, are preferably used. Examples of phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, etc. Triester, diester, monoester of phosphorous acid, etc. Is mentioned.
　リン酸エステルとしては、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリス（ノニルフェニル）ホスフェート、２－エチルフェニルジフェニルホスフェート等が挙げられる。これらリン系酸化防止剤は単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate, and the like. These phosphorus antioxidants may be used alone or in combination of two or more.
　フェノール系の酸化防止剤としては、α－トコフェロール、ブチルヒドロキシトルエン、シナピルアルコール、ビタミンＥ、ｎ－オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネイト、２－ｔｅｒｔ－ブチル－６－（３’－ｔｅｒｔ－ブチル－５'－メチル－２'－ヒドロキシベンジル）－４－メチルフェニルアクリレート、２，６－ジ－ｔｅｒｔ－ブチル－４－（Ｎ，Ｎ－ジメチルアミノメチル）フェノール、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホネイトジエチルエステル、及びテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシメチル］メタン等が例示され、これらは単独で又は２種以上を組み合せて使用することができる。 Examples of phenolic antioxidants include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2- tert-Butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethyl) Aminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, and tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane Etc., and these can be used alone or in combination of two or more. wear.
　本発明のシートの用途は特に限定されず、例えば、包装用、段ボール、壁紙等の種々の用途に使用できるが、引き裂き強度、弾性率が良好であることから、これらの物性が求められる用途、例えば、包装用、段ボールとして使用するのに適している。 The use of the sheet of the present invention is not particularly limited, and for example, it can be used for various uses such as packaging, cardboard, wallpaper, etc., but since the tear strength and elastic modulus are good, these physical properties are required, For example, it is suitable for use as packaging and cardboard.
　本発明の樹脂組成物から構成されるシートは、常法にしたがって製造することができる。例えば、上述の熱可塑性樹脂、無機物質粒子、親水性基を有するポリオレフィン系樹脂を、混練、溶融し、押出機によりシート状に成形することで製造することができる。 The sheet composed of the resin composition of the present invention can be produced according to a conventional method. For example, it can be produced by kneading and melting the above-mentioned thermoplastic resin, inorganic substance particles, and a polyolefin-based resin having a hydrophilic group, and forming the sheet into a sheet shape by an extruder.
　＜包装容器＞
　本発明は、上述のシートにより形成された包装容器を包含する。 <Packing container>
The present invention includes a packaging container formed by the above-described sheet.
　ポリプロピレン樹脂として、ポリプロピレン単独重合体（日本ポリプロ（株）製：ＥＡ９）（略号ＰＰ１）、表面処理炭酸カルシウムとして、ライトンＳ―４（備北粉化工業（株）製　平均粒子径　２．２μｍ）（略号ＣＣ１）、滑剤としてステアリン酸マグネシウム（略号ＭＳ１）、添加剤として、酸変性ポリオレフィン系樹脂（三洋化成（株）製ユーメリックス　１００１、酸価度：２６（ｍｇＫＯＨ／ｇ））（略号ＣＡ１）を使用した。 As polypropylene resin, polypropylene homopolymer (manufactured by Nippon Polypro Co., Ltd .: EA9) (abbreviation PP1), as surface-treated calcium carbonate, Ryton S-4 (Bihoku Flour & Chemical Co., Ltd. average particle size 2.2 μm) ( Abbreviation CC1), magnesium stearate (abbreviation MS1) as a lubricant, and acid-modified polyolefin resin (Umelix 1001, manufactured by Sanyo Chemical Co., Ltd., acid value: 26 (mgKOH / g)) (abbreviation CA1) as an additive. did.
