JP2010013590A - Polyethylene-based resin composition and back sheet of sanitary good using it - Google Patents
Polyethylene-based resin composition and back sheet of sanitary good using it Download PDFInfo
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- 239000011342 resin composition Substances 0.000 title claims abstract description 62
- 229920005678 polyethylene based resin Polymers 0.000 title claims description 15
- 229920005989 resin Polymers 0.000 claims abstract description 85
- 239000011347 resin Substances 0.000 claims abstract description 85
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 51
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 50
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 41
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 31
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- 238000000465 moulding Methods 0.000 claims abstract description 23
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- 239000004698 Polyethylene Substances 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003086 colorant Substances 0.000 description 6
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
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- 238000009835 boiling Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
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- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 206010021639 Incontinence Diseases 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 230000000474 nursing effect Effects 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
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- 239000005083 Zinc sulfide Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
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- 239000002216 antistatic agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- CXUJOBCFZQGUGO-UHFFFAOYSA-F calcium trimagnesium tetracarbonate Chemical compound [Mg++].[Mg++].[Mg++].[Ca++].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O CXUJOBCFZQGUGO-UHFFFAOYSA-F 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229910000515 huntite Inorganic materials 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
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- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- Absorbent Articles And Supports Therefor (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、ポリエチレン系樹脂組成物及びそれを使用する衛生用品のバックシートに関し、詳しくは、シートにおける引張特性と成形性が共に優れ、生理用ナプキンやオムツなどの衛生用品におけるバックシートの材料として有用なポリエチレン系樹脂組成物に係わるものである。 The present invention relates to a polyethylene resin composition and a hygiene article backsheet using the same, and more particularly, as a material for a backsheet in a hygiene article such as a sanitary napkin or a diaper. The present invention relates to a useful polyethylene resin composition.
ポリエチレン系樹脂は、プラスチック材料のなかで、各種の物性や成形汎用性及び経済性や環境問題適応性などに万遍なく優れているので、種々の日用品材料及び産業用資材などとして重用されている。
日用品においては、日常生活における利便性向上や清潔性志向のために、日用品のひとつとして生理用ナプキンや使い捨てオムツなどが多用されるようになり、従来から、ポリエチレン系樹脂が、生理用ナプキンやオムツなどの衛生用品（衛生材料）の原料として汎用されている。
Polyethylene resin is widely used as various daily necessities and industrial materials because it is excellent in various physical properties, molding versatility, economy and adaptability to environmental problems among plastic materials. .
In daily necessities, sanitary napkins and disposable diapers are frequently used as daily necessities in order to improve convenience and cleanliness in daily life. Conventionally, polyethylene resins have been used as sanitary napkins and diapers. It is widely used as a raw material for sanitary products (sanitary materials).
生理用ナプキンや失禁用パッド及びオムツや授乳パッドなどの衛生用品は、経血や尿などの体液を確実に吸収保持して外部に漏洩させないために使用されるので、通常は基本的には、液体透過性のトップシートと液体不透過性のバックシート、及びこれらの両シート間に挟持された液体吸収体と、バックシート面を下着や肌に接着し固定するための粘着剤層とを有している。
このような衛生用品は、剥離性向上の処理がされた包装用フィルムによって、下着や肌に固定するための粘着剤層との接着を介して、個別に包装されているものが主流になっている。消費者が使用する時には、包装用フィルムを粘着剤層から剥離除去し、包装を解いて本体を取り出し、下着の内側や肌に直接に（使用態様によっては、バックシートの端部を折り込んで）貼着して使用する。
Sanitary products such as sanitary napkins, incontinence pads, diapers, and nursing pads are used to ensure that body fluids such as menstrual blood and urine are absorbed and kept from leaking outside. It has a liquid-permeable top sheet, a liquid-impermeable back sheet, a liquid absorber sandwiched between these two sheets, and an adhesive layer for adhering and fixing the back sheet surface to underwear and skin. is doing.
Such hygiene products are mainly packaged individually through the adhesive film for fixing to the underwear and the skin with a packaging film that has been treated to improve peelability. Yes. When used by consumers, the packaging film is peeled off from the adhesive layer, unpacked, taken out of the main body, and directly on the inside of the underwear or on the skin (depending on the usage, the end of the backsheet may be folded) Stick and use.
衛生用品の使用装着時に衛生用品がずれて移動して使用者に不快感を与えないように、また体液を確実に吸収して漏洩しないように、本体と下着などとは確実に粘着している必要があるが、そのために粘着剤の強度を高めると、使用後に下着等から剥離し難くなるという易剥離性の低下が生じ、強く剥離するとバックシートが破れたり、破れないまでも伸びてしまう問題が派生している。 The body and underwear are firmly adhered so that the sanitary product does not move when the sanitary product is worn and moved and does not cause discomfort to the user, and so as not to absorb and leak body fluids. However, if the strength of the pressure-sensitive adhesive is increased for that purpose, it will be difficult to peel off from underwear after use, resulting in a decrease in easy peelability. Is derived.
そこで、機械的強度を高めたバックシート用材料として、バックシート用樹脂組成物において、密度とＭＦＲと引張強さ及び融点と１％モジュラスなどが特定された、直鎖状エチレン・α−オレフィン共重合体１００重量部と気相法低密度エチレン・α−オレフィン共重合体２５〜５５重量部と高圧ラジカル重合長鎖分岐型低密度エチレン２０〜４０重量部及び無機系又は有機系着色剤０．５〜１０重量部とからなるポリエチレン系樹脂組成物が提案されている（特許文献１）。しかしながら、かかる樹脂組成物はシート成形の成形速度を高くでき生産性に優れているとしても依然として強度と成形加工性とのバランスが劣り、この樹脂組成物から成形されたシート材料は、バックシートが破けたり伸ばされずに衛生用品本体を使用後に下着などから剥離する、易剥離性も充分に改善されているとはいえなかった。 Therefore, as a backsheet material with increased mechanical strength, a linear ethylene / α-olefin copolymer in which density, MFR, tensile strength, melting point, 1% modulus, etc. are specified in the backsheet resin composition. 100 parts by weight of polymer, 25 to 55 parts by weight of gas phase low density ethylene / α-olefin copolymer, 20 to 40 parts by weight of high pressure radical polymerization long chain branched low density ethylene, and inorganic or organic colorant A polyethylene-based resin composition composed of 5 to 10 parts by weight has been proposed (Patent Document 1). However, even though such a resin composition can increase the molding speed of sheet molding and is excellent in productivity, the balance between strength and molding processability is still inferior, and the sheet material molded from this resin composition is a back sheet. It could not be said that the easy peelability, which peels from the underwear after use of the sanitary product body without being torn or stretched, has been sufficiently improved.
バックシート用材料として、結晶性プロピレン系樹脂マトリックスとエチレン−α−オレフィン共重合体ゴム分散相との分散構造樹脂組成物（特許文献２）、プロピレン−エチレン共重合体と六員環構造を有すβ晶核剤を含む樹脂組成物（特許文献３）なども知られているが、これらは主として衛生用品の通気性や風合い（柔らかさ）を向上させるものであり、成形加工性及び引張強度や伸び特性が充分良好とはいえず、衛生用品のシートの易剥離性も充分に改善されているとはいえない。 As a backsheet material, it has a dispersion structure resin composition of a crystalline propylene resin matrix and an ethylene-α-olefin copolymer rubber dispersed phase (Patent Document 2), and has a propylene-ethylene copolymer and a six-membered ring structure. Resin compositions containing β-crystal nucleating agents (Patent Document 3) are also known, but these mainly improve the breathability and texture (softness) of sanitary products, and are easy to process and have tensile strength. Further, it cannot be said that the elongation characteristics are sufficiently good, and the easy peelability of the sanitary product sheet is not sufficiently improved.
