JP4677370B2 - Oxygen indicator composition and packaging material using the composition - Google Patents
Oxygen indicator composition and packaging material using the composition Download PDFInfo
- Publication number
- JP4677370B2 JP4677370B2 JP2006167144A JP2006167144A JP4677370B2 JP 4677370 B2 JP4677370 B2 JP 4677370B2 JP 2006167144 A JP2006167144 A JP 2006167144A JP 2006167144 A JP2006167144 A JP 2006167144A JP 4677370 B2 JP4677370 B2 JP 4677370B2
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- JP
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- Prior art keywords
- oxygen indicator
- oxygen
- indicator composition
- water
- printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 103
- 239000001301 oxygen Substances 0.000 title claims description 103
- 229910052760 oxygen Inorganic materials 0.000 title claims description 103
- 239000000203 mixture Substances 0.000 title claims description 73
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- 239000000049 pigment Substances 0.000 claims description 17
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
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- SQNNHEYXAJPPKH-UHFFFAOYSA-N chloroethene;prop-2-enoic acid Chemical compound ClC=C.OC(=O)C=C SQNNHEYXAJPPKH-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
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- 238000002845 discoloration Methods 0.000 description 1
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- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000007644 letterpress printing Methods 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
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- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000003755 preservative agent Substances 0.000 description 1
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- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
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- 210000003813 thumb Anatomy 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Description
本発明は、食品、医薬品、電子部材、電子製品等を保存するための脱酸素包装材において、包装材内が無酸素状態であるか否かを色の変化により識別し得るための酸素インジケーター組成物および該組成物を用いてなる包装材に関する。 The present invention relates to a deoxygenated packaging material for preserving foods, pharmaceuticals, electronic components, electronic products, etc., and an oxygen indicator composition for distinguishing whether or not the inside of the packaging material is oxygen-free by color change And a packaging material using the composition.
食品、医薬品、電子部材、電子製品等の内容物の酸化を防止し、長期間保存する方法として、ガスバリア性を有する包装材で上記内容物を包装し、不活性ガスである窒素や炭酸ガスを封入し酸素と置換させる方法や包装材内に脱酸素剤を内容物と一緒に封入することで脱酸素状態にする方法等がある。
これらの方法により内容物は酸化劣化することなく長期間保存することが可能となる。しかし、包装材の欠損やバリア性低下、窒素や炭酸ガスの封入失敗や脱酸素剤の能力低下、あるいは流通などの運搬過程における衝撃などが原因によるピンホールやシール不良などが発生した場合には、包装材内に酸素が混入し、酸化劣化による内容物の腐敗や変質が生じる恐れがあるが、酸素の混入に気づかないまま流通される場合があった。包装材内に酸素が混入したとしても、外観的にそれを検知できない場合が多かった。
As a method of preventing oxidation of contents such as foods, pharmaceuticals, electronic parts, electronic products, etc. and storing them for a long period of time, the above contents are packaged with a packaging material having a gas barrier property, and nitrogen or carbon dioxide gas which is an inert gas is used. There are a method of encapsulating and replacing oxygen, a method of encapsulating a deoxygenating agent together with contents in a packaging material, and a method of deoxidizing.
By these methods, the contents can be stored for a long time without oxidative degradation. However, if a pinhole or seal failure occurs due to a loss of packaging material, reduced barrier properties, failure to enclose nitrogen or carbon dioxide gas, reduced capacity of oxygen scavenger, or impact during transportation or other transportation processes In addition, oxygen may be mixed into the packaging material and the contents may be spoiled or deteriorated due to oxidative degradation, but there are cases in which it is distributed without being aware of the mixing of oxygen. Even if oxygen was mixed in the packaging material, it could not be detected in appearance.
そこで、包装材の欠損、脱酸素剤の能力低下などによる酸素の混入を検知し、内容物が確実に脱酸素状態で保存されているかを確認する方法として、酸素の存在の有無により色相を変化する酸素インジケーターを含有する包装材が開発されている。酸素インジケーターの形態として広く使用されているのは錠剤型であり、直径１ｃｍ程度の大きさに打錠成形され、ポリエチレンやポリプロピレンなどの包材に微細孔を開けた状態で個包装され内容物、脱酸素剤と共にガスバリア性を有する包装材に封入されている。例えば、(a)メチレンブルー、(b)グルコース、(c)ケイ酸ナトリウム、シリカおよび水酸化ナトリウムよりなるアルカリ性剤、(d)低融点高分子よりなる結合剤、(e)有機酸コバルト、(f)水、(g)充填剤からなる錠剤型の酸素検知剤が提案され、実用化されている。しかし、錠剤型の酸素インジケーターは、（１）個々に錠剤を包装しなければならない、（２）小袋に空けた穴を通して崩壊した錠剤粉末が外部へ流出する場合がある、（３）錠剤の誤飲事故に繋がる危険性がある、（４）錠剤を包装材内に固定することが困難である、（５）錠剤が包装材内で動き、外部から目視検知しにくいなど種々の問題点を有していた。 Therefore, as a method of detecting whether oxygen is introduced due to a lack of packaging material, a decrease in the capacity of the oxygen scavenger, etc., and confirming that the contents are reliably stored in a deoxygenated state, the hue changes depending on the presence or absence of oxygen. Packaging materials containing oxygen indicators have been developed. The oxygen indicator is widely used in the form of tablets, which are tableted to a size of about 1 cm in diameter and individually packed with fine holes in a packaging material such as polyethylene or polypropylene. It is enclosed in a packaging material having gas barrier properties together with an oxygen scavenger. For example, (a) methylene blue, (b) glucose, (c) sodium silicate, an alkaline agent composed of silica and sodium hydroxide, (d) a binder composed of a low melting point polymer, (e) an organic acid cobalt, (f A tablet-type oxygen detector comprising water) and (g) filler has been proposed and put into practical use. However, the tablet-type oxygen indicator has the following features: (1) Tablets must be individually packaged, (2) Disintegrated tablet powder may flow out through a hole in a pouch, (3) Tablet error There are various problems such as risk of drinking accidents, (4) difficult to fix tablets in packaging materials, (5) tablets move in packaging materials and difficult to detect visually from outside. Was.