　（株）パーカーコーポレーション製同方向回転ニ軸混錬押出機ＨＫ－２５Ｄ（φ２５ｍｍ、Ｌ／Ｄ＝４１）を用い、最上流からＰＰ１、ＰＰ１＋ＣＡ１樹脂を重量式振動フィーダーで投入し、シリンダー中程からＣＣ１及びＭＳ１を重量式ニ軸スクリューフィーダーで投入し、ストランド押出後、冷却、カットすることでペレット化した。ＰＰ１、ＰＰ１＋ＣＡ１樹脂投入部のシリンダー温度は１５０℃、ＣＣ１及びＭＳ１投入部のシリンダー温度は１９０～２００℃に設定した。このようにして作製したペレットを（株）東洋精機製作所製ラボプラストミル一軸Ｔダイ押出成形装置（（φ２０ｍｍ、Ｌ／Ｄ＝２５）により、２２０℃で押出し、厚さ０．３ｍｍのシートに成形した。 Using a co-rotating twin-screw kneading extruder HK-25D (φ25mm, L / D = 41) manufactured by Parker Corporation, PP1 and PP1 + CA1 resin were introduced from the uppermost stream with a heavy-weight vibration feeder, and from the middle of the cylinder CC1 and MS1 were charged by a gravimetric biaxial screw feeder, and after extruding the strand, cooled and cut to be pelletized. The cylinder temperature of the PP1, PP1 + CA1 resin charging portion was set to 150 ° C., and the cylinder temperature of the CC1 and MS1 charging portions was set to 190 to 200 ° C. The pellets thus produced were extruded at 220 ° C. by a Laboplast mill uniaxial T-die extrusion molding apparatus ((φ20 mm, L / D = 25) manufactured by Toyo Seiki Seisakusho Co., Ltd., and formed into a sheet having a thickness of 0.3 mm. did.
　押出し成形したシートの引っ張り試験は（株）東洋精機製作所ストログラフ引張試験機Ｅ３－Ｌを用い、ＪＩＳＫ７１２７に準じて行った。 The tensile test of the extruded sheet was performed according to JISK7127 using a Toyo Seiki Seisakusho Strograph Tensile Tester E3-L.
　＜実施例１＞
　ＰＰ１＋ＣＡ１（ＰＰ１に対し５重量％）／ＣＣ１／ＭＳ１＝６０／４０／０．５の比率で調整したペレットをシートに成形した。シートの弾性率は１８４６ＭＰａ、降伏点強度は２６．１ＭＰａであった。 <Example 1>
Pellets prepared at a ratio of PP1 + CA1 (5% by weight with respect to PP1) /CC1/MS1=60/40/0.5 were formed into a sheet. The elastic modulus of the sheet was 1846 MPa, and the yield point strength was 26.1 MPa.
　＜実施例２＞
　ＰＰ１＋ＣＡ１（ＰＰ１に対し５重量％）／ＣＣ１／ＭＳ１＝８０／２０／０．５の比率で調整したペレットをシートに成形した。シートの弾性率は１５１５ＭＰａ、降伏点強度は３６．４ＭＰａであった。 <Example 2>
Pellets prepared at a ratio of PP1 + CA1 (5% by weight with respect to PP1) /CC1/MS1=80/20/0.5 were formed into a sheet. The elastic modulus of the sheet was 1515 MPa, and the yield point strength was 36.4 MPa.
　＜実施例３＞
　ＰＰ１＋ＣＡ１（ＰＰ１に対し５重量％）／ＣＣ１／ＭＳ１＝４０／６０／０．５の比率で調整したペレットをシートに成形した。シートの弾性率は１９４３ＭＰａ、降伏点強度は１９．７ＭＰａであった。 <Example 3>
Pellets prepared at a ratio of PP1 + CA1 (5% by weight with respect to PP1) /CC1/MS1=40/60/0.5 were formed into a sheet. The elastic modulus of the sheet was 1943 MPa, and the yield point strength was 19.7 MPa.
　＜比較例１＞
　ＰＰ１／ＣＣ１／ＭＳ１＝６０／４０／０．５の比率で調整したペレットをシートに成形した。シートの弾性率は１４３４ＭＰａ、降伏点強度は２４．３ＭＰａであった。 <Comparative Example 1>
Pellets prepared at a ratio of PP1 / CC1 / MS1 = 60/40 / 0.5 were formed into sheets. The elastic modulus of the sheet was 1434 MPa, and the yield point strength was 24.3 MPa.
