JP4712902B1 - Heat-sealing adhesive and heat-sealing lid - Google Patents
Heat-sealing adhesive and heat-sealing lid Download PDFInfo
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- JP4712902B1 JP4712902B1 JP2010135512A JP2010135512A JP4712902B1 JP 4712902 B1 JP4712902 B1 JP 4712902B1 JP 2010135512 A JP2010135512 A JP 2010135512A JP 2010135512 A JP2010135512 A JP 2010135512A JP 4712902 B1 JP4712902 B1 JP 4712902B1
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- 238000007789 sealing Methods 0.000 title claims abstract description 51
- 239000012945 sealing adhesive Substances 0.000 title claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011888 foil Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 abstract description 26
- 239000011347 resin Substances 0.000 abstract description 26
- 238000000034 method Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- -1 cyclohexane Chemical class 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229920006015 heat resistant resin Polymers 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
【課題】熱封緘温度の熱封緘性接着強度への影響が小さい熱封緘性接着剤およびそれを用いた熱封緘性蓋材を提供する。
【解決手段】基材１６と、その表面に設けられたデザイン層１６と、その裏面に設けられた熱封緘性樹脂層１８とからなる熱封緘性蓋材１２。熱封緘性樹脂層１８は、カルボン酸変性プロピレン（共）重合体が溶剤に溶解または分散された液状組成物に、シリカを分散させた熱封緘性接着剤を基材１６に塗工し、乾燥して形成される。
【選択図】図１The present invention provides a heat-sealing adhesive having a small influence on the heat-sealing adhesive strength of the heat-sealing temperature, and a heat-sealing lid material using the same.
A heat sealable lid member 12 comprising a base material 16, a design layer 16 provided on the surface thereof, and a heat sealable resin layer 18 provided on the back surface thereof. The heat-sealing resin layer 18 is formed by applying a heat-sealing adhesive in which silica is dispersed to a base material 16 in a liquid composition in which a carboxylic acid-modified propylene (co) polymer is dissolved or dispersed in a solvent, and drying. Formed.
[Selection] Figure 1
Description
本発明は、熱封緘性接着剤および熱封緘性蓋材に関する。詳しくは、医薬品等を包装するＰＴＰ（Press Through Pack）包装材に用いられる熱封緘性接着剤および熱封緘性蓋材に関する。 The present invention relates to a heat sealable adhesive and a heat sealable lid material. More specifically, the present invention relates to a heat-sealing adhesive and a heat-sealing lid material used for PTP (Press Through Pack) packaging materials for packaging pharmaceutical products and the like.
ＰＴＰ包装体は、内容物を格納するための容器の部分となるポケットを成形したプラスチックシートの加工成形体（プラスチック容器または包装材）と、その容器口部を密封するための蓋の部分となる、金属箔、特にアルミニウム箔の基材の一面に熱封緘性樹脂層を設けた熱封緘性蓋材との二つの部分からなる。 The PTP package body is a plastic sheet processed molded body (plastic container or packaging material) in which a pocket serving as a container portion for storing contents is molded, and a lid portion for sealing the container mouth. It consists of two parts: a heat-sealing lid material provided with a heat-sealing resin layer on one surface of a metal foil, particularly an aluminum foil substrate.
加工成形体を形成するプラスチックシートとしては、加工性に優れているため古くから塩化ビニル樹脂シートが使用されている。しかし、近年、防湿性に優れかつ安価であるところから、プロピレン樹脂シートが使用されるようになってきている。一方、蓋材の基材としては、金属箔、特にアルミニウム箔が通常採用されている。なお、破裂を容易にするための加工を施したプラスチックフィルムも提案されているが、未だ実用されるに至っていない。 As a plastic sheet for forming a processed molded body, a vinyl chloride resin sheet has been used for a long time because of its excellent processability. However, in recent years, a propylene resin sheet has come to be used because it is excellent in moisture resistance and inexpensive. On the other hand, a metal foil, particularly an aluminum foil is usually employed as a base material for the lid. In addition, although the plastic film which gave the process for making it easy to burst has been proposed, it has not yet been put into practical use.