そのため、包装材に酸素インジケーター機能が一体となって設けられるように、酸素インジケーターを印刷により基材上に形成する包装材の開発が種々検討されている。例えば、酸化還元色素であるメチレンブルー、還元剤であるアスコルビン酸とからなる酸素インジケーター組成物が開示されているが、アスコルビン酸は、光や熱により劣化しやすいという課題があった。アスコルビン酸に耐光性や耐熱性を付与するため、ヒンダードアミン系薬剤を添加する方法が提案されているが、酸素インジケーター製造後の長期保管、流通時に安定した性能を発揮するには至っていない。 For this reason, various developments of packaging materials for forming an oxygen indicator on a substrate by printing so that the oxygen indicator function is integrally provided in the packaging material have been studied. For example, an oxygen indicator composition comprising methylene blue as a redox dye and ascorbic acid as a reducing agent has been disclosed. However, ascorbic acid has a problem of being easily deteriorated by light or heat. In order to impart light resistance and heat resistance to ascorbic acid, a method of adding a hindered amine chemical has been proposed, but it has not yet achieved stable performance during long-term storage and distribution after the production of the oxygen indicator.
酸化還元色素、還元剤、着色剤を基材上に固着するために用いられるバインダーとして、ポリアセタール樹脂が用いられる酸素インジケーター組成物も開示されている。しかし、印刷により酸素インジケーターを基材上に形成した場合、次工程であるラミネート加工に移るまで印刷物を巻きの状態で保管した場合において、酸素インジケーター組成物が基材の非印刷面(裏面)に移行するブロッキングのトラブルが発生する場合があった。 An oxygen indicator composition in which a polyacetal resin is used as a binder used for fixing a redox dye, a reducing agent, and a colorant on a substrate is also disclosed. However, when the oxygen indicator is formed on the base material by printing, the oxygen indicator composition is applied to the non-printed surface (back surface) of the base material when the printed material is stored in a wound state until the next process of laminating. There were cases where blocking trouble occurred.
還元剤としてアスコルビン酸を用いた場合、酸化還元色素の呈色反応を促進し、発色を安定させるためには酸素インジケーター組成物にグリセリン、エチレングリコール、プロピレングリコールなどの保湿剤を添加する必要があるが、これら保湿剤の添加はブロッキングを更に低下させる原因となっていた。
また、市販されている多くの酸素インジケーターは、着色剤として酸化還元色素であるメチレンブルー以外に、更に赤系着色剤を添加することによって、無酸素時は赤〜ピンク色、有酸素時は青〜紫色となり、酸素の存在有無をより識別しやすいように着色されている。酸素インジケーター組成物は、還元剤の酸化を促進する目的でアルカリ化剤が添加され、一般的にはｐＨ１０〜１４の範囲で使用されるが、アルカリ化剤の添加により赤系着色剤の変色や退色が生じ、発色が安定しないという問題があった。
In addition, many commercially available oxygen indicators have red to pink when no oxygen is present and blue when aerobic by adding a red colorant in addition to redox methylene blue as a colorant. It is purple so that it is easier to identify the presence or absence of oxygen. The oxygen indicator composition is added with an alkalinizing agent for the purpose of promoting the oxidation of the reducing agent, and is generally used within a pH range of 10 to 14. There was a problem that fading occurred and color development was not stable.
本発明の目的は、従来技術に基づく既存の酸素インジケーターでは解決し得なかった前記の欠点を解決することである。即ち、優れた耐ブロッキング性を有し、長期保管、流通時にも安定した発色を発現し、包装材の欠損、脱酸素剤の能力低下などによる包材内への酸素の混入を確実に検知し得る酸素インジケーター組成物および該組成物が印刷により基材上に形成され、酸素インジケーター機能が包装材および／または脱酸素剤と一体となった酸素インジケーターを提供することにある。
The object of the present invention is to solve the above-mentioned drawbacks that could not be solved by existing oxygen indicators based on the prior art. In other words, it has excellent blocking resistance, develops stable color development during long-term storage and distribution, and reliably detects oxygen contamination in the packaging material due to loss of packaging material, reduced capacity of oxygen scavenger, etc. It is an object of the present invention to provide an obtained oxygen indicator composition and an oxygen indicator in which the composition is formed on a substrate by printing, and the oxygen indicator function is integrated with a packaging material and / or an oxygen scavenger.
本発明者らは、前記の如き従来の問題点を解決すべく鋭意検討を重ねた結果、少なくとも酸化還元色素であるメチレンブルー、還元剤であるＤ−グルコース、酸価が５０〜３００ｍｇＫＯＨ／ｇであるとともにガラス転移点が１０〜７０℃であるアクリル系共重合体とからなる酸素インジケーター組成物が優れた耐ブロッキング性と長期保存性を有することを見出し、本発明に至った。
すなわち本発明の第１の発明は、
少なくとも、水と、
酸化還元色素であるメチレンブルーと、
還元剤であるＤ−グルコースと、
酸価が５０〜３００ｍｇＫＯＨ／ｇであるとともにガラス転移点が１０〜７０℃であり、アクリル酸、スチレン、及び、（メタ）アクリル酸エステルを重合してなる
アルカリ可溶型水溶性アクリル系重合体またはエマルジョン型アクリル系共重合体
とからなることを特徴とする酸素インジケーター組成物である。
第２の発明は、上記酸素インジケーター組成物に、更に着色剤として不溶性アゾ顔料、縮合アゾ顔料、縮合多環系顔料の群から選択される少なくとも１種以上の赤系顔料を含有することを特徴とする酸素インジケーター組成物である。
第３の発明は、上記酸素インジケーター組成物が印刷により基材上に形成され、酸素インジケーター機能が包装材および／または脱酸素剤と一体となっていることを特徴とする酸素インジケーターである。
As a result of intensive studies to solve the conventional problems as described above, the present inventors have at least methylene blue as a redox dye, D-glucose as a reducing agent, and an acid value of 50 to 300 mgKOH / g. In addition, the present inventors have found that an oxygen indicator composition comprising an acrylic copolymer having a glass transition point of 10 to 70 ° C. has excellent blocking resistance and long-term storability, leading to the present invention.
That is, the first invention of the present invention is
At least with water,
Methylene blue, which is a redox dye,
D-glucose as a reducing agent;
10 to 70 ° C. Der glass transition point with an acid value of from 50 to 300 / g is, acrylic acid, styrene, and (meth) obtained by polymerizing an acrylic acid ester <br/> alkali-soluble water It is an oxygen indicator composition characterized by comprising a water-soluble acrylic polymer or an emulsion-type acrylic copolymer.
According to a second aspect of the present invention, the oxygen indicator composition further contains at least one red pigment selected from the group of insoluble azo pigments, condensed azo pigments, and condensed polycyclic pigments as a colorant. And an oxygen indicator composition.
A third invention is an oxygen indicator, wherein the oxygen indicator composition is formed on a substrate by printing, and an oxygen indicator function is integrated with a packaging material and / or an oxygen scavenger.