　＜比較例２＞
　ＰＰ１／ＣＣ１／ＭＳ１＝８０／２０／０．５の比率で調整したペレットをシートに成形した。シートの弾性率は１４１７ＭＰａ、降伏点強度は３２．０ＭＰａであった。 <Comparative example 2>
Pellets prepared at a ratio of PP1 / CC1 / MS1 = 80/20 / 0.5 were formed into sheets. The elastic modulus of the sheet was 1417 MPa, and the yield point strength was 32.0 MPa.
　＜比較例３＞
　ＰＰ１単独で調製したペレットをシートに成形した。シートの弾性率は９５５ＭＰａ、降伏点強度は２９．１ＭＰａであった。 <Comparative Example 3>
Pellets prepared with PP1 alone were formed into sheets. The elastic modulus of the sheet was 955 MPa, and the yield point strength was 29.1 MPa.
　上記にとおり、実施例１と比較例１、実施例２と比較例２の比較からわかるように、ＣＡ１（酸変性ポリオレフィン系樹脂）を加えることで、弾性率、降伏点強度が上昇した。また、実施例２と比較例３の比較からわかるように、石油系素材のみ（ＰＰのみ）の比較例３より、実施例２は炭酸カルシウムを含むにもかかわらず、弾性率のみでなく降伏点強度も良好となることがわかった。 As described above, as can be seen from the comparison between Example 1 and Comparative Example 1 and Example 2 and Comparative Example 2, the modulus of elasticity and the yield strength were increased by adding CA1 (acid-modified polyolefin resin). Further, as can be seen from the comparison between Example 2 and Comparative Example 3, compared to Comparative Example 3 in which only the petroleum-based material (PP only) is used, Example 2 includes not only the elastic modulus but also the yield point in spite of containing calcium carbonate. It was found that the strength was also good.
　＜顕微鏡観察＞
　実施例２に係るシート、比較例２に係るシートについて、顕微鏡観察を行った。顕微鏡は日立ハイテクノロジーズ社製のＴＭ３０００を用いた。観察結果を図１に示す。図１中、（ａ）が実施例２に係るシートの画像であり、（ｂ）が比較例２に係るシートの画像である。 <Microscope observation>
The sheet according to Example 2 and the sheet according to Comparative Example 2 were observed with a microscope. The microscope used was TM3000 manufactured by Hitachi High-Technologies Corporation. The observation results are shown in FIG. In FIG. 1, (a) is an image of a sheet according to Example 2, and (b) is an image of a sheet according to Comparative Example 2.
　図１に示すように、ＣＡ１（酸変性ポリオレフィン系樹脂）を含まない比較例２においては炭酸カルシウム粒子の周りに空間が空いてたり、樹脂との境界が明らかであるが、ＣＡ１（酸変性ポリオレフィン系樹脂）を含む実施例２においては、ＣＡ１（酸変性ポリオレフィン系樹脂）により炭酸カルシウム粒子が覆われていることがわかった。 As shown in FIG. 1, in Comparative Example 2 that does not contain CA1 (acid-modified polyolefin resin), there is a space around the calcium carbonate particles, or the boundary with the resin is clear. In Example 2 including a resin, it was found that the calcium carbonate particles were covered with CA1 (acid-modified polyolefin resin).

Claims (8)

  1. 　シートであって、
    　熱可塑性樹脂と、無機物質粒子とを８５：１５～２０：８０の比率で含み、さらに、親水性基を有するポリオレフィン系樹脂を含む樹脂組成物によって構成され、シートの弾性率が１，０００ＭＰａ以上であるシート。     A sheet,
    The sheet is composed of a resin composition that includes a thermoplastic resin and inorganic substance particles in a ratio of 85:15 to 20:80, and further includes a polyolefin-based resin having a hydrophilic group. The elastic modulus of the sheet is 1,000 MPa or more. Is a sheet.