前記蓋材は、通常、金属箔、特にアルミニウム箔の基材の片面又は両面に文字やデザインを印刷し、更にその上に一方の面（外側になる面）には、必要により、無色または着色した透明な耐熱性被覆剤を塗工するか、または、プラスチックフィルムを積層することにより熱封緘時に文字やデザインなどの印刷層を保護するための耐熱性樹脂層を設ける。反対の面（接着される面）には加工成形体に加熱圧着によって熱封緘させるために、文字やデザインあるいは全面着色の印刷層を印刷し、更にその上に熱封緘性接着剤を塗布して熱封緘性樹脂層を形成させることにより製造されている。 The cover material is usually printed with characters or designs on one or both sides of a metal foil, particularly an aluminum foil base material, and further, on one side (the outer side), it is colorless or colored as necessary. A transparent heat-resistant coating agent is applied or a plastic film is laminated to provide a heat-resistant resin layer for protecting printed layers such as letters and designs during heat sealing. On the opposite surface (the surface to be bonded), in order to heat-seal the processed molded body by thermocompression bonding, print a printed layer of characters, design or full color, and then apply a heat-sealing adhesive on it. It is manufactured by forming a heat-sealing resin layer.
包装作業における内容物の充填操作は、前記容器となるポケットを設けた塩化ビニル樹脂シートやプロピレン樹脂シートの加工成形体に内容物を格納した後、その開口面側に前記のアルミニウム箔を基材とする蓋材をその熱封緘性樹脂層が接触するように積層し、蓋材の耐熱封緘性樹脂層を設けた面からヒートシールバーあるいは熱封緘ドラムにより加熱下に圧着することにより加工成形体の非ポケット部分に熱融着させることによって遂行される。 The filling operation of the contents in the packaging operation is performed by storing the contents in a processed molded body of a vinyl chloride resin sheet or a propylene resin sheet provided with a pocket serving as the container, and then using the aluminum foil as a base material on the opening surface side. The heat-sealing resin layer is laminated so that the heat-sealing resin layer is in contact with the heat-sealing resin layer on the surface of the lid material, and the heat-sealing resin layer is pressed under heat with a heat seal bar or heat-sealing drum. This is accomplished by heat-sealing to the non-pocket portion of.
加熱加圧条件は蓋材の基材の厚みや圧着時間等の条件によって異なるが、熱封緘温度は１２０〜２８０℃の間で行われており、熱封緘圧力は０．１０〜０．２９Ｐａに設定されていることが多い。 The heating and pressing conditions vary depending on conditions such as the thickness of the base material of the lid and the pressure bonding time, but the heat sealing temperature is 120 to 280 ° C., and the heat sealing pressure is 0.10 to 0.29 Pa. Often set.
前記蓋材の熱封緘性樹脂層は、通常、熱可塑性樹脂からなり、加工成形体の材質により、それぞれ塩化ビニル（共）重合体、プロピレン（共）重合体等の樹脂を主成分とする樹脂組成物が使用されているが、プロピレン樹脂製容器に対してはカルボン酸変性プロピレン（共）重合体が使用されてきている（特許文献１、２、３参照）。 The heat-sealing resin layer of the lid is usually made of a thermoplastic resin, and a resin mainly composed of a resin such as vinyl chloride (co) polymer or propylene (co) polymer, depending on the material of the processed molded body. Although the composition is used, a carboxylic acid-modified propylene (co) polymer has been used for a propylene resin container (see Patent Documents 1, 2, and 3).
前述のようにＰＴＰ包装体は蓋材の熱封緘性樹脂層を加工成形体の非ポケット部分にヒートシールバーあるいは熱封緘ドラムにより加熱圧着することにより形成されるのであるが、熱封緘強度がある熱封緘温度以上で一定値にならないで低下してくるという問題があった。
本発明は、ある熱封緘温度以上で一定の熱封緘強度が得られる安定な熱封緘性接着剤およびそれを用いた熱封緘性蓋材を提供することを目的とする。
As described above, the PTP package is formed by heat-sealing the heat-sealing resin layer of the cover material to the non-pocket portion of the processed molded body with a heat-sealing bar or a heat-sealing drum, but has a heat-sealing strength. There was a problem that the temperature did not become a constant value at a temperature higher than the heat sealing temperature.
An object of the present invention is to provide a stable heat-sealing adhesive capable of obtaining a certain heat-sealing strength at a certain heat-sealing temperature or higher and a heat-sealing lid material using the same.