本発明は、背景技術の段落０００４〜０００６に前述したところの、衛生用品のバックシートにおいて派生している問題とその状況を鑑みて、バックシートにおける、引張強度と伸び特性を向上させて、使用後におけるバックシートの下着等からの易剥離性を高めることができ、併せて成形加工性も改良された、バックシート用材料として有用なポリエチレン系樹脂組成物を開発することを、発明が解決すべき課題とするものである。 In view of the problem and the situation derived from the sanitary article backsheet described above in paragraphs 0004 to 0006 of the background art, the present invention improves the tensile strength and elongation characteristics of the backsheet and uses it. The invention solves the development of a polyethylene-based resin composition useful as a backsheet material, which can improve ease of peeling from the backsheet underwear, etc., and has improved molding processability. It should be a challenge.
本発明者は、上記の発明の課題を解決することを目指して、バックシートにおける、引張強度と伸び特性を向上させて、引張強度を高く保持しつつ使用後におけるバックシートの下着等からの易剥離性を高めることを図り、ポリエチレン系樹脂材料及びその密度やＭＦＲなどの各種の物性、樹脂組成物における樹脂の種類と組み合わせ、更には、衛生用品のバックシートにおける所要の各種物性などについて、考察勘案し試行実証を重ねて、その過程において、ポリエチレン系樹脂組成物の主成分における特定の物性である、引張試験における荷重と伸度の特別の関係物性が、バックシートの易剥離性に深く関与することを見い出すことができ、更に、他の樹脂成分の種類とその配合割合及び各樹脂成分の密度とＭＦＲなどの物性を検案し特定することにより、上記した発明の課題を解決することができる、ポリエチレン系樹脂組成物の新規な本発明を創作するに至った。 The present inventor aims to solve the above-described problems of the invention by improving the tensile strength and elongation characteristics of the backsheet, and easily maintaining the tensile strength high from the underwear of the backsheet after use. In order to enhance the releasability, various physical properties such as polyethylene resin materials and their density and MFR, combinations with the types of resins in the resin composition, and various physical properties required for the back sheet of sanitary goods, etc. In consideration of repeated trials and demonstrations, in the process, the specific physical properties of the main component of the polyethylene resin composition, the special physical properties related to the load and elongation in the tensile test, are deeply related to the easy peelability of the backsheet. In addition, the types and proportions of other resin components, the density of each resin component, and physical properties such as MFR are proposed. By, you can solve the problems of the invention described above, leading to the creation of the novel invention of the polyethylene resin composition.
かくして、本発明は、ポリエチレン系樹脂組成物の主成分として、線状低密度ポリエチレン系樹脂（いわゆるＬＬＤＰＥ）を選択し、その特定の物性である、引張試験における荷重と伸度の特別の関係物性として、引張試験における伸度荷重曲線の微分値（ｄＮ／ｄＳ）を選定してｄＮ／ｄＳの最小値＞０と規定することを構成の主たる要件とするものである。そして、本発明は、主成分の密度も特定し、他成分として、二種の分岐状低密度ポリエチレン系樹脂を選び、それらのＭＦＲをも特定し、更に樹脂組成物の各成分の配合割合を規定する。 Thus, according to the present invention, a linear low density polyethylene resin (so-called LLDPE) is selected as the main component of the polyethylene resin composition, and the specific physical properties thereof are the special physical properties related to the load and elongation in the tensile test. As a main requirement of the configuration, the differential value (dN / dS) of the elongation load curve in the tensile test is selected and the minimum value of dN / dS is defined as> 0. The present invention also specifies the density of the main component, selects two kinds of branched low density polyethylene resins as other components, specifies their MFR, and further specifies the blending ratio of each component of the resin composition. Stipulate.
しかして、本発明における基本発明は、「密度が０．８８０〜０．９３０ｇ/ｃｍ３であり、引張試験における伸度荷重曲線の微分値（ｄＮ／ｄＳ）の最小値が０より大きい線状低密度ポリエチレン系樹脂（Ａ）４０〜８７重量％と、メルトフローレート（ＭＦＲ：ＪＩＳ−Ｋ７２１０に準拠して、１９０℃、２１．１８Ｎ荷重の条件で測定；以下において同じ）が６ｇ／１０分未満の分岐状低密度ポリエチレン系樹脂（Ｂ）１０〜４０重量％と、ＭＦＲが６ｇ／１０分以上の分岐状低密度ポリエチレン系樹脂（Ｃ）３〜２０重量％とを含有することを特徴とするポリエチレン系樹脂組成物。」となり、衛生用品のバックシートなどとして格別に有用な新規なポリエチレン系の樹脂組成物の発明を構成する。
なお、重要なことであるが、この基本発明における主要な構成の要件は、後記する実施例の実験データ及び実施例と比較例の対照により、その合理性と有意性が実証されている。
Therefore, the basic invention in the present invention is “a linear shape in which the density is 0.880 to 0.930 g / cm 3 and the minimum value of the differential value (dN / dS) of the elongation load curve in the tensile test is greater than zero. 40 to 87% by weight of low density polyethylene resin (A) and melt flow rate (MFR: measured under conditions of 190 ° C. and 21.18 N load according to JIS-K7210; the same applies below) 6 g / 10 min Less than 10 to 40% by weight of a branched low density polyethylene resin (B) and 3 to 20% by weight of a branched low density polyethylene resin (C) having an MFR of 6 g / 10 min or more. And constitutes an invention of a novel polyethylene-based resin composition that is particularly useful as a back sheet for sanitary goods.
Importantly, the rationality and significance of the requirements of the main components in this basic invention have been proved by experimental data of examples described later and by comparison of examples and comparative examples.
そして、上記の基本発明における実施の態様としては、後に詳述するとおりに、線状低密度ポリエチレン系樹脂（Ａ）が、メタロセン系触媒により製造されたものであり、ポリエチレン系樹脂組成物が、ＭＦＲは２．０〜５．０ｇ／１０分であり、密度は０．９１８〜０．９２６ｇ／ｃｍ３であり、線状低密度ポリエチレン系樹脂（Ａ）のＭＦＲは０．１〜５０ｇ／１０分であり、分岐状低密度ポリエチレン系樹脂（Ｂ）の密度は０．９１５〜０．９３０ｇ／ｃｍ３であり、分岐状低密度ポリエチレン系樹脂（Ｃ）の密度は０．９１５〜０．９３０ｇ／ｃｍ３であり、分岐状低密度ポリエチレン系樹脂（Ｂ）のＭＦＲと分岐状低密度ポリエチレン系樹脂（Ｃ）のＭＦＲとが、関係式０．１≦ｌｏｇ（ＭＦＲｃ／ＭＦＲｂ）≦１を満たし、更に、ポリエチレン系樹脂組成物を成形したシート（フィルムを含む）により形成される衛生用品用バックシートである、各態様である。 And as an embodiment in the above-mentioned basic invention, as described in detail later, the linear low density polyethylene resin (A) is produced by a metallocene catalyst, and the polyethylene resin composition is The MFR is 2.0 to 5.0 g / 10 min, the density is 0.918 to 0.926 g / cm 3 , and the MFR of the linear low density polyethylene resin (A) is 0.1 to 50 g / 10. The density of the branched low density polyethylene resin (B) is 0.915 to 0.930 g / cm 3 , and the density of the branched low density polyethylene resin (C) is 0.915 to 0.930 g. / cm 3 and a MFR of MFR and branched low-density polyethylene resin branched low-density polyethylene resin (B) (C) is, satisfies the relationship 0.1 ≦ log (MFRc / MFRb) ≦ 1 , Further A backsheet for sanitary articles which are formed by a sheet formed by molding polyethylene resin composition (including films), which are the aspects.
ところで、背景技術の各参考文献及びその他の特許文献を精査しても、段落００１１に前記した本発明の基本発明における特別の構成は些かも窺うことはできない。
そして、本発明は、（ｉ）衛生用品のバックシートにおける、引張強度と伸び特性を向上させて、バックシートが高い粘着力を有していても、使用後におけるバックシートの下着等からの易剥離性を高めることができ、（ｉｉ）併せて成形加工性も改良され、（ｉｉｉ）バックシート用材料として特に有用なポリエチレン系樹脂組成物であり、格別の特徴（作用効果と用途）を奏するものである。これらの特徴は、後記する実施例の実験データ及び実施例と比較例の対照により、実証されている。
By the way, even if each reference document of the background art and other patent documents are scrutinized, the special configuration in the basic invention of the present invention described in paragraph 0011 cannot be obtained.