本発明の酸素インジケーター組成物は、従来の酸素インジケーター組成物と比較して、流動性やレベリング性、溶解性や版かぶり性といった印刷適性および耐ブロッキング性や接着性といった塗膜物性に優れ、安定した発色、有酸素状態→脱酸素状態および脱酸素状態→有酸素状態の変化に対する変色も極めて良好である。
また、本発明のインジケーターは、酸素インジケーター組成物が印刷により基材上に形成され、酸素インジケーター機能が包装材および／または脱酸素剤と一体となっている為、現在広く実用化されている錠剤型の酸素インジケーターの（１）個々に錠剤を包装しなければならない、（２）小袋に空けた穴を通して崩壊した錠剤粉末が外部へ流出する場合がある、（３）錠剤の誤飲事故に繋がる危険性がある、（４）錠剤を包装材内に固定することが困難である、（５）錠剤が包装材内で動き、外部から目視検知しにくいなどの種々の問題点を一気に解決する事が可能となり、その工業的価値は極めて多大である。
Compared with conventional oxygen indicator compositions, the oxygen indicator composition of the present invention has excellent printing properties such as fluidity, leveling properties, solubility and plate fogging, and coating film properties such as blocking resistance and adhesiveness, and is stable. The developed color, aerobic state → deoxygenated state and deoxygenated state → color change with respect to the change of aerobic state are also very good.
Moreover, the indicator of the present invention is a tablet that is currently widely used because the oxygen indicator composition is formed on a substrate by printing and the oxygen indicator function is integrated with the packaging material and / or the oxygen scavenger. Oxygen indicator of the mold (1) The tablets must be individually packaged, (2) Disintegrated tablet powder may flow out through the hole in the sachet, (3) It will lead to accidental ingestion of tablets There are dangers, (4) It is difficult to fix the tablet in the packaging material, (5) The tablet moves in the packaging material, and it is difficult to visually detect it from the outside. And its industrial value is enormous.
次に、本発明の酸素インジケーター組成物および酸素インジケーターについて詳細に説明する。本発明における酸素インジケーター組成物は、酸化還元色素、還元剤、アクリル系共重合体、アルカリ化剤、溶媒から構成され、更に酸化還元色素以外の着色剤、必要に応じて保湿剤、消泡剤や分散剤などの各種添加剤が使用される。 Next, the oxygen indicator composition and oxygen indicator of the present invention will be described in detail. The oxygen indicator composition in the present invention is composed of a redox dye, a reducing agent, an acrylic copolymer, an alkalizing agent, and a solvent. Further, a colorant other than the redox dye, and if necessary, a humectant and an antifoaming agent. And various additives such as dispersants are used.
本発明の酸素インジケーター組成物に用いられる酸化還元色素としては、着色力および水やアルコールに対する溶解性の観点よりメチレンブルーが使用される。メチレンブルーは無酸素下では還元剤の働きによって還元型、すなわち無色を呈し、有酸素下では酸素により酸化され、青色を呈する。
メチレンブルーの含有量は、有酸素下で十分な青色濃度を得る観点から０．００１重量％以上、水やアルコールに対する溶解性の観点から１０．０重量％以下の範囲が好ましく、更に０．０５〜５．０重量％の範囲がより好ましい。
As the redox dye used in the oxygen indicator composition of the present invention, methylene blue is used from the viewpoint of coloring power and solubility in water and alcohol. Methylene blue exhibits a reduced form, that is, colorless by the action of a reducing agent in the absence of oxygen, and is oxidized by oxygen and exhibits a blue color in the presence of oxygen.
The content of methylene blue is preferably 0.001% by weight or more from the viewpoint of obtaining a sufficient blue density under aerobic conditions, and 10.0% by weight or less from the viewpoint of solubility in water or alcohol, and more preferably 0.05 to A range of 5.0% by weight is more preferred.
本発明の酸素インジケーター組成物に用いられる還元剤としては、耐光性や耐熱性、長期保存、流通時の発色の安定性の観点よりＤ−グルコースが使用される。還元剤の含有量は、５．０〜６０．０重量％の範囲が好ましいが、１０．０〜５０．０重量％の範囲とするのがより好ましい。含有量が５．０重量％未満であるとメチレンブルーを十分に還元することができず、６０．０重量％を超えるとラミネート強度やブロッキングが低下するため好ましくない。 As the reducing agent used in the oxygen indicator composition of the present invention, D-glucose is used from the viewpoint of light resistance, heat resistance, long-term storage, and stability of color development during distribution. The content of the reducing agent is preferably in the range of 5.0 to 60.0% by weight, but more preferably in the range of 10.0 to 50.0% by weight. If the content is less than 5.0% by weight, methylene blue cannot be sufficiently reduced, and if it exceeds 60.0% by weight, the laminate strength and blocking are undesirably lowered.
酸化還元色素やそれ以外の着色剤、還元剤などを基材上に固着するためのバインダーとしては、アクリル系共重合体を挙げることができる。アクリル系樹脂は、アルカリ可溶型水溶性アクリル系共重合体またはエマルション型アクリル系共重合体を単独または併用して使用することができる。
アルカリ可溶型水溶性アクリル系共重合体またはエマルション型アクリル系共重合体は，従来からよく知られている塊状重合，溶液重合，乳化重合，懸濁重合などの重合法に従い製造できる。
アルカリ可溶型水溶性アクリル系共重合体としては、アクリル系、スチレン系、その他ラジカル重合可能なビニルモノマーから通常の方法により得られる共重合体樹脂であり、無機アルカリまたは有機アミン等で中和し、水溶化した物を用いることができる。用いられるビニルモノマーとしては、例えば、（メタ）アクリル酸エステル類、（メタ）アクリル酸、（メタ）アクリルアミド類、アクリロニトリル等の各種アクリル系モノマー、スチレン、α−メチルスチレン、ブチルスチレン等のスチレン等のスチレン系モノマー、マレイン酸、マレイン酸ハーフエステル類、マレイン酸ジエステル類、その他不飽和カルボン酸エステル等が挙げられ、これらは１種または２種以上を混合して使用できる。
Examples of the binder for fixing the redox dye, other colorant, reducing agent, etc. on the base material include acrylic copolymers. As the acrylic resin, an alkali-soluble water-soluble acrylic copolymer or an emulsion-type acrylic copolymer can be used alone or in combination.
The alkali-soluble water-soluble acrylic copolymer or emulsion-type acrylic copolymer can be produced according to polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization that are well known in the art.
Alkali-soluble water-soluble acrylic copolymer is a copolymer resin obtained from acrylic, styrene, or other radically polymerizable vinyl monomers by a conventional method, and neutralized with an inorganic alkali or organic amine. However, a water-soluble product can be used. Examples of vinyl monomers used include (meth) acrylic acid esters, (meth) acrylic acid, (meth) acrylamides, various acrylic monomers such as acrylonitrile, styrene such as styrene, α-methylstyrene, and butylstyrene. Styrene monomers, maleic acid, maleic acid half esters, maleic acid diesters, and other unsaturated carboxylic acid esters. These may be used alone or in combination of two or more.