本発明の熱封緘性接着剤は、カルボン酸変性プロピレン（共）重合体が溶剤に溶解または分散された液状組成物に、シリカを分散させたものであって、前記シリカが液状組成物中の固形分に対して５〜３５重量％分散されていることを特徴としている。
本発明の熱封緘性蓋材は、本発明の熱封緘性接着剤をアルミニウム箔基材に塗工し、乾燥させて得ることを特徴としている。
The heat sealable adhesive of the present invention is obtained by dispersing silica in a liquid composition in which a carboxylic acid-modified propylene (co) polymer is dissolved or dispersed in a solvent, and the silica is contained in the liquid composition. It is characterized by being dispersed by 5 to 35% by weight with respect to the solid content .
The heat-sealing lid material of the present invention is obtained by applying the heat-sealing adhesive of the present invention to an aluminum foil base material and drying it.
本発明の熱封緘性接着剤は、カルボン酸変性プロピレン（共）重合体が溶剤に溶解または分散された液状組成物に、シリカを分散させているため、熱封緘性接着強度が高い。比較的広い熱封緘温度で好ましい熱封緘性接着強度が得られる。 The heat-sealing adhesive of the present invention has high heat-sealing adhesive strength because silica is dispersed in a liquid composition in which a carboxylic acid-modified propylene (co) polymer is dissolved or dispersed in a solvent. A preferable heat-sealing adhesive strength can be obtained at a relatively wide heat-sealing temperature.
本発明の熱封緘性蓋材は、本発明の熱封緘性接着剤を用いているため、蓋材と加工成形体とが接着したＰＴＰ包装体を安定して製造することができる。 Since the heat-sealing lid material of the present invention uses the heat-sealing adhesive material of the present invention, a PTP package in which the lid material and the processed molded body are bonded can be stably produced.
図１ａのＰＴＰ包装体１０は、プラスチックシートからなる加工成形体１１と、蓋材（熱封緘性蓋材）１２とからなる。符号Ｔがこの包装体１０に収容された錠剤である。
加工成形体１１は、図１ｂに示すように、従来公知のものであり、複数のポケット１１ａが設けられている。
この加工成形体１１のプラスチックシートとしては、塩化ビニル樹脂製シートおよびプロピレン樹脂製シートが主として使用される。
The
As shown in FIG. 1b, the processed molded
As the plastic sheet of the processed molded
蓋材１２は、図１ｃに示すように、基材１６と、その表面に設けられたデザイン層１７と、その裏面に設けられた熱封緘性樹脂層１８とからなる。基材１６としては、金属箔、特にアルミニウム箔が用いられる。そのため、ＰＴＰ包装体として用いたとき、容易に破裂させることができる。デザイン層１７は、基材１６の表面に設けられる文字やデザインの印刷層１９と、その上に設けられる耐熱性樹脂層２０とからなる。また印刷層１９を設けず直接耐熱性樹脂層２０を設けてもよい。
As shown in FIG. 1 c, the
熱封緘性樹脂層１８は、熱封緘性接着剤を基材１６の裏面に塗工し、乾燥して形成される。また、基材１６と熱封緘性樹脂層１８との間に文字やデザイン等の印刷層を設けてもよい。
熱封緘性接着剤は、カルボン酸変性プロピレン（共）重合体およびそれを溶解あるいは分散する溶剤からなる液状組成物と、その液状組成物に分散されたシリカとからなる。
The heat-sealing
The heat-sealing adhesive comprises a liquid composition comprising a carboxylic acid-modified propylene (co) polymer and a solvent for dissolving or dispersing it, and silica dispersed in the liquid composition.
カルボン酸変性プロピレン（共）重合体として、マレイン酸、フマル酸、イタコン酸等
の不飽和カルボン酸によって変性されたプロピレン（共）重合体が挙げられる。
Examples of carboxylic acid-modified propylene (co) polymers include propylene (co) polymers modified with unsaturated carboxylic acids such as maleic acid, fumaric acid, and itaconic acid.