And this invention improves (i) the tensile strength and the elongation characteristic in the back sheet of sanitary goods, and even if the back sheet has a high adhesive strength, it is easy from the underwear of the back sheet after use. Peelability can be enhanced, (ii) molding processability is also improved, and (iii) a polyethylene-based resin composition particularly useful as a backsheet material, which exhibits exceptional characteristics (effects and uses). Is. These characteristics are demonstrated by the experimental data of the Example mentioned later and the comparison of an Example and a comparative example.
以上において、本発明の創作の経緯と、発明の構成と特徴などについて概括的に記述したので、ここで、本発明の全体を俯瞰するために、本発明全体の構成を明確に記載すると、本発明は次の発明単位群から成るものであって、［１］に記載のものが基本発明であり、［２］以下の各発明は基本発明の実施の態様に係るものである。（なお、本発明群全体をまとめて「本発明」と称している。） In the above, the background of the creation of the present invention, the configuration and features of the invention, etc. have been described generally. Here, in order to give an overview of the entire present invention, the overall configuration of the present invention is described clearly. The invention is composed of the following invention unit groups, the one described in [1] is a basic invention, and [2] each invention below relates to an embodiment of the basic invention. (The present invention group as a whole is collectively referred to as “the present invention”.)
［１］ 密度が０．８８０〜０．９３０ｇ/ｃｍ３であり、引張試験における伸度荷重曲線の微分値（ｄＮ／ｄＳ）の最小値が０より大きい線状低密度ポリエチレン系樹脂（Ａ）４０〜８７重量％と、メルトフローレート（ＭＦＲ：１９０℃・２１．１８Ｎ荷重の条件）が６ｇ／１０分未満の分岐状低密度ポリエチレン系樹脂（Ｂ）１０〜４０重量％と、ＭＦＲが６ｇ／１０分以上の分岐状低密度ポリエチレン系樹脂（Ｃ）３〜２０重量％とを含有することを特徴とするポリエチレン系樹脂組成物。 [1] A linear low density polyethylene resin (A) having a density of 0.880 to 0.930 g / cm 3 and having a minimum differential value (dN / dS) of an elongation load curve in a tensile test greater than 0. 10 to 40% by weight of a branched low density polyethylene resin (B) having a melt flow rate (MFR: condition of 190 ° C. and 21.18 N load) of less than 6 g / 10 minutes, and an MFR of 6 g. A polyethylene-based resin composition containing 3 to 20% by weight of a branched low-density polyethylene-based resin (C) for 10 minutes or more.
［２］衛生用品のバックシート用材料に使用されることを特徴とする、［１］におけるポリエチレン系樹脂組成物。
［３］ 線状低密度ポリエチレン系樹脂（Ａ）が、メタロセン系触媒により製造されたものであることを特徴とする、［１］又は［２］におけるポリエチレン系樹脂組成物。
［４］ポリエチレン系樹脂組成物が、ＭＦＲは２．０〜５．０ｇ／１０分であり、密度は０．９１８〜０．９２６ｇ／ｃｍ３であることを特徴とする、［１］〜［３］のいずれかにおけるポリエチレン系樹脂組成物。
［５］線状低密度ポリエチレン系樹脂（Ａ）のＭＦＲは０．１〜５０ｇ／１０分であり、分岐状低密度ポリエチレン系樹脂（Ｂ）の密度は０．９１５〜０．９３０ｇ／ｃｍ３であり、分岐状低密度ポリエチレン系樹脂（Ｃ）の密度は０．９１５〜０．９３０ｇ／ｃｍ３であることを特徴とする、［１］〜［４］のいずれかにおけるポリエチレン系樹脂組成物。
［６］分岐状低密度ポリエチレン系樹脂（Ｂ）のＭＦＲと分岐状低密度ポリエチレン系樹脂（Ｃ）のＭＦＲとが、次の関係式を満たしていることを特徴とする、［１］〜［５］のいずれかにおけるポリエチレン系樹脂組成物。
０．１≦ｌｏｇ（ＭＦＲｃ／ＭＦＲｂ）≦１
［７］［１］〜［６］のいずれかにおけるポリエチレン系樹脂組成物を成形したシートにより形成される、衛生用品のバックシート。
[2] The polyethylene resin composition according to [1], which is used as a material for a back sheet of a sanitary product.
[3] The polyethylene resin composition according to [1] or [2], wherein the linear low density polyethylene resin (A) is produced by a metallocene catalyst.
[4] The polyethylene resin composition has an MFR of 2.0 to 5.0 g / 10 min and a density of 0.918 to 0.926 g / cm 3 . 3]. The polyethylene resin composition according to any one of [3].
[5] The linear low density polyethylene resin (A) has an MFR of 0.1 to 50 g / 10 min, and the branched low density polyethylene resin (B) has a density of 0.915 to 0.930 g / cm 3. The polyethylene-based resin composition according to any one of [1] to [4], wherein the density of the branched low-density polyethylene resin (C) is 0.915 to 0.930 g / cm 3 . .
[6] The MFR of the branched low density polyethylene resin (B) and the MFR of the branched low density polyethylene resin (C) satisfy the following relational expressions: [1] to [1] 5]. The polyethylene resin composition according to any one of [5].
0.1 ≦ log (MFRc / MFRb) ≦ 1
[7] A sanitary article backsheet formed by a sheet obtained by molding the polyethylene resin composition according to any one of [1] to [6].
本発明は、（ｉ）衛生用品のバックシートにおける、引張強度と伸び特性を向上させて、バックシートが高い粘着力を有していても、使用後におけるバックシートの下着等からの易剥離性を高めることができ、（ｉｉ）併せて成形加工性も改良され、（ｉｉｉ）バックシート用材料として特に有用なポリエチレン系樹脂組成物である。 The present invention (i) improves the tensile strength and elongation characteristics of a sanitary article backsheet, and even if the backsheet has a high adhesive strength, it is easily peelable from the backsheet underwear after use. (Ii) is a polyethylene-based resin composition that is particularly useful as a backsheet material.
以下においては、本発明における発明群を詳細に説明するために、発明の実施の形態を具体的に詳しく説明する。 In the following, in order to describe the invention group in the present invention in detail, embodiments of the invention will be described in detail.
１．本発明のポリエチレン系樹脂組成物の基本構成について
密度が０．８８０〜０．９３０ｇ/ｃｍ３であり、引張試験における伸度荷重曲線の微分値（ｄＮ／ｄＳ）の最小値が０より大きい線状低密度ポリエチレン系樹脂（Ａ）４０〜８７重量％と、ＭＦＲが６ｇ／１０分未満の分岐状低密度ポリエチレン系樹脂（Ｂ）１０〜４０重量％と、ＭＦＲが６ｇ／１０分以上の分岐状低密度ポリエチレン系樹脂３〜２０重量％とを含有することを特徴とするポリエチレン系樹脂組成物である。
1. Basic structure of the polyethylene-based resin composition of the present invention A line having a density of 0.880 to 0.930 g / cm 3 and a minimum value of the differential value (dN / dS) of the elongation load curve in the tensile test is greater than zero. Branched low density polyethylene resin (A) 40-87% by weight, branched low density polyethylene resin (B) 10-40% by weight with an MFR of less than 6 g / 10 min, and MFR 6 g / 10 min or more. It is a polyethylene-type resin composition characterized by containing 3-20 weight% of a low-density polyethylene-type resin.