重合開始剤としては，過酸化ベンゾイル，アゾビスイソブチロニトリル等の触媒を用いることができる。また，反応系には必要に応じてメルカプタン類等を添加することができ，これにより適宜重合度を調整することができる。 As the polymerization initiator, a catalyst such as benzoyl peroxide or azobisisobutyronitrile can be used. Further, mercaptans and the like can be added to the reaction system as necessary, and the degree of polymerization can be adjusted accordingly.
重合反応終了後，反応系内にアンモニア、モノエタノールアミン、ジエタノールアミン、N,N-ジメチルアミノエタノール等の有機アミン類、水酸化ナトリウム、水酸化カリウム等の無機アルカリ類等の中和剤を添加して中和させることにより，所望の水溶性樹脂とすることができる。中和剤の添加量は，樹脂中のカルボキシル基の中和率が約７０〜１２０％となる範囲が好適である。 After completion of the polymerization reaction, neutralizing agents such as ammonia, monoethanolamine, diethanolamine, organic amines such as N, N-dimethylaminoethanol, and inorganic alkalis such as sodium hydroxide and potassium hydroxide are added to the reaction system. The desired water-soluble resin can be obtained by neutralization. The addition amount of the neutralizing agent is preferably in a range where the neutralization rate of the carboxyl group in the resin is about 70 to 120%.
次にエマルション型アクリル系共重合体としては、例えばアクリル系、スチレン系、その他の前述ビニルモノマーを通常の乳化重合により得られる樹脂を用いることが出来る。乳化重合の際に用いられる界面活性剤としては、アニオン系界面活性剤、ノニオン系界面活性剤等通常に用いられるものが使用できる。或いは界面活性剤の代わりにポリマー粒子の分散保護能を有するアルカリ可溶型水溶性アクリル系共重合体のような高分子活性剤の存在下、上記記載のラジカル重合可能なビニルモノマーを乳化重合することにより得ることができる。 Next, as the emulsion type acrylic copolymer, for example, an acrylic resin, a styrene resin, or other resins obtained by usual emulsion polymerization of the aforementioned vinyl monomers can be used. As the surfactant used in the emulsion polymerization, those usually used such as an anionic surfactant and a nonionic surfactant can be used. Alternatively, the above-described radically polymerizable vinyl monomer is emulsion-polymerized in the presence of a polymer surfactant such as an alkali-soluble water-soluble acrylic copolymer that has the ability to protect the dispersion of polymer particles in place of the surfactant. Can be obtained.
アルカリ可溶型水溶性アクリル系共重合体またはエマルション型アクリル系共重合体の酸価は、５０〜３００ｍｇＫＯＨ／ｇの範囲であることが必要だが、１００〜２５０ｍｇＫＯＨ／ｇの範囲とするのがより好ましい。酸価が５０ｍｇＫＯＨ／ｇ未満であるとアクリル系共重合体は水溶性に乏しく、酸素インジケーター組成物として使用した際に溶解性が不良となり、版かぶりや版詰まりといったトラブルが生じる。また樹脂の保湿効果が乏しく、発色が安定しない。酸価が３００ｍｇＫＯＨ／ｇを超えるとアルカリ化剤の添加によりアクリル系共重合体の増粘によって酸素インジケーター組成物の粘度が上昇、流動性が低下し、レベリング性や版かぶり性などの印刷適性に悪影響を与えるため好ましくない。 The acid value of the alkali-soluble water-soluble acrylic copolymer or emulsion-type acrylic copolymer needs to be in the range of 50 to 300 mgKOH / g, but is more preferably in the range of 100 to 250 mgKOH / g. preferable. When the acid value is less than 50 mgKOH / g, the acrylic copolymer is poor in water solubility, and when used as an oxygen indicator composition, the solubility becomes poor, causing problems such as plate fog and plate clogging. In addition, the moisturizing effect of the resin is poor and the color development is not stable. When the acid value exceeds 300 mgKOH / g, the viscosity of the oxygen indicator composition increases due to the thickening of the acrylic copolymer due to the addition of the alkalizing agent, the fluidity decreases, and the printability such as leveling and plate fogging is improved. Unfavorable because it adversely affects.
アルカリ可溶型水溶性アクリル系共重合体またはエマルション型アクリル系共重合体のガラス転移点は、１０〜７０℃の範囲であることが必要だが、２０〜６０℃の範囲とするのがより好ましい。ガラス転移点が１０℃未満であるとブロッキングが低下し、ガラス転移点が７０℃を超えると、印刷時の乾燥熱風で十分に造膜せず、基材への接着性が低下するため好ましくない。アルカリ可溶型水溶性アクリル系共重合体またはエマルション型アクリル系共重合体の含有量は、基材との十分な接着性を得る観点から３．０重量％以上、耐ブロッキング性や酸素インジケーター組成物の粘度の観点から３０．０重量％以下の範囲が好ましく、更に５．０〜２０．０重量％の範囲がより好ましい。 The glass transition point of the alkali-soluble water-soluble acrylic copolymer or emulsion-type acrylic copolymer needs to be in the range of 10 to 70 ° C, but more preferably in the range of 20 to 60 ° C. . When the glass transition point is less than 10 ° C., blocking is reduced, and when the glass transition point exceeds 70 ° C., it is not preferable because the film is not sufficiently formed with dry hot air at the time of printing and the adhesion to the substrate is reduced. . The content of the alkali-soluble water-soluble acrylic copolymer or emulsion-type acrylic copolymer is 3.0% by weight or more from the viewpoint of obtaining sufficient adhesion to the base material, blocking resistance and oxygen indicator composition From the viewpoint of the viscosity of the product, a range of 30.0% by weight or less is preferable, and a range of 5.0 to 20.0% by weight is more preferable.