カルボン酸変性プロピレン（共）重合体を溶解または分散させるための溶剤は、トルエン、キシレン等の芳香族炭化水素類；シクロヘキサン、Ｎ−ヘキサン、ベンジン、メチルシクロヘキサン等の脂肪族炭化水素；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；酢酸エチル、酢酸ブチル、酢酸プロピル等のエステル類等、またそれらの混合溶剤を使用することができる。 Solvents for dissolving or dispersing the carboxylic acid-modified propylene (co) polymer include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane, N-hexane, benzine and methylcyclohexane; acetone and methyl ethyl ketone Ketones such as methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate and propyl acetate; and mixed solvents thereof can be used.
シリカ（二酸化ケイ素）は、天然シリカ、合成シリカが挙げられる。また、合成シリカも湿式法及び乾式法のどちらで製造されたものでもよい。いずれのシリカも熱封緘性強度に対する効果に大きな差異はないが、塗工面の透明性が求められる場合には、乾式法による合成シリカの使用が適当である。その平均粒子径としては、０．００１μｍ〜１５μｍが好ましく、特に０．００１μｍ〜５μｍが好ましい。シリカへの表面処理の有無は特に影響はなく、無機物処理および有機物処理のシリカも使用できる。比表面積は、１００〜７００ｍ2／ｇが好ましく、吸油量は１０〜５００ｍｌ／１００ｇが好ましく、さらに好ましいのは１００〜４００ｍｌ／１００ｇである。
このようなシリカの添加量は、酸変性ポリオレフィンとシリカとからなる固形分に対する量が、５〜３５重量％、特に１０〜３０重量％となるようにするのが好ましい。５重量％より小さいと、シリカの効果が小さい。３５重量％より大きいと熱封緘性接着強度の低下が見られるようになる。
Examples of silica (silicon dioxide) include natural silica and synthetic silica. Synthetic silica may also be produced by either a wet method or a dry method. There is no significant difference in the effect on the heat sealing strength of any silica, but when the transparency of the coated surface is required, it is appropriate to use synthetic silica by a dry method. The average particle diameter is preferably 0.001 μm to 15 μm, particularly preferably 0.001 μm to 5 μm. The presence or absence of surface treatment on silica has no particular effect, and inorganic treatment and organic treatment silica can also be used. The specific surface area is preferably 100 to 700 m 2 / g, the oil absorption is preferably 10 to 500 ml / 100 g, and more preferably 100 to 400 ml / 100 g.
The amount of such silica added is preferably such that the amount relative to the solid content of the acid-modified polyolefin and silica is 5 to 35% by weight, particularly 10 to 30% by weight. If it is less than 5% by weight, the effect of silica is small. When it is larger than 35% by weight, the heat-sealing adhesive strength is lowered.
また、熱封緘性接着剤には、必要に応じて、接着剤、塗料、印刷インキに通常使用されるブロッキング防止剤、スリップ剤、着色剤、酸化防止剤、充填剤、紫外線吸収剤等の各種添加剤を入れてもよい。 In addition, the heat-sealing adhesive includes various types such as an anti-blocking agent, a slip agent, a colorant, an antioxidant, a filler, and an ultraviolet absorber that are usually used for adhesives, paints, and printing inks as necessary. Additives may be added.
この熱封緘性接着剤の製造方法は、溶剤およびカルボン酸変性プロピレン（共）重合体を混合し、室温または加温下で攪拌しながらカルボン酸変性プロピレン（共）重合体を溶解または分散させる。カルボン酸変性プロピレン（共）重合体溶解液または分散液に一定量のシリカを混合して、分散させて製造する。 In this method for producing a heat-sealing adhesive, a solvent and a carboxylic acid-modified propylene (co) polymer are mixed, and the carboxylic acid-modified propylene (co) polymer is dissolved or dispersed while stirring at room temperature or under heating. A certain amount of silica is mixed and dispersed in a carboxylic acid-modified propylene (co) polymer solution or dispersion.
ＰＴＰ包装体１０の製造方法は、加工成形体１１のポケット１１ａに内容物を格納した後、その開口面側の非ポケット部１１ｂに蓋材１２の熱封緘性樹脂層１８（裏面）が接触するように積層し、蓋材の表面からヒートシールバーあるいは熱封緘ドラム等により加熱および加圧する。これにより加工成形体１１の非ポケット部１１ｂと蓋材１２の裏面とが熱融着し、ポケット１１ａが密閉される。
このような加熱加圧条件は積層材料によって異なるが、熱封緘温度は８０〜２８０度、好ましくは１２０〜２５０度の間で行われ、その熱封緘圧力は０．１０〜０．５４ＭＰａの間で行われる。
In the manufacturing method of the
Such heat and pressure conditions vary depending on the laminated material, but the heat sealing temperature is 80 to 280 degrees, preferably 120 to 250 degrees, and the heat sealing pressure is 0.10 to 0.54 MPa. Done.