２．線状低密度ポリエチレン系樹脂（Ａ）成分について
（１）線状低密度ポリエチレン系樹脂（Ａ）
本発明に係る線状低密度ポリエチレン系樹脂（ＬＬＤＰＥ）とは、エチレンと炭素数３〜２０のα−オレフィンより選ばれる一種以上のα−オレフィンとの共重合体である。
この炭素数３〜２０のα−オレフィンとしては、好ましくは炭素数３〜１２のものであり、具体的にはプロピレン、１−ブテン、１−ペンテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、１−ドデセンなどが挙げられる。また、これらのα−オレフィンの含有量は、合計で通常３０モル％以下、好ましくは１〜２０モル％の範囲で選択される。
2. About linear low density polyethylene resin (A) component (1) Linear low density polyethylene resin (A)
The linear low density polyethylene resin (LLDPE) according to the present invention is a copolymer of ethylene and one or more α-olefins selected from α-olefins having 3 to 20 carbon atoms.
The α-olefin having 3 to 20 carbon atoms is preferably one having 3 to 12 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene. 1-octene, 1-decene, 1-dodecene and the like. Further, the content of these α-olefins is selected in the range of usually 30 mol% or less, preferably 1 to 20 mol% in total.
（２）線状ポリエチレン系樹脂（Ａ）の密度とＭＦＲ
線状低密度ポリエチレン系樹脂（Ａ）の密度は、０．８８０〜０．９３０ｇ／ｃｍ３、好ましくは０．８９５〜０．９２５ｇ／ｃｍ３、より好ましくは０．９１０〜０．９２０ｇ／ｃｍ３である。密度が０．８８０ｇ／ｃｍ３未満では、当組成物によるシートの腰が弱くて取り扱い難く、０．９３０ｇ／ｃｍ３を超えると、引張降伏点後にネッキングが発生することから易剥離性が劣る。なお、密度の値は、ＪＩＳ−Ｋ７１１２に準拠して測定した値である。
(2) Density and MFR of linear polyethylene resin (A)
The density of the linear low density polyethylene resin (A) is 0.880 to 0.930 g / cm 3 , preferably 0.895 to 0.925 g / cm 3 , more preferably 0.910 to 0.920 g / cm 3 . 3 . If the density is less than 0.880 g / cm 3 , the sheet of the composition is weak and difficult to handle, and if it exceeds 0.930 g / cm 3 , necking occurs after the tensile yield point, resulting in poor easy peelability. The density value is a value measured in accordance with JIS-K7112.
線状低密度ポリエチレン系樹脂（Ａ）のＭＦＲは、特に限定されないが、好ましくは０．１〜５０ｇ／１０分、より好ましくは０．３〜３０ｇ／１０分、更に好ましくは０．５〜２０ｇ／１０分、特に好ましくは１．５〜１０ｇ／１０分である。ＭＦＲが０．１ｇ／１０分未満では、成形加工性が劣る場合があり、５０ｇ／１０分を超えると機械的強度などが低下する惧れが生じる。 The MFR of the linear low density polyethylene resin (A) is not particularly limited, but is preferably 0.1 to 50 g / 10 minutes, more preferably 0.3 to 30 g / 10 minutes, and still more preferably 0.5 to 20 g. / 10 minutes, particularly preferably 1.5 to 10 g / 10 minutes. If the MFR is less than 0.1 g / 10 min, the moldability may be inferior, and if it exceeds 50 g / 10 min, the mechanical strength and the like may be reduced.
（３）引張試験における伸度荷重曲線の特性
線状低密度ポリエチレン系樹脂（Ａ）は、引張試験における伸度荷重曲線の微分値（ｄＮ／ｄＳ）の最小値が０より大きく、好ましくは０．００１より大きく、より好ましくは０．００２より大きいと規定される。微分値（ｄＮ／ｄＳ）の最小値が０以下となると、易剥離性が低下する。
ここで、本発明における易剥離性とは、具体的には、例えば、使用後における衛生用品のバックシートを下着等から剥離する易剥離性であり、より具体的には、粘着剤層が設けられたバックシートが破けたり伸ばされずに衛生用品本体を下着等の被貼着物から剥離する、易剥離性を意味する。
(3) Properties of elongation load curve in tensile test The linear low-density polyethylene resin (A) has a minimum value of the differential value (dN / dS) of the elongation load curve in the tensile test, preferably 0. Greater than 0.001, more preferably greater than 0.002. When the minimum value of the differential value (dN / dS) is 0 or less, easy peelability is reduced.
Here, the easy releasability in the present invention is specifically, for example, easy releasability to peel a back sheet of a sanitary article after use from underwear, and more specifically, an adhesive layer is provided. This means that the hygienic article body is peeled off from an adherend such as underwear without the back sheet being broken or stretched.
バックシートの引張試験における荷重と伸度の特別の関係物性が、バックシートの易剥離性に深く関与するのであって、具体的には、上記のとおり、引張試験による伸度荷重曲線における特性としての微分値（ｄＮ／ｄＳ）が、関与することになる。
ここで引張試験における伸度荷重曲線の微分値（ｄＮ／ｄＳ）は、実施例の段落００４３に記載した手順で求めることができ、具体的には任意の荷重量において、一定量伸びた時（例えば５％伸びた時）の荷重の変化量が０より大きいかを求める。
The special relationship between the load and the elongation in the tensile test of the backsheet is deeply related to the easy peelability of the backsheet. Specifically, as described above, as a characteristic in the elongation load curve by the tensile test The differential value of (dN / dS) will be involved.
Here, the differential value (dN / dS) of the elongation load curve in the tensile test can be obtained by the procedure described in paragraph 0043 of the example. Specifically, when a certain amount of elongation is obtained at an arbitrary load amount ( For example, it is determined whether or not the amount of change in load is greater than 0 when the elongation is 5%.
後記する実施例１と比較例１においての、引張試験における伸度荷重曲線の具体例が図１のグラフ図に例示され、引張試験における伸度に対する特性値としての微分値（ｄＮ／ｄＳ）の変化の具体例が図２のグラフ図に例示されている。 図２のグラフ図において明らかにされているとおりに、本発明の実施例１では、伸度（％）の全領域において微分値はｄＮ／ｄＳ＞０であるが、比較例１では伸度（％）が１００％以下の領域において微分値はｄＮ／ｄＳ＜０となっている。
そして、上記のとおり、伸度荷重曲線の微分値（ｄＮ／ｄＳ）の最小値が０より大きいと、易剥離性が高くなり、微分値（ｄＮ／ｄＳ）の最小値が０以下となると、易剥離性が低下する。
A specific example of the elongation load curve in the tensile test in Example 1 and Comparative Example 1 to be described later is illustrated in the graph of FIG. 1, and the differential value (dN / dS) as a characteristic value with respect to the elongation in the tensile test is illustrated. A specific example of the change is illustrated in the graph of FIG. As clearly shown in the graph of FIG. 2, in Example 1 of the present invention, the differential value is dN / dS> 0 in the whole area of elongation (%), whereas in Comparative Example 1, the elongation ( %) Is 100% or less, the differential value is dN / dS <0.
And as mentioned above, when the minimum value of the differential value (dN / dS) of the elongation load curve is larger than 0, the easy peelability increases, and when the minimum value of the differential value (dN / dS) becomes 0 or less, Easy peelability decreases.
（４）線状低密度ポリエチレン系樹脂（Ａ）の製造
本発明で使用される線状低密度ポリエチレン系樹脂（Ａ）は、重合用触媒の存在下に、エチレンとα−オレフィンとを共重合されることにより得ることができる。ここで重合用触媒には制限はないが、生成重合体における組成分布と分子量分布が狭く、高強度の成形品が得られ易いメタロセン系触媒により製造されたものであることが好ましい。また、上記特性を損なわない範囲でコスト低減化のためにチーグラー系触媒などのメタロセン系触媒以外の触媒で得られた線状低密度ポリエチレン系樹脂をブレンドして使用してもよい。
メタロセン触媒とは、通常に知られているメタロセン−アルモキサン触媒、又はメタロセン化合物と反応して安定なアニオンとなる化合物などからなる触媒である。
本発明に係る線状低密度ポリエチレン系樹脂においては、その製造方法に制限はなく、スラリー重合や気相重合及び溶液重合などの方法により行うことができる。
(4) Production of Linear Low Density Polyethylene Resin (A) The linear low density polyethylene resin (A) used in the present invention is a copolymer of ethylene and α-olefin in the presence of a polymerization catalyst. Can be obtained. Although there is no restriction | limiting in this case for a polymerization catalyst, It is preferable that it is what was manufactured with the metallocene catalyst which has a narrow composition distribution and molecular weight distribution in a production | generation polymer, and is easy to obtain a high intensity | strength molded article. In addition, a linear low density polyethylene resin obtained with a catalyst other than a metallocene catalyst such as a Ziegler catalyst may be blended and used for cost reduction within a range not impairing the above characteristics.