更に必要に応じて、アルカリ可溶型水溶性アクリル系共重合体またはエマルション型アクリル系共重合体には水性樹脂を併用することもできる。併用する水性樹脂は、一般の水性インキおよび水性塗料などに使用される水溶性または水分散性樹脂であり、例えばポリウレタン樹脂、ポリウレタンウレア樹脂、アクリル変性ウレタン樹脂、アクリル変性ウレタンウレア樹脂、スチレン−マレイン酸共重合樹脂、ポリエステル樹脂、シェラック、ロジン変性マレイン酸樹脂、塩化ビニル−酢酸ビニル共重合樹脂、塩化ビニル−アクリル酸共重合樹脂、塩素化ポリプロピレン樹脂、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ブチラールなどを挙げることができる。これらの樹脂は、単独で、または２種以上を混合して用いることができる。 Further, if necessary, an aqueous resin can be used in combination with the alkali-soluble water-soluble acrylic copolymer or emulsion-type acrylic copolymer. The water-based resin used in combination is a water-soluble or water-dispersible resin used for general water-based inks and water-based paints. For example, polyurethane resin, polyurethane urea resin, acrylic modified urethane resin, acrylic modified urethane urea resin, styrene-malein. Examples include acid copolymer resins, polyester resins, shellac, rosin-modified maleic acid resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-acrylic acid copolymer resins, chlorinated polypropylene resins, hydroxyethyl cellulose, hydroxypropyl cellulose, butyral, etc. be able to. These resins can be used alone or in admixture of two or more.
酸価が５０〜３００ｍｇＫＯＨ／ｇであるとともにガラス転移点が１０〜７０℃であるアクリル系共重合体の中和剤としての役割と、還元剤の酸化を促進する目的で含有されるアルカリ化剤としては、本発明酸素インジケーター組成物をアルカリ性にすることのできるものであればよい。その例としては、アンモニア、有機アミン類、アルカリ金属又はアルカリ土類金属の水酸化物、炭酸塩、炭酸水素塩、リン酸塩、ホウ酸塩等の水溶性化合物等が挙げられる。これらは含水物でも無水物でもよい。具体的には、例えばアンモニア、トリエチルアミン、アミノメチルプロパノール、モノエタノールアミン、ジエチルアミノエタノール、ホウ酸ナトリウム、水酸化ナトリウム、珪酸ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、水酸化リチウム、リン酸カリウム、水酸化バリウム、水酸化マグネシウム、リン酸カリウム等が例示できる。これらの中でもホウ酸ナトリウム、水酸化ナトリウム、珪酸ナトリウムは好適に使用できる。これらはその一種を単独で用いてもよく二種以上を併用することもできる。 A role as a neutralizing agent for an acrylic copolymer having an acid value of 50 to 300 mgKOH / g and a glass transition point of 10 to 70 ° C., and an alkalizing agent contained for the purpose of promoting oxidation of the reducing agent As long as it is possible to make the oxygen indicator composition of the present invention alkaline. Examples thereof include ammonia, organic amines, alkali metal or alkaline earth metal hydroxides, water-soluble compounds such as carbonates, bicarbonates, phosphates and borates. These may be hydrated or anhydrous. Specifically, for example, ammonia, triethylamine, aminomethylpropanol, monoethanolamine, diethylaminoethanol, sodium borate, sodium hydroxide, sodium silicate, sodium carbonate, sodium bicarbonate, lithium hydroxide, potassium phosphate, barium hydroxide Examples thereof include magnesium hydroxide and potassium phosphate. Among these, sodium borate, sodium hydroxide, and sodium silicate can be preferably used. These may be used alone or in combination of two or more.
アルカリ化剤は、酸素インジケーター組成物が印刷時にｐＨ１０〜１４の範囲となるように添加される。しかし、高アルカリ領域で酸素インジケーター組成物が長期間貯蔵された場合、還元剤の酸化劣化が生じて十分な色調変化反応が得られない場合がある。酸素インジケーター組成物はｐＨ７〜１０の範囲となるよう調整して貯蔵し、印刷直前にｐＨ１０〜１４の範囲となるよう更にアルカリ化剤を添加する方法が好ましい。 The alkalizing agent is added so that the pH of the oxygen indicator composition is in the range of 10 to 14 at the time of printing. However, when the oxygen indicator composition is stored for a long period of time in a high alkali region, there may be a case where a sufficient color change reaction cannot be obtained due to oxidative degradation of the reducing agent. The oxygen indicator composition is preferably adjusted and stored so that the pH is in the range of 7 to 10, and further an alkalinizing agent is added so that the pH is in the range of 10 to 14 immediately before printing.
本発明の酸素インジケーター組成物は、酸素の存在有無による色相変化をより一層明確なものとするために、酸素の存在有無に係わらず色相の変化を伴わない着色剤を併用することもできる。
併用する着色剤としては、一般のインキ、塗料、および記録剤などに使用されている有機、無機顔料や染料を挙げることができる。
The oxygen indicator composition of the present invention can be used in combination with a colorant that does not cause a change in hue regardless of the presence or absence of oxygen in order to further clarify the hue change due to the presence or absence of oxygen.
Examples of the colorant used in combination include organic and inorganic pigments and dyes used in general inks, paints, and recording agents.
有機顔料としては、アゾ系、フタロシアニン系、アントラキノン系、ペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサジン系、イソインドリノン系、キノフタロン系、アゾメチンアゾ系、ジクトピロロピロール系、イソインドリン系などの顔料が挙げられる。無機顔料としては、カーボンブラック、酸化チタン、酸化亜鉛、硫化亜鉛、硫酸バリウム、炭酸カルシウム、酸化クロム、シリカ、ベンガラなどが挙げられる。染料としては、アゾ系、アンスラキノン系、ペリレン系、ペリノン系、チオインジゴ系などの顔料が挙げられる。これらの顔料や染料は、単独で、または色相および濃度の調整などを目的として２種以上を混合して用いることもできるが、耐光性の観点より顔料の使用が好ましい。 Organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, isoindoline, etc. Pigments. Examples of inorganic pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, and bengara. Examples of the dye include azo, anthraquinone, perylene, perinone, and thioindigo pigments. These pigments and dyes can be used alone or in admixture of two or more for the purpose of adjusting hue and density, but the use of pigments is preferred from the viewpoint of light resistance.
市販されている多くの酸素インジケーターは、酸化還元色素としてメチレンブルーを用い、更に赤系着色剤を添加することによって、無酸素時は赤〜ピンク色、有酸素時は青〜紫色となり、酸素の存在有無をより識別しやすいように着色されている。
メチレンブルーに併用する赤系着色剤としては、C.I.Pigment Red 23、C.I.Pigment Red 146、C.I.Pigment Red 185、C.I.Pigment Red 238等の不溶性アゾ顔料、C.I.Pigment Red 144、C.I.Pigment Red 166、C.I.Pigment Red 220、C.I.Pigment Red 211、C.I.Pigment Red 242等の縮合アゾ顔料、C.I.Pigment Red 122等の縮合多環系顔料が好適に使用できる。
メチレンブルーに併用する赤系着色剤の含有量は、無酸素下で十分な赤色濃度を得る観点から０．１重量％以上、有酸素時にはメチレンブルーの青色と混色して紫色を呈し、酸素の存在有無を識別しやすくするために５．０％重量％以下の範囲が好ましい。
C.I.Pigment Red 48:1、C.I.Pigment Red 48:2、C.I.Pigment Red 57:1等のアゾレーキ顔料は、ホウ酸ナトリウム、水酸化ナトリウム、珪酸ナトリウム等のアルカリ化剤の添加により着色剤の変色や退色が生じ、発色が安定しないため好ましくない。
Many commercially available oxygen indicators use methylene blue as a redox dye, and by adding a red colorant, red to pink when anoxic, blue to purple when aerobic, and the presence of oxygen It is colored to make it easier to identify the presence or absence.