  2. 　包装用である、請求項１に記載のシート。 The sheet according to claim 1, which is for packaging.
  3. 　段ボールに用いられる、請求項１又は２に記載のシート。 The sheet according to claim 1 or 2, which is used for cardboard.
  4. 　前記ポリオレフィン系樹脂がカルボン酸又は無水カルボン酸のセグメントを有する酸変性ポリオレフィン系樹脂である、請求項１から３のいずれかに記載のシート。 The sheet according to any one of claims 1 to 3, wherein the polyolefin resin is an acid-modified polyolefin resin having a carboxylic acid or carboxylic anhydride segment.
  5. 　酸変性ポリオレフィン系ポリオレフィンが酸変性ポリプロピレンである、請求項４に記載のシート。 The sheet according to claim 4, wherein the acid-modified polyolefin-based polyolefin is acid-modified polypropylene.
  6. 　前記樹脂組成物が、前記ポリオレフィン系樹脂を前記樹脂組成物の全体の質量に対して０．２～１０％含有する、請求項１から５のいずれかに記載のシート。 The sheet according to any one of claims 1 to 5, wherein the resin composition contains 0.2 to 10% of the polyolefin resin with respect to the total mass of the resin composition.
  7. 　前記無機物質粒子が炭酸カルシウム粒子を含む、請求項１から６のいずれかに記載のシート。 The sheet according to any one of claims 1 to 6, wherein the inorganic substance particles include calcium carbonate particles.
  8. 　請求項１から７のいずれかに記載のシートにより形成された包装容器。 A packaging container formed by the sheet according to any one of claims 1 to 7.
PCT/JP2017/033000 2016-09-20 2017-09-13 Sheet and packaging container WO2018056136A1 (en)

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JP7251964B2 (en) * 2018-12-19 2023-04-04 藤森工業株式会社 Packaging bag with spout, and manufacturing method thereof
JP7251965B2 (en) * 2018-12-19 2023-04-04 藤森工業株式会社 Packaging bag with spout, and manufacturing method thereof
JP7292047B2 (en) * 2019-02-13 2023-06-16 藤森工業株式会社 Synthetic resin film and packaging bag made of the synthetic resin film
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JPS5169553A (en) * 1974-12-13 1976-06-16 Mitsubishi Petrochemical Co
JPS5896640A (en) * 1981-12-04 1983-06-08 Idemitsu Petrochem Co Ltd Polypropylene-based resin composition and its manufacture
WO2002051930A1 (en) * 2000-12-22 2002-07-04 Samsung General Chemicals Co., Ltd. Polypropylene resin composition having thermal resistance, high rigidity and low warpage properties
JP2004068017A (en) * 2002-07-25 2004-03-04 Yupo Corp Resin oriented film
WO2005005524A1 (en) * 2003-07-14 2005-01-20 Tae Won Jeong Method for fabricating polyethylene composition having glass fiber
JP2006103027A (en) * 2004-10-01 2006-04-20 Honda Motor Co Ltd Laminated sheet
WO2014068699A1 (en) * 2012-10-31 2014-05-08 第一大宮株式会社 Folding container

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JPS5169553A (en) * 1974-12-13 1976-06-16 Mitsubishi Petrochemical Co
JPS5896640A (en) * 1981-12-04 1983-06-08 Idemitsu Petrochem Co Ltd Polypropylene-based resin composition and its manufacture
WO2002051930A1 (en) * 2000-12-22 2002-07-04 Samsung General Chemicals Co., Ltd. Polypropylene resin composition having thermal resistance, high rigidity and low warpage properties
JP2004068017A (en) * 2002-07-25 2004-03-04 Yupo Corp Resin oriented film
WO2005005524A1 (en) * 2003-07-14 2005-01-20 Tae Won Jeong Method for fabricating polyethylene composition having glass fiber
JP2006103027A (en) * 2004-10-01 2006-04-20 Honda Motor Co Ltd Laminated sheet
WO2014068699A1 (en) * 2012-10-31 2014-05-08 第一大宮株式会社 Folding container

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