The metallocene catalyst is a catalyst composed of a conventionally known metallocene-alumoxane catalyst or a compound that reacts with a metallocene compound to become a stable anion.
The linear low density polyethylene resin according to the present invention is not limited in its production method, and can be carried out by methods such as slurry polymerization, gas phase polymerization and solution polymerization.
３．分岐状低密度ポリエチレン系樹脂成分について
（１）分岐状低密度ポリエチレン系樹脂（Ｂ）
本発明に係る分岐状低密度ポリエチレン系樹脂（Ｂ）は、長鎖分岐を有するポリエチレン系樹脂であり、例えばエチレンを高圧ラジカル重合法で重合することによって得られるポリエチレンである。高圧ラジカル重合法によって得られるポリエチレンは、高圧法低密度ポリエチレン（いわゆるＨＰ−ＬＤＰＥ）とも呼称される。分岐状低密度ポリエチレン系樹脂（Ｂ）は、エチレンとα−オレフィンとの共重合体でもよい。
分岐状低密度ポリエチレン系樹脂は、製造方法が限定されるものではなく、公知の製造方法が採用でき、例えば、チューブラープロセスやオートクレーブプロセスなどが挙げられる。なお、ＭＦＲ値の調整は、重合温度を変化させることにより行うことが可能である。
3. Branched low density polyethylene resin component (1) Branched low density polyethylene resin (B)
The branched low-density polyethylene-based resin (B) according to the present invention is a polyethylene-based resin having a long chain branch, and is, for example, polyethylene obtained by polymerizing ethylene by a high-pressure radical polymerization method. The polyethylene obtained by the high pressure radical polymerization method is also referred to as a high pressure method low density polyethylene (so-called HP-LDPE). The branched low density polyethylene resin (B) may be a copolymer of ethylene and an α-olefin.
The production method of the branched low-density polyethylene resin is not limited, and a known production method can be adopted, and examples thereof include a tubular process and an autoclave process. The MFR value can be adjusted by changing the polymerization temperature.
分岐状低密度ポリエチレン系樹脂（Ｂ）は、ＭＦＲが６ｇ／１０分未満、好ましくは０．５〜５ｇ／１０分、より好ましくは１．５〜４ｇ／１０分である。ＭＦＲが６ｇ／１０分以上であると、本発明のポリエチレン系樹脂組成物によるシートの腰が不足する。
密度は、特に限定されないが、好ましくは０．９１５〜０．９３０ｇ／ｃｍ３、より好ましくは０．９１８〜０．９３０ｇ／ｃｍ３である。この範囲であれば、本発明のポリエチレン系樹脂組成物において、引張伸びに対する荷重の増加が大きく、シートの腰が有ることから取り扱い易いシートとなる。
The branched low density polyethylene resin (B) has an MFR of less than 6 g / 10 minutes, preferably 0.5 to 5 g / 10 minutes, more preferably 1.5 to 4 g / 10 minutes. If the MFR is 6 g / 10 min or more, the sheet of the polyethylene resin composition of the present invention is insufficient.
Although a density is not specifically limited, Preferably it is 0.915-0.930 g / cm < 3 >, More preferably, it is 0.918-0.930 g / cm < 3 >. If it is this range, in the polyethylene-type resin composition of this invention, the increase of the load with respect to tensile elongation will be large, and since it has the seat | waist of a sheet | seat, it will become a sheet | seat which is easy to handle.
（２）分岐状低密度ポリエチレン系樹脂（Ｃ）
本発明に係る分岐状低密度ポリエチレン系樹脂（Ｃ）の製造は、段落００２７に記載された、分岐状低密度ポリエチレン系樹脂（Ｂ）の製造と同様に行われる。また、分岐状低密度ポリエチレン系樹脂（Ｃ）は、エチレンとα−オレフィンとの共重合体でもよい。
分岐状低密度ポリエチレン系樹脂（Ｃ）は、ＭＦＲが６ｇ／１０分以上、好ましくは７〜２０ｇ／１０分、より好ましくは８〜１５ｇ／１０分である。ＭＦＲが６ｇ／１０分未満であると、本発明のポリエチレン系樹脂組成物の加工性が不足する。
密度は、特に限定されないが、好ましくは０．９１５〜０．９３０ｇ／ｃｍ３、より好ましくは０．９１８〜０．９３０ｇ／ｃｍ３である。この範囲であれば、本発明のポリエチレン系樹脂組成物において、引張伸びに対する荷重の増加が大きく、シートの腰が有ることから取り扱い易いシートとなる。
(2) Branched low density polyethylene resin (C)
Production of the branched low density polyethylene resin (C) according to the present invention is carried out in the same manner as the production of the branched low density polyethylene resin (B) described in paragraph 0027. The branched low-density polyethylene resin (C) may be a copolymer of ethylene and α-olefin.
The branched low density polyethylene resin (C) has an MFR of 6 g / 10 min or more, preferably 7 to 20 g / 10 min, more preferably 8 to 15 g / 10 min. When the MFR is less than 6 g / 10 minutes, the processability of the polyethylene resin composition of the present invention is insufficient.
The density is not particularly limited, but is preferably 0.915 to 0.930 g / cm 3 , more preferably 0.918 to 0.930 g / cm 3 . If it is this range, in the polyethylene-type resin composition of this invention, the increase of the load with respect to tensile elongation will be large, and since it has the seat | waist of a sheet | seat, it will become a sheet | seat which is easy to handle.
ここで、本発明に係る分岐状低密度ポリエチレン系樹脂（Ｂ）のＭＦＲ（ＭＦＲｂ）と本発明に係る分岐状低密度ポリエチレン系樹脂（Ｃ）のＭＦＲ（ＭＦＲｃ）とは次の関係式を満たしていることが好ましい。
０．１≦ｌｏｇ（ＭＦＲｃ／ＭＦＲｂ）≦１
この関係式を満たすことにより、ポリエチレン系樹脂組成物における加工性とシートの腰が良好であるのみならず、ムラの発生がなく、シート表面の外観が優れるといった利点がある。
Here, the MFR (MFRb) of the branched low density polyethylene resin (B) according to the present invention and the MFR (MFRc) of the branched low density polyethylene resin (C) according to the present invention satisfy the following relational expression. It is preferable.
0.1 ≦ log (MFRc / MFRb) ≦ 1
By satisfying this relational expression, there are advantages that not only the processability and the waist of the sheet are good in the polyethylene resin composition, but also the occurrence of unevenness and the appearance of the sheet surface are excellent.
４．本発明のポリエチレン系樹脂組成物について
（１）組成物の組成割合
本発明のポリエチレン系樹脂組成物における組成割合は、線状低密度ポリエチレン系樹脂（Ａ）成分は４０〜８７重量％、好ましくは４４〜８０重量％、より好ましくは５０〜７０重量％であり、分岐状低密度ポリエチレン系樹脂（Ｂ）成分は１０〜４０重量％、好ましくは１５〜３８重量％、より好ましくは２０〜３５重量％であり、分岐状低密度ポリエチレン系樹脂（Ｃ）成分は３〜２０重量％、好ましくは５〜１８重量％、より好ましくは１０〜１５重量％である。
4). About the polyethylene resin composition of the present invention (1) Composition ratio of the composition The composition ratio of the polyethylene resin composition of the present invention is 40 to 87% by weight of the linear low density polyethylene resin (A) component, preferably 44 to 80% by weight, more preferably 50 to 70% by weight, and the branched low density polyethylene resin (B) component is 10 to 40% by weight, preferably 15 to 38% by weight, more preferably 20 to 35% by weight. The branched low density polyethylene resin (C) component is 3 to 20% by weight, preferably 5 to 18% by weight, and more preferably 10 to 15% by weight.