メチルシクロヘキサン（ＭＣＨ）およびメチルエチルケトン（ＭＥＫ）の混合溶剤に、表１の配合に基づいて酸変性ポリプロピレン（酸変性ＰＰ）を溶解または分散させて液状組成物を生成した。その後、その液状組成物に表１に基づいた添加剤を一定量分散させて、比較例１〜５および実施例１の熱封緘性接着剤を製造した。表１において、固形分とは、酸変性ポリプロピレンとそれぞれの添加剤の量を示す。 Based on the formulation in Table 1, acid-modified polypropylene (acid-modified PP) was dissolved or dispersed in a mixed solvent of methylcyclohexane (MCH) and methyl ethyl ketone (MEK) to produce a liquid composition. Thereafter, a certain amount of additives based on Table 1 were dispersed in the liquid composition to produce heat-sealing adhesives of Comparative Examples 1 to 5 and Example 1. In Table 1, the solid content indicates the amount of acid-modified polypropylene and each additive.
比較例１〜５および実施例１の使用原料詳細は以下の通りである。
・酸変性ポリプロピレン：トーヨータック ＰＭＡ−ＬＺ（東洋紡績株式会社）
・シリカ（湿式法、平均粒子径１．５μｍ、給油量２５０ｍｌ／１００ｇ）：ファインシール Ｔ−３２（株式会社トクヤマ）
・タルク：ミクロエース Ｌ−１（日本タルク株式会社）
・酸化チタン：ＴＩＴＯＮ Ｒ−５Ｎ（堺化学工業株式会社）
・炭酸カルシウム；白艶華 ＣＣＲ（白石工業株式会社）
・沈降性硫酸バリウム：＃１００（堺化学工業株式会社）
Details of the raw materials used in Comparative Examples 1 to 5 and Example 1 are as follows.
-Acid-modified polypropylene: Toyotac PMA-LZ (Toyobo Co., Ltd.)
Silica (wet method, average particle size 1.5 μm, oil supply amount 250 ml / 100 g): Fine seal T-32 (Tokuyama Corporation)
・ Talc: Microace L-1 (Nippon Talc Co., Ltd.)
・ Titanium oxide: TITON R-5N (Sakai Chemical Industry Co., Ltd.)
・ Calcium carbonate; Shiraka Hana CCR (Shiraishi Industrial Co., Ltd.)
・ Precipitable barium sulfate: # 100 (Sakai Chemical Industry Co., Ltd.)
これらの熱封緘性接着剤をバーコーターにてアルミニウム箔（２０μｍ）の艶消面に塗布し、その後、オーブンにて１８０度で１０秒乾燥し、熱封緘性蓋材を製造した。この熱封緘性蓋材をポリプロピレンシート（住友化学製ＮＳ３４５１）へ、０．２９ＭＰａの圧力で１４０度から２０度毎に２６０度までの温度で各１秒間熱封緘した。それぞれを裁断機にて１５ｍｍ幅に切断し、オートグラフにて、剥離角度１８０度、剥離速度２００ｍｍ／分の条件で熱封緘性接着強度を測定した。その結果を表２に示す。 These heat sealable adhesives were applied to the matte surface of an aluminum foil (20 μm) with a bar coater, and then dried in an oven at 180 degrees for 10 seconds to produce a heat sealable lid material. This heat-sealing lid material was heat-sealed to a polypropylene sheet (NS3451 manufactured by Sumitomo Chemical Co., Ltd.) at a pressure of 0.29 MPa at a temperature from 140 degrees to 260 degrees every 20 degrees for 1 second each. Each was cut into a width of 15 mm with a cutter, and the heat sealing adhesive strength was measured with an autograph under the conditions of a peeling angle of 180 degrees and a peeling speed of 200 mm / min. The results are shown in Table 2.