Red colorants used in combination with methylene blue include insoluble azo pigments such as CIPigment Red 23, CIPigment Red 146, CIPigment Red 185, and CIPigment Red 238, CIPigment Red 144, CIPigment Red 166, CIPigment Red 220, CIPigment Red 211, and CIPigment Red Condensed azo pigments such as 242 and condensed polycyclic pigments such as CIPigment Red 122 can be suitably used.
The content of the red colorant used in combination with methylene blue is 0.1% by weight or more from the viewpoint of obtaining a sufficient red density in the absence of oxygen. Is preferably in the range of 5.0% by weight or less.
Azo lake pigments such as CIPigment Red 48: 1, CIPigment Red 48: 2 and CIPigment Red 57: 1 cause discoloration and fading of the colorant due to the addition of an alkalinizing agent such as sodium borate, sodium hydroxide, sodium silicate, This is not preferable because the color development is not stable.
溶媒としては、水あるいは水混和性有機溶剤を使用することができる。水混和性有機溶剤としては，メチルアルコール，エチルアルコール，イソプロピルアルコール，N-プロピルアルコール等のアルコール類，エチレングリコール，プロピレングリコール等のグリコール類，グリセリン等の多価アルコール類、メチルセロソルブ，エチルセロソルブ，ブチルセロソルブ，プロピレングリコール，プロピレングリコールモノメチルエーテル，ジエチレングリコールモノメチルエーテル，ジエチレングリコールモノエチルエーテル，ジエチレングリコールモノブチルエーテル等のグリコールエーテル類が挙げられる。これらの水や水混和性有機溶剤は単独で、または２種以上を混合して用いることができる。この中でエチレングリコール，プロピレングリコール等のグリコール類，グリセリン等の多価アルコール類は、酸素インジケーター組成物中の水分を保持し、酸化還元色素の呈色反応を促進する保湿剤としての働きがあるが、含有量が５％を超えるとブロッキングが低下する。本発明の酸素インジケーター組成物は、還元剤であるＤ−グルコースやバインダーであるアルカリ可溶型水溶性アクリル系共重合体またはエマルション型アクリル系共重合体も保湿剤の役割も果たすので、グリコール類や多価アルコール類等の保湿剤の含有量は５重量％以下とすることが可能である。 As the solvent, water or a water-miscible organic solvent can be used. Examples of water-miscible organic solvents include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and N-propyl alcohol, glycols such as ethylene glycol and propylene glycol, polyhydric alcohols such as glycerin, methyl cellosolve, ethyl cellosolve, Examples include glycol ethers such as butyl cellosolve, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. These water and water-miscible organic solvents can be used alone or in admixture of two or more. Among them, glycols such as ethylene glycol and propylene glycol, and polyhydric alcohols such as glycerin function as a moisturizing agent that retains moisture in the oxygen indicator composition and promotes a color reaction of the redox dye. However, if the content exceeds 5%, blocking is reduced. Since the oxygen indicator composition of the present invention also serves as a moisturizing agent as well as D-glucose as a reducing agent and an alkali-soluble water-soluble acrylic copolymer or emulsion acrylic copolymer as a binder, glycols The content of humectants such as polyhydric alcohols and the like can be 5% by weight or less.
本発明の酸素インジケーター組成物は、その他、必要に応じて体質顔料、顔料分散剤、レベリング剤、消泡剤、ワックス、硬化剤、シランカップリング剤、防錆剤、防腐剤、可塑剤、赤外線吸収剤、紫外線吸収剤、耐光性向上剤、芳香剤、難燃剤などの添加剤を加えることもできる。 The oxygen indicator composition of the present invention may be an extender pigment, a pigment dispersant, a leveling agent, an antifoaming agent, a wax, a curing agent, a silane coupling agent, a rust preventive, a preservative, a plasticizer, and an infrared ray as necessary. Additives such as an absorbent, an ultraviolet absorber, a light fastness improver, a fragrance, and a flame retardant can also be added.
レベリング剤としては、アセチレンジオール、変性ポリシロキサン、フッ素系界面活性剤、アニオン系界面活性剤、ポリオキシレン直鎖脂肪族アルコールやポリオキシレン分岐脂肪族アルコール、非イオン性界面活性剤例えば脂肪族アルコールアルキレンオキサイド付加物、アルキルフェノールアルキレンオキサイド付加物、脂肪族アルキレンオキサイド付加物、高級アルキルアミンアルキレンオキサイド付加物、脂肪族アミドアルキレンオキサイド付加物、ソルビトール又はソルビタンの脂肪族エステル等を挙げることができ、単独で、または２種以上を混合して用いることができる。上記のうち、レベリング性および消泡性の観点よりアセチレンジオール系レベリング剤を使用することが好ましい。 Examples of the leveling agent include acetylene diol, modified polysiloxane, fluorine-based surfactant, anionic surfactant, polyoxylene linear aliphatic alcohol and polyoxylene branched aliphatic alcohol, nonionic surfactant such as aliphatic alcohol alkylene. Oxide adducts, alkylphenol alkylene oxide adducts, aliphatic alkylene oxide adducts, higher alkyl amine alkylene oxide adducts, aliphatic amide alkylene oxide adducts, sorbitol or aliphatic esters of sorbitan, etc. Or 2 or more types can be mixed and used. Among the above, it is preferable to use an acetylenic diol leveling agent from the viewpoint of leveling properties and antifoaming properties.