線状低密度ポリエチレン系樹脂（Ａ）成分が多過ぎると、引張伸びに対する荷重の増加が小さい取り扱い難いシートとなり、少な過ぎるとシートが伸びずに破断し易い。分岐状低密度ポリエチレン系樹脂（Ｂ）成分が多過ぎるとシート成形時の樹脂圧力が高くなって成形し難くなり、少な過ぎると引張伸びに対する荷重の増加が小さい取り扱い難いシートとなる。分岐状低密度ポリエチレン系樹脂（Ｃ）成分が多過ぎると引張伸びに対する荷重の増加が小さい取り扱い難いシートとなり、少な過ぎるとシート成形時の樹脂圧力が高くなり成形し難くなる。 When the amount of the linear low density polyethylene resin (A) component is too large, the increase in the load with respect to the tensile elongation is small and the sheet is difficult to handle. When the amount is too small, the sheet is not stretched and easily breaks. When there are too many branched low density polyethylene-type resin (B) components, the resin pressure at the time of sheet | seat shaping | molding will become high, and it will become difficult to shape | mold, and when too small, it will become a sheet which is difficult to handle with a small increase in load with respect to tensile elongation. When there are too many branched low density polyethylene-type resin (C) components, it will become a difficult-to-handle sheet | seat with a small increase in the load with respect to tensile elongation, and when too small, the resin pressure at the time of sheet shaping | molding will become high, and it will become difficult to shape | mold.
（２）組成物の密度とＭＦＲ
本発明のポリエチレン系樹脂組成物においては、特に限定されないが、密度は好ましくは０．９１８〜０．９２６ｇ／ｃｍ３、より好ましくは０．９１９〜０．９２５ｇ／ｃｍ３であり、ＭＦＲは好ましくは２．０〜５．０ｇ／１０分、より好ましくは３．０〜４．０ｇ／１０分である。
(2) Composition density and MFR
In the polyethylene resin composition of the present invention, although not particularly limited, the density is preferably 0.918 to 0.926 g / cm 3 , more preferably 0.919 to 0.925 g / cm 3 , and MFR is preferably Is 2.0 to 5.0 g / 10 min, more preferably 3.0 to 4.0 g / 10 min.
５．組成物におけるその他の成分
（１）着色剤
本発明のポリエチレン樹脂組成物には、着色剤を配合することができる。着色剤としては、酸化チタン、硫酸バリウム、硫酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、タルク、シリカ、アルミナ、リトポン、酸化亜鉛、硫化亜鉛、炭酸鉛、酸化アンチモン、ゼオライト、クリストバライト、ハンタイト、マグネサイト、水酸化アルミニウム、水酸化マグネシウム、白色顔料、白色染料、その他の色の顔料や染料などが挙げられ、特に白色系の酸化チタンが望ましい。
着色剤はバックシートの透明性をなくし、オムツなどの衛生用品の内部を見えなくするもので、ポリエチレン系樹脂組成物１００重量部に対して０．５〜１０重量部を配合することが好ましい。
5). Other components in composition (1) Colorant A colorant can be blended in the polyethylene resin composition of the present invention. Colorants include titanium oxide, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, silica, alumina, lithopone, zinc oxide, zinc sulfide, lead carbonate, antimony oxide, zeolite, cristobalite, huntite, magnesite, water Examples thereof include aluminum oxide, magnesium hydroxide, white pigment, white dye, and other color pigments and dyes. White titanium oxide is particularly desirable.
The colorant eliminates the transparency of the back sheet and makes the inside of sanitary goods such as diapers invisible, and it is preferable to blend 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyethylene resin composition.
（２）添加剤
本発明のポリエチレン系樹脂組成物には、本発明の効果を損なわない範囲で、物性をより高め或いは他の物性を付与するために、ポリエチレン系樹脂において通常に使用される各種の添加剤を配合してもよい。
各種の添加剤としては、酸化防止剤、耐候性改良剤、熱安定剤、光安定剤、紫外線吸収剤、中和剤、滑剤、防曇剤、アンチブロッキング剤、粘着付与剤、帯電防止剤、スリップ剤、核剤、発泡剤、難燃剤、架橋剤、抗菌剤、有機充填剤、無機充填剤、香料、加工助剤などが挙げられる。
(2) Additives The polyethylene resin composition of the present invention can be variously used in polyethylene resins in order to further enhance the physical properties or impart other physical properties within the range not impairing the effects of the present invention. These additives may be blended.
Various additives include antioxidants, weather resistance improvers, heat stabilizers, light stabilizers, UV absorbers, neutralizers, lubricants, antifogging agents, antiblocking agents, tackifiers, antistatic agents, Examples include slip agents, nucleating agents, foaming agents, flame retardants, crosslinking agents, antibacterial agents, organic fillers, inorganic fillers, fragrances, and processing aids.
（３）他の樹脂成分
本発明のポリエチレン系樹脂組成物には、本発明の効果を損なわない範囲で、他の樹脂成分を、それらの性能を部分的に付加するために、任意に配合することができる。
他の樹脂成分としては、例えば、高密度ポリエチレン、エチレン・α−オレフィン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸エステル共重合体、アイオノマー、ポリプロピレン、エチレン系エラストマー、スチレン系エラストマーなどが挙げられる。
(3) Other resin components In the polyethylene-based resin composition of the present invention, other resin components are optionally blended in order to partially add those performances within the range that does not impair the effects of the present invention. be able to.
Examples of other resin components include high-density polyethylene, ethylene / α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ionomer, polypropylene, ethylene-based elastomer, and styrene-based elastomer. Etc.
６．本発明のポリエチレン系樹脂組成物及びそれを使用するシートの各製造
（１）ポリエチレン系樹脂組成物の製造
本発明のポリエチレン系樹脂組成物は、線状低密度ポリエチレン系樹脂（Ａ）成分及び分岐状低密度ポリエチレン系樹脂（Ｂ）成分と分岐状低密度ポリエチレン系樹脂（Ｃ）成分とを、必要に応じて他の成分の着色剤や他の樹脂成分或いは添加剤などを付与して、混合することにより製造される。
混合方法には特に制限はなく、通常のヘンシェルミキサー、スーパーミキサー、タンブラー型などの公知の混合機を用いて混合する。その後、通常の一軸或いは二軸スクリュー押出機や連続混練機などによって混練し、ペレット化してもよい。
6). Production of polyethylene resin composition of the present invention and sheet using the same (1) Production of polyethylene resin composition The polyethylene resin composition of the present invention comprises a linear low density polyethylene resin (A) component and a branch. The low-density polyethylene-based resin (B) component and the branched low-density polyethylene-based resin (C) component are mixed with other components as necessary, such as colorants, other resin components or additives. It is manufactured by doing.
The mixing method is not particularly limited, and mixing is performed using a known mixer such as a normal Henschel mixer, a super mixer, or a tumbler type. Thereafter, the mixture may be kneaded and pelletized by a normal uniaxial or biaxial screw extruder or a continuous kneader.
（２）ポリエチレン系樹脂組成物によるシートの製造
本発明のポリエチレン系樹脂組成物を用いて、インフレーション成形やＴダイ成形などの公知の成形方法により、厚さ１０〜５０μｍのシートを製造し、衛生用品のバックシートとすることができる。
(2) Production of Sheet Using Polyethylene Resin Composition Using the polyethylene resin composition of the present invention, a sheet having a thickness of 10 to 50 μm is produced by a known molding method such as inflation molding or T-die molding. It can be used as a back sheet for supplies.
７．本発明のポリエチレン系樹脂組成物の用途
本発明のポリエチレン系樹脂組成物は成形加工性に優れているので、フィルムやシートの製造に適している。
特に、本発明のポリエチレン系樹脂組成物によるシートは、引張強度と伸び特性を向上させて、使用後におけるバックシートの下着等からの易剥離性を高くされているので、生理用ナプキンや失禁用パッド及びオムツや授乳パッドなどの衛生用品におけるバックシートとして好適に用いることができる。
7). Use of the polyethylene resin composition of the present invention The polyethylene resin composition of the present invention is excellent in molding processability, and is therefore suitable for the production of films and sheets.