実施例１の熱封緘性接着剤は、熱封緘温度が１４０℃では何も添加していない比較例１より熱封緘性接着強度が小さくなったが、１６０〜２６０℃では比較例１より高い熱封緘性接着強度が得られた。実施例１の熱封緘性接着剤は、熱封緘温度が２６０℃であっても比較的高い熱封緘性接着強度が得られた。また１６０〜２６０℃の熱封緘温度の範囲では、熱封緘性接着強度への影響が小さいことがわかる。さらに、実施例１の熱封緘性接着剤によって形成される熱封緘性樹脂層は、成膜直後の表面粘着性が無かった。
一方、比較例２〜５の熱封緘性接着剤は、特に顕著な結果が得られなかった。また、いずれも熱封緘温度が２６０℃を超えると大きく低下した。また、比較例２〜５の熱封緘性接着剤は、添加物が上手く分散されず、直ぐ沈降した。
The heat-sealing adhesive of Example 1 had a heat-sealing adhesive strength lower than that of Comparative Example 1 in which nothing was added at a heat sealing temperature of 140 ° C., but heat higher than that of Comparative Example 1 at 160 to 260 ° C. Sealing adhesive strength was obtained. The heat-sealing adhesive of Example 1 had a relatively high heat-sealing adhesive strength even when the heat-sealing temperature was 260 ° C. It can also be seen that in the range of 160 to 260 ° C. heat sealing temperature, the influence on the heat sealing adhesive strength is small. Furthermore, the heat-sealing resin layer formed by the heat-sealing adhesive of Example 1 had no surface tackiness immediately after film formation.
On the other hand, the heat-sealing adhesives of Comparative Examples 2 to 5 did not give particularly remarkable results. Moreover, in all cases, when the heat sealing temperature exceeded 260 ° C., the temperature greatly decreased. Moreover, the heat-sealing adhesives of Comparative Examples 2 to 5 settled immediately without the additive being well dispersed.
次に、固形物中のシリカの量による影響を検討した。実施例２〜７の熱封緘性接着剤を表３の配合に基づいて製造した。そして、それらを１４０度から２０度毎に２２０度で熱封緘した熱封緘性接着強度を測定した。その結果を表４に示す。ここで、固形分とは、酸変性ポリプロピレンとシリカの総量を示す。 Next, the influence of the amount of silica in the solid material was examined. The heat-sealing adhesives of Examples 2 to 7 were produced based on the formulations shown in Table 3. And the heat-sealing adhesive strength which heat-sealed them at 220 degree | times every 140 to 20 degree | times was measured. The results are shown in Table 4. Here, solid content shows the total amount of acid-modified polypropylene and silica.
実施例３〜７の熱封緘性接着剤は、熱封緘温度が１６０〜２４０℃の範囲で高い熱封緘性接着強度を示した。つまり、固形分に対するシリカの添加量が５．０〜２８．３重量％で広い熱封緘温度における高い接着強度を見せた。一方、固形分に対するシリカの添加量が３．８重量％を下回るといずれの熱封緘温度でも熱封緘性接着強度が比較例１と同程度となった。さらに、固形分に対するシリカの添加量が３５重量％を超えると、いずれの温度による熱封緘でも、その熱封緘性接着強度が著しく低下した。そのため、ある一定量を超えるとシリカが樹脂の接着を阻害することがわかった。 The heat-sealing adhesives of Examples 3 to 7 exhibited high heat-sealing adhesive strength when the heat sealing temperature was in the range of 160 to 240 ° C. That is, the addition amount of silica with respect to the solid content was 5.0 to 28.3 wt%, and high adhesive strength at a wide heat sealing temperature was exhibited. On the other hand, when the addition amount of silica with respect to the solid content is less than 3.8% by weight, the heat sealing adhesive strength is comparable to that of Comparative Example 1 at any heat sealing temperature. Furthermore, when the addition amount of silica with respect to the solid content exceeds 35% by weight, the heat sealing adhesive strength is remarkably lowered at any temperature. For this reason, it has been found that silica exceeds the adhesion of the resin when a certain amount is exceeded.
次に、シリカの粒径による影響を検討した。実施例２〜４の熱封緘性接着剤を表５の配合に基づいて製造した。そして、それらを１４０度から２０度毎に２２０度で熱封緘した熱封緘性接着強度を測定した。その結果を表６に示す。 Next, the influence of the particle size of silica was examined. The heat-sealing adhesives of Examples 2 to 4 were produced based on the formulations shown in Table 5. And the heat-sealing adhesive strength which heat-sealed them at 220 degree | times every 140 to 20 degree | times was measured. The results are shown in Table 6.