消泡剤としては、シリコーン系消泡剤例えばジメチルポリシロキサン、メチルフェニルポリシロキサン、メチルビニルポリシロキサンなどのシリコーンオイルを微粉末シリカと混合したオイルコンパウンド型消泡剤、これらのオイルコンパウンドを界面活性剤と共に水中に分散してなるエマルジョン型消泡剤、ポリエーテル系消泡剤例えばステアリルアルコール、ジプロピレングリコール、グリセリンおよびソルビタンなどの１価〜多価のアルコールにアルキレンオキシドを付加したものやアルキルフェノールにアルキレンオキシドを付加したもの、またはこれらの末端水酸基をエステル化したもの、鉱油系消泡剤、油脂系消泡剤、脂肪酸系消泡剤、脂肪酸エステル系消泡剤、高級アルコール系消泡剤、金属セッケン系消泡剤等を挙げることができ、単独で、または２種以上を混合して用いることができる。 Antifoaming agents include silicone-based antifoaming agents such as dimethylpolysiloxane, methylphenylpolysiloxane, methylvinylpolysiloxane, and other oil compound type antifoaming agents mixed with fine powdered silica, and these oil compounds are surface active. Emulsion-type antifoaming agent dispersed in water together with the agent, polyether antifoaming agents such as those obtained by adding alkylene oxide to monohydric to polyhydric alcohols such as stearyl alcohol, dipropylene glycol, glycerin and sorbitan, and alkylphenols Those added with alkylene oxide, or those obtained by esterifying these terminal hydroxyl groups, mineral oil-based antifoaming agents, fat-based antifoaming agents, fatty acid-based antifoaming agents, fatty acid ester-based antifoaming agents, higher alcohol-based antifoaming agents, Name metal soap antifoam Can, it can be used alone or in combination of two or more.
耐光性向上剤としては、酢酸コバルト、安息香酸コバルト、ステアリン酸コバルト等を挙げることができ、単独で、または２種以上を混合して用いることができる。 Examples of the light fastness improver include cobalt acetate, cobalt benzoate, and cobalt stearate, and these can be used alone or in combination of two or more.
本発明の酸素インジケーター組成物は、一般に使用される分散機、例えばディソルバー、ローラーミル、ボールミル、ペブルミル、アトライター、サンドミルなどを用いて製造することができる。酸素インジケーター組成物中に気泡や予期せずに粗大粒子などが含まれる場合は、印刷物品質を低下させるため、濾過などにより取り除くことが好ましい。濾過器は従来公知のものを使用することができる。
本発明の酸素インジケーター組成物の粘度は、顔料の沈降を防ぐ観点から１０ｍＰａ・ｓ以上、酸素インジケーター組成物製造時や印刷時の作業性や版かぶり性、レベリング性などの印刷適性の観点から１０００ｍＰａ・ｓ以下が好ましい。更に１０〜５００ｍＰａ・ｓの範囲がより好ましい。尚、本発明における粘度とは、回転粘度計(ＢＭ型粘度計、２５℃下測定)を用いた方法で得られた値である。
The oxygen indicator composition of the present invention can be produced using a commonly used disperser such as a dissolver, a roller mill, a ball mill, a pebble mill, an attritor, and a sand mill. When bubbles or unexpectedly large particles are contained in the oxygen indicator composition, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.
The viscosity of the oxygen indicator composition of the present invention is 10 mPa · s or more from the viewpoint of preventing pigment settling, and 1000 mPa from the viewpoint of printing suitability such as workability, plate fogging, and leveling properties at the time of producing or printing the oxygen indicator composition. -S or less is preferable. Furthermore, the range of 10-500 mPa * s is more preferable. The viscosity in the present invention is a value obtained by a method using a rotational viscometer (BM type viscometer, measured at 25 ° C.).
本発明の酸素インジケーター組成物を塗布する方法としては、グラビア印刷、フレキソ印刷、凸版印刷、スクリーン印刷、オフセット印刷などの印刷法や、ロールコーティング、スプレーコーティング、ディップコーティングなどのコーティング法が挙げられるが、グラビア印刷法またはフレキソ印刷法による塗布が好適である。 Examples of the method of applying the oxygen indicator composition of the present invention include printing methods such as gravure printing, flexographic printing, letterpress printing, screen printing, and offset printing, and coating methods such as roll coating, spray coating, and dip coating. Application by gravure printing or flexographic printing is preferred.
本発明の酸素インジケーター組成物は上記印刷法により基材上に形成された後、他のフィルムや紙などと積層され、酸素インジケーター機能が一体となった包装材および／または脱酸素剤となる。 The oxygen indicator composition of the present invention is formed on a substrate by the above printing method, and then laminated with another film or paper to become a packaging material and / or an oxygen scavenger with an integrated oxygen indicator function.
酸素インジケーター機能が一体となった包装材において使用される基材としては、例えばポリ塩化ビニリデン(ＰＶＤＣ)系フィルム、ポリビニルアルコール(ＰＶＡ、ビニロン)系フィルム、ＥＶＯＨ(エチレンとビニルアルコールの共重合体)系フィルム、ＭＸＤ(メチルキシリレンジアミン)系フィルム、金属酸化物蒸着(透明蒸着)系フィルム、アクリル酸系樹脂コートフィルムなどのガスバリア性フィルムが挙げられる。
上記ガスバリア性フィルムに積層するシーラントフィルムとしては、ポリエチレン、ポリプロピレン、ポリエステル、ポリスチレン、ポリメチルペンテンなどが挙げられるが、特にガス透過性と熱接着性を有する低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、アイオノマー、エチレン−酢酸ビニル共重合体が好適に使用される。微細孔シーラントフィルムを使用することもできる。
Examples of the base material used in the packaging material in which the oxygen indicator function is integrated include, for example, polyvinylidene chloride (PVDC) film, polyvinyl alcohol (PVA, vinylon) film, EVOH (copolymer of ethylene and vinyl alcohol). Examples thereof include gas barrier films such as film, MXD (methylxylylenediamine) film, metal oxide vapor deposition (transparent vapor deposition) film, and acrylic acid resin coat film.
Examples of the sealant film laminated on the gas barrier film include polyethylene, polypropylene, polyester, polystyrene, polymethylpentene, and the like. Particularly, low-density polyethylene, linear low-density polyethylene having gas permeability and thermal adhesiveness, Polypropylene, ionomer, and ethylene-vinyl acetate copolymer are preferably used. A microporous sealant film can also be used.
上記基材とシーラントを積層する方法としては、ドライラミネート法やウェットラミネート法、エクストルージョンラミネート法、ホットメルトラミネート法等、公知の積層方法が利用できる。
酸素インジケーター組成物をガスバリア性フィルムに塗布した後にシーラントフィルムと積層しても良いし、酸素インジケーター組成物をシーラントフィルムに塗布した後にガスバリア性フィルムと積層することもできる。酸素インジケーター組成物をガスバリア性フィルムとシーラントフィルムの両方に塗布する事も可能である。
上記方法によって積層された包装材に、食品、医薬品、電子部材、電子製品などの内容物とともに脱酸素剤が充填される。
As a method of laminating the base material and the sealant, a known laminating method such as a dry laminating method, a wet laminating method, an extrusion laminating method, or a hot melt laminating method can be used.