In particular, the sheet made of the polyethylene-based resin composition of the present invention has improved tensile strength and elongation characteristics, and is easily peelable from the underwear of the back sheet after use, so that it can be used for sanitary napkins and incontinence. It can be suitably used as a back sheet in sanitary products such as pads and diapers and nursing pads.
以下においては、本発明について更に具体的に説明するために実施例を示し、更に比較例との対照を掲示して、本発明における構成の要件の合理性と有意性及び従来技術に対する卓越性を明らかにする。 In the following, examples will be shown in order to explain the present invention more specifically, and contrasts with comparative examples will be posted to show the rationality and significance of the requirements of the constitution in the present invention and the superiority over the prior art. To clarify.
［各種の物性の測定］
（１）メルトフローレート（ＭＦＲ）
ＪＩＳ−Ｋ７２１０に準拠して、１９０℃・２１．１８Ｎ荷重の条件で測定した。
[Measurement of various physical properties]
(1) Melt flow rate (MFR)
Based on JIS-K7210, it measured on the conditions of 190 degreeC and 21.18N load.
（２）密度
ペレットを熱プレスして２ｍｍ厚のプレスシートを作成し、該シートを１０００ｍｌ容量のビーカーに入れ蒸留水を満たし、時計皿で蓋をしてマントルヒーターで加熱した。蒸留水が沸騰してから６０分間煮沸後、ビーカーを木製台の上に置き放冷した。この時６０分煮沸後の沸騰蒸留水は５００ｍｌとし室温になるまでの時間は６０分以下にならないように調整した。また、試験シートはビーカー及び水面に接しないように水中のほぼ中央部に浸漬した。
シートを２３℃・湿度５０％の条件で１６時間以上２４時間以内でアニーリングを行った後、縦横２ｍｍになるように打ち抜き、試験温度２３℃でＪＩＳ−Ｋ７１１２に準拠して測定した。
(2) Density The pellets were hot-pressed to prepare a press sheet having a thickness of 2 mm. The sheet was placed in a beaker having a capacity of 1000 ml, filled with distilled water, covered with a watch glass, and heated with a mantle heater. After boiling boiling water for 60 minutes, the beaker was placed on a wooden table and allowed to cool. At this time, the boiling distilled water after boiling for 60 minutes was adjusted to 500 ml so that the time until reaching room temperature was not less than 60 minutes. Moreover, the test sheet was immersed in the substantially central part of the water so as not to contact the beaker and the water surface.
The sheet was annealed at a temperature of 23 ° C. and a humidity of 50% for 16 hours or more and within 24 hours, then punched out to 2 mm in length and width, and measured at a test temperature of 23 ° C. according to JIS-K7112.
（３）引張試験
幅６００ｍｍ・リップ幅０．８ｍｍのＴダイを備えた４０／６５／４０ｍｍφＴダイフィルム成形装置により、成形温度を２４０℃・キャストロール速度１００ｍ／ｍｉｎで坪量２３．５ｇ／ｍ２となるように成形したシートから幅２５ｍｍの縦方向の試験片を切り出し、２００ｍｍ／分の引張速度で試験を行い、降伏点荷重、破断点荷重、破断点伸度を求めた。標線間距離は５０ｍｍとした。更に微分値の算出については、伸度と荷重のデータを伸度０から破断まで（但し５００％を上限とする）伸度１％毎に計測し、前後各二点（計五点）のデータから表計算ソフト（エクセル）のＳＬＯＰＥ関数機能を用いて伸度１％毎の微分値とした。
(3) Tensile test Using a 40/65/40 mmφ T die film molding apparatus equipped with a T die with a width of 600 mm and a lip width of 0.8 mm, the molding temperature is 240 ° C., the cast roll speed is 100 m / min, and the basis weight is 23.5 g / m. A test piece in the longitudinal direction having a width of 25 mm was cut out from the sheet formed so as to be 2, and tested at a tensile speed of 200 mm / min to obtain a yield point load, a breaking point load, and a breaking point elongation. The distance between the marked lines was 50 mm. Furthermore, regarding the calculation of the differential value, the elongation and load data are measured from
（４）シート成形時の樹脂圧力
幅６００ｍｍ・リップ幅０．８ｍｍのＴダイを備えた４０／６５／４０ｍｍφＴダイフィルム成形装置により、成形温度を２４０℃・キャストロール速度１００ｍ／ｍｉｎで坪量２３．５ｇ／ｍ２のシートを成形する際の樹脂圧力を測定した。樹脂圧力が低いほど加工性が優れる。
(4) Resin pressure at the time of sheet molding A 40/65/40 mmφ T die film molding apparatus equipped with a T-die having a width of 600 mm and a lip width of 0.8 mm has a basis weight of 23 at a molding temperature of 240 ° C. and a cast roll speed of 100 m / min. The resin pressure when molding a sheet of 0.5 g / m 2 was measured. The lower the resin pressure, the better the processability.
（５）易剥離性
１５０×２００ｍｍに切り出したシートの片面にアクリル系粘着剤を塗工した。塗工面に１５０×２００ｍｍの市販の綿製の布を重ね合わせ、４５℃で２４時間及び２３℃で２４時間、１５０Ｎの荷重をかけた状態で養生した。荷重を除去後、手でシートと布とを引き剥がした後の、シートの状態を観察した。
○：変化なし ×：破れたり、回復不能な変形が残る。
(5) Easy peelability An acrylic pressure-sensitive adhesive was applied to one side of a sheet cut out to 150 × 200 mm. A commercially available cotton cloth of 150 × 200 mm was superposed on the coated surface and cured under a load of 150 N at 45 ° C. for 24 hours and at 23 ° C. for 24 hours. After removing the load, the state of the sheet after the sheet and cloth were peeled off by hand was observed.
○: No change ×: Breaking or unrecoverable deformation remains.
［実施例１］
線状低密度ポリエチレン（密度０．９１８ｇ／ｃｍ３、ＭＦＲ３．５ｇ／１０分、微分値ｄＮ／ｄＳの最小値は０．００２、日本ポリエチレン製、商品名：ＮＣ５６４Ａ）５６重量％、分岐状低密度ポリエチレン（密度０．９２３ｇ／ｃｍ３、ＭＦＲ３．７ｇ／１０分、日本ポリエチレン製、商品名：ＬＣ５２０）３２重量％、分岐状低密度ポリエチレン（密度０．９２１ｇ／ｃｍ３、ＭＦＲ９．４ｇ／１０分、日本ポリエチレン製、商品名：ＬＣ７２０）１２重量％をミキサーにて混合した後に、フィルム成形機に供してシートを成形した。成形したシートの評価の結果を表１に示す。
[Example 1]
Linear low-density polyethylene (density 0.918 g / cm 3 , MFR 3.5 g / 10 min, differential dN / dS minimum value is 0.002, made by Nippon Polyethylene, trade name: NC564A) 56% by weight, branched low Density polyethylene (density 0.923 g / cm 3 , MFR 3.7 g / 10 min, manufactured by Nippon Polyethylene, trade name: LC520) 32% by weight, branched low density polyethylene (density 0.921 g / cm 3 , MFR 9.4 g / 10) Minute, manufactured by Nippon Polyethylene, trade name: LC720) 12% by weight was mixed with a mixer, and then subjected to a film forming machine to form a sheet. Table 1 shows the results of evaluation of the molded sheet.