・シリカ２（乾式法、平均粒子径約１６ｎｍ、疎水性）：ＡＥＲＯＳＩＬ Ｒ９７２（日本アエロジル株式会社）
・シリカ３（湿式法、平均粒子径１．５μｍ、給油量２５０ｍｌ／１００ｇ）：ファインシール Ｔ−３２（株式会社トクヤマ）
・シリカ４（湿式法、平均粒子径２．０μｍ、給油量２５０ｍｌ／１００ｇ）：ファインシール Ｔ−５０（株式会社トクヤマ）
・シリカ５（湿式法、平均粒子径４．５μｍ、給油量２９０ｍｌ／１００ｇ）：サイロスフェア Ｃ−１５０４（富士シリシア化学株式会社）
Silica 2 (dry method, average particle diameter of about 16 nm, hydrophobic): AEROSIL R972 (Nippon Aerosil Co., Ltd.)
Silica 3 (wet method, average particle size 1.5 μm, oil supply amount 250 ml / 100 g): Fine seal T-32 (Tokuyama Corporation)
Silica 4 (wet method, average particle size 2.0 μm, oil supply amount 250 ml / 100 g): Fine seal T-50 (Tokuyama Corporation)
Silica 5 (wet method, average particle size 4.5 μm, oil supply amount 290 ml / 100 g): Pyrosphere C-1504 (Fuji Silysia Chemical Ltd.)
実施例１０〜１４の熱封緘性接着剤を１６０〜２６０℃で熱封緘した場合、いずれも高い熱封緘性接着強度が得られた。そのため、粒径０．００７μｍ〜４．５μｍの範囲においては、粒径はあまり影響がないことがわかる。また、製法（乾式法または湿式法）による合成シリカの種類も影響がないことがわかった。 When the heat-sealing adhesives of Examples 10 to 14 were heat-sealed at 160 to 260 ° C., high heat-sealing adhesive strength was obtained in all cases. Therefore, it can be seen that the particle size has little influence in the particle size range of 0.007 μm to 4.5 μm. Moreover, it turned out that the kind of synthetic silica by a manufacturing method (dry method or wet method) has no influence.
Ｔ 錠剤
１０ ＰＴＰ包装材
１１ 加工成形体
１１ａ ポケット
１１ｂ 非ポケット部
１２ 蓋材
１６ 基材
１７ デザイン層
１８ 熱封緘性樹脂層
１９ 印刷層
２０ 耐熱性樹脂層
Claims (2)
前記シリカが液状組成物中の固形分に対して５〜３５重量％分散されている、
熱封緘性接着剤。 It is those carboxylic acid-modified propylene (co) polymer is dispersed by silica dissolved or dispersed liquid composition in a solvent,
The silica is dispersed in an amount of 5 to 35% by weight based on the solid content in the liquid composition.
Heat-sealing adhesive.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5936655B2 (en) * | 1975-01-07 | 1984-09-05 | ニホンセキユカガク カブシキガイシヤ | Method for producing polyolefin composition |
| JPS6026031B2 (en) * | 1977-12-26 | 1985-06-21 | 三井化学株式会社 | How to improve adhesion between laminates |
| JP2006307104A (en) * | 2005-05-02 | 2006-11-09 | Yokohama Rubber Co Ltd:The | Adhesive composition |
| JP2009126924A (en) * | 2007-11-22 | 2009-06-11 | Riidaa:Kk | Heat-sealing adhesive and heat-sealing lid material coated with the adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5936655B2 (en) * | 1975-01-07 | 1984-09-05 | ニホンセキユカガク カブシキガイシヤ | Method for producing polyolefin composition |
| JPS6026031B2 (en) * | 1977-12-26 | 1985-06-21 | 三井化学株式会社 | How to improve adhesion between laminates |
| JP2006307104A (en) * | 2005-05-02 | 2006-11-09 | Yokohama Rubber Co Ltd:The | Adhesive composition |
| JP2009126924A (en) * | 2007-11-22 | 2009-06-11 | Riidaa:Kk | Heat-sealing adhesive and heat-sealing lid material coated with the adhesive |
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