［比較例１］
線状低密度ポリエチレン（密度０．９３５ｇ／ｃｍ３、ＭＦＲ５．０ｇ／１０分、微分値ｄＮ／ｄＳの最小値は−０．０３８、日本ポリエチレン製、商品名：ＵＦ９６０）５６重量％、分岐状低密度ポリエチレン（密度０．９２３ｇ／ｃｍ３、ＭＦＲ３．７ｇ／１０分、日本ポリエチレン製、商品名：ＬＣ５２０）３２重量％、分岐状低密度ポリエチレン（密度０．９２１ｇ／ｃｍ３、ＭＦＲ９．４ｇ／１０分、日本ポリエチレン製、商品名：ＬＣ７２０）１２重量％をミキサーにて混合した後に、フィルム成形機に供してシートを成形した。成形したシートの評価の結果を表１に示す。
なお、使用した線状低密度ポリエチレンの伸度荷重挙動が適切でなかったため（ｄＮ／ｄＳ≦０）、剥離試験において回復不能の変形が生じた。
[Comparative Example 1]
Linear low density polyethylene (density 0.935 g / cm 3 , MFR 5.0 g / 10 min, differential dN / dS minimum value is −0.038, manufactured by Nippon Polyethylene, trade name: UF960) 56% by weight, branched Low-density polyethylene (density 0.923 g / cm 3 , MFR 3.7 g / 10 min, manufactured by Nippon Polyethylene, trade name: LC520) 32% by weight, branched low-density polyethylene (density 0.921 g / cm 3 , MFR 9.4 g / 10 minutes, Nippon Polyethylene, trade name: LC720) 12% by weight was mixed with a mixer and then subjected to a film forming machine to form a sheet. Table 1 shows the results of evaluation of the molded sheet.
In addition, since the elongation load behavior of the used linear low density polyethylene was not appropriate (dN / dS ≦ 0), unrecoverable deformation occurred in the peel test.
［比較例２］
線状低密度ポリエチレン（密度０．９１８ｇ／ｃｍ３、ＭＦＲ３．５ｇ／１０分、微分値ｄＮ／ｄＳの最小値は０．００２、日本ポリエチレン製、商品名：ＮＣ５６４Ａ）５６重量％、分岐状低密度ポリエチレン（密度０．９２０ｇ／ｃｍ３、ＭＦＲ６．０ｇ／１０分、日本ポリエチレン製、商品名：ＬＣ６０８Ｂ）４４重量％、をミキサーにて混合した後に、フィルム成形機に供してシートを成形した。成形したシートの評価の結果を表１に示す。
なお、実施例１において相互にＭＦＲの異なる二種類の分岐状低密度ポリエチレンを、中間のＭＦＲを有する一種類の分岐状低密度ポリエチレンに置き換えたところ（（Ｂ）成分を使用しない）、加工性が低下し、剥離試験において回復不能の変形が生じた。
[Comparative Example 2]
Linear low-density polyethylene (density 0.918 g / cm 3 , MFR 3.5 g / 10 min, differential dN / dS minimum value is 0.002, made by Nippon Polyethylene, trade name: NC564A) 56% by weight, branched low Density polyethylene (density 0.920 g / cm 3 , MFR 6.0 g / 10 min, manufactured by Nippon Polyethylene, trade name: LC608B) 44% by weight was mixed with a mixer, and then subjected to a film molding machine to form a sheet. Table 1 shows the results of evaluation of the molded sheet.
In Example 1, two kinds of branched low density polyethylenes having different MFRs were replaced with one kind of branched low density polyethylene having an intermediate MFR (component (B) was not used). Decreased and unrecoverable deformation occurred in the peel test.
［実施例と比較例の結果の考察］
本発明の請求項１における構成の要件を全て満たす実施例１においては、フィルム物性における引張強度と引張伸度の特性が優れ、線状低密度ポリエチレン系樹脂（Ａ）成分の引張試験における伸度荷重曲線の微分値（ｄＮ／ｄＳ）の最小値が＞０なので、衛生用品のバックシートを下着等から剥離する際に剥し易く、粘着剤層が設けられたバックシートが破けたり伸ばされずに衛生用品本体を下着等から剥離できる、易剥離性を備えている。また、フィルム成形加工性の指標である樹脂圧力が小さく、成形加工性も優れていることが示されている。
一方、比較例１では、フィルム物性における引張強度と引張伸度の特性は概ね優れ、フィルム成形加工性の指標である樹脂圧力も小さいが、線状低密度ポリエチレン系樹脂（Ａ）成分の密度が高過ぎ、また、微分値（ｄＮ／ｄＳ）の最小値が≦０なので、バックシートにおける易剥離性を欠いている。
比較例２では、分岐状低密度ポリエチレン系樹脂（Ｂ）成分が配合されていないので、フィルム物性における引張強度と引張伸度の特性及びフィルム成形加工性が共に劣り、バックシートにおける易剥離性も欠いている。
以上の実施例と比較例の対照結果よりして、本発明のポリエチレン系樹脂組成物が従来の材料より、バックシートの剥離性と各性能において悉く優れており、本発明の構成の要件の合理性と有意性が実証され、従来技術への卓越性も明らかにされている。
[Consideration of results of Examples and Comparative Examples]
In Example 1 which satisfies all the requirements of the constitution of claim 1 of the present invention, the tensile strength and tensile elongation characteristics of the film properties are excellent, and the elongation in the tensile test of the linear low density polyethylene resin (A) component Since the minimum value of the differential value (dN / dS) of the load curve is> 0, it is easy to peel off when the sanitary article backsheet is peeled off from underwear, etc. Easily peelable from the underwear etc. Further, it is shown that the resin pressure, which is an index of film forming processability, is small and the forming processability is excellent.
On the other hand, in Comparative Example 1, the properties of tensile strength and tensile elongation in film properties are generally excellent, and the resin pressure that is an index of film forming processability is small, but the density of the linear low density polyethylene resin (A) component is small. Since it is too high and the minimum value of the differential value (dN / dS) is ≦ 0, it is not easily peelable on the backsheet.
In Comparative Example 2, since the branched low-density polyethylene-based resin (B) component is not blended, both the tensile strength and tensile elongation characteristics and film forming processability in film properties are inferior, and the easy peelability in the back sheet is also achieved. Lacks.
From the comparison results of the above examples and comparative examples, the polyethylene resin composition of the present invention is far superior to the conventional materials in the peelability and performance of the backsheet, and the requirements for the constitution of the present invention are rational. Sexuality and significance are demonstrated, and the superiority to the prior art is also revealed.
Claims (7)
０．１≦ｌｏｇ（ＭＦＲｃ／ＭＦＲｂ）≦１ The MFR of the branched low density polyethylene resin (B) and the MFR of the branched low density polyethylene resin (C) satisfy the following relational expression: The polyethylene-type resin composition described in one.
0.1 ≦ log (MFRc / MFRb) ≦ 1
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06197928A (en) * | 1992-12-28 | 1994-07-19 | Nippon Unicar Co Ltd | Resin composition for back seat of diaper and back seat of diaper prepared of the composition |
| JPH07265358A (en) * | 1994-03-29 | 1995-10-17 | Nippon Unicar Co Ltd | Resin composition for breathing diaper back sheet and breathing diaper back sheet manufactured from the same |
| JPH10120841A (en) * | 1996-10-18 | 1998-05-12 | Asahi Chem Ind Co Ltd | Polyethylene resin composition for extrusion lamination and extrusion laminate produced therefrom |
| JP2004359911A (en) * | 2003-06-09 | 2004-12-24 | Mitsui Chemicals Inc | Polyolefin composition improved in calendering processability and wall paper using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06197928A (en) * | 1992-12-28 | 1994-07-19 | Nippon Unicar Co Ltd | Resin composition for back seat of diaper and back seat of diaper prepared of the composition |
| JPH07265358A (en) * | 1994-03-29 | 1995-10-17 | Nippon Unicar Co Ltd | Resin composition for breathing diaper back sheet and breathing diaper back sheet manufactured from the same |
| JPH10120841A (en) * | 1996-10-18 | 1998-05-12 | Asahi Chem Ind Co Ltd | Polyethylene resin composition for extrusion lamination and extrusion laminate produced therefrom |
| JP2004359911A (en) * | 2003-06-09 | 2004-12-24 | Mitsui Chemicals Inc | Polyolefin composition improved in calendering processability and wall paper using the same |
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