The oxygen indicator composition may be applied to the gas barrier film and then laminated with the sealant film, or the oxygen indicator composition may be applied to the sealant film and then laminated with the gas barrier film. It is also possible to apply the oxygen indicator composition to both the gas barrier film and the sealant film.
The packaging material laminated by the above method is filled with an oxygen scavenger together with contents such as foods, pharmaceuticals, electronic members, and electronic products.
脱酸素剤の代表的な積層構成としては、例えば微細孔フィルム／撥水撥油剤コート紙／微細孔シーラントフィルム(／脱酸素剤)が挙げられる。
酸素インジケーター機能が一体となった脱酸素剤において使用される微細孔フィルムとしては、例えば二軸延伸ポリプロピレン、無延伸ポリプロピレン、ポリエステル、ナイロンなど、ドライラミネート法やエクストルージョンラミネート法などの積層方法によって紙と接着可能なフィルムを使用する事ができる。あらかじめ微細孔加工されたフィルムを用いることもできるし、酸素インジケーター組成物を塗布した後に細孔を開ける事も可能である。
上記撥水撥油剤コート紙としては、撥水撥油剤コート剤を塗布した紙が挙げられる。微細孔シーラントフィルムとしては、熱接着性を有する低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、アイオノマー、エチレン−酢酸ビニル共重合体が好適に使用できる。
上記微細孔フィルムと撥水撥油剤コート紙と微細孔シーラントフィルムとを積層する方法としては、ドライラミネート法やウェットラミネート法、エクストルージョンラミネート法、ホットメルトラミネート法等の公知の積層方法が利用できる。撥水撥油剤コート紙と微細孔シーラントフィルムとを積層する場合には、接着剤やアンカーコート剤を使用せずに、熱圧着にて積層するサーマルラミネート方式を利用することも可能である。
As a typical laminated structure of the oxygen scavenger, for example, a microporous film / water / oil repellent coated paper / microporous sealant film (/ oxygen scavenger) can be mentioned.
As a microporous film used in an oxygen scavenger with an integrated oxygen indicator function, for example, biaxially stretched polypropylene, unstretched polypropylene, polyester, nylon, etc., paper by a laminating method such as a dry laminating method or an extrusion laminating method is used. And a film that can be glued can be used. It is also possible to use a film that has been finely processed in advance, or to open pores after applying the oxygen indicator composition.
Examples of the water / oil repellent coated paper include paper coated with a water / oil repellent coated agent. As the microporous sealant film, low-density polyethylene having thermal adhesion, linear low-density polyethylene, polypropylene, ionomer, and ethylene-vinyl acetate copolymer can be suitably used.
As a method for laminating the microporous film, the water / oil repellent coated paper and the microporous sealant film, a known laminating method such as a dry laminating method, a wet laminating method, an extrusion laminating method, or a hot melt laminating method can be used. . When laminating the water / oil repellent coated paper and the microporous sealant film, it is also possible to use a thermal laminating method in which lamination is performed by thermocompression bonding without using an adhesive or an anchor coat agent.
酸素インジケーター組成物は、上記フィルムや微細孔フィルムまたは／および撥水撥油剤コート紙にグラビア印刷、フレキソ印刷など公知の方法によって塗布される。酸素インジケーター組成物を紙に塗布した後に撥水撥油剤コート剤を塗布する事も可能である。
ガスバリア性フィルムとシーラントフィルムが積層されて形成された包装材に、食品、医薬品、電子部材、電子製品などの内容物とともに、酸素インジケーター機能が一体となった脱酸素剤が充填される。
酸素インジケーター機能は包装材および脱酸素剤の両方に付与することもできる。
The oxygen indicator composition is applied to the film, microporous film, and / or water / oil repellent coated paper by a known method such as gravure printing or flexographic printing. It is also possible to apply a water / oil repellent coating agent after the oxygen indicator composition is applied to paper.
A packaging material formed by laminating a gas barrier film and a sealant film is filled with an oxygen scavenger integrated with an oxygen indicator function together with contents such as food, pharmaceuticals, electronic members, and electronic products.
The oxygen indicator function can also be imparted to both the packaging material and the oxygen scavenger.
以下、本発明の実施例について具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、実施例および比較例中の部は重量部を、％は重量％を表す。 Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. In addition, the part in an Example and a comparative example represents a weight part, and% represents weight%.
〔製造例１〕攪拌装置、温度計、滴下装置および還流冷却管を備えた反応容器に、水３００部、アニオン系活性剤(ローヌ・プーラン社製「Alipol C0436」)１部および重合開始剤として過硫酸アンモニウム塩２部を仕込み６０℃に昇温後窒素ガス置換した。次に、表１中の製造例１および２に示す組成のモノマー混合物２００部を２時間で滴下した。この間、反応温度は６０〜７５℃に保った。モノマー混合物を滴下後、７５℃で２時間熟成させて固形分４０％のアクリル系共重合体エマルション(ａ)および(ｂ)を得た。 [Production Example 1] In a reaction vessel equipped with a stirrer, a thermometer, a dropping device and a reflux condenser, 300 parts of water, 1 part of an anionic activator ("Alipol C0436" manufactured by Rhone-Poulenc) and a polymerization initiator 2 parts of ammonium persulfate was charged, and the temperature was raised to 60 ° C., followed by replacement with nitrogen gas. Next, 200 parts of a monomer mixture having the composition shown in Production Examples 1 and 2 in Table 1 was dropped in 2 hours. During this time, the reaction temperature was kept at 60-75 ° C. After dropping the monomer mixture, the mixture was aged at 75 ° C. for 2 hours to obtain acrylic copolymer emulsions (a) and (b) having a solid content of 40%.
〔製造例３〜９〕攪拌装置、温度計、滴下装置および還流冷却管を備えた反応容器に、イソプロピルアルコール３００部を仕込み８３℃に昇温後窒素ガス置換し、表１中の製造例３〜９に示す組成のモノマー混合物２００部および重合開始剤としてアゾビスイソブチロニトリル６部を２時間で滴下した後、８３℃で４時間反応させた。次に、反応生成物中のカルボキシル基と当量のアンモニアを含有するアンモニア水６００部を添加した後、イソプロピルアルコールを減圧留去させて固形分２５％の水溶性アクリル系共重合体(ｃ)、(ｄ)、(ｅ)、(ｆ)、(ｇ)、(ｈ)、(ｉ)を得た。 [Production Examples 3 to 9] In a reaction vessel equipped with a stirrer, a thermometer, a dripping device and a reflux condenser, 300 parts of isopropyl alcohol was charged, and the temperature was raised to 83 ° C., followed by replacement with nitrogen gas. Production Example 3 in Table 1 200 parts of a monomer mixture having the composition shown in FIG. 9 and 6 parts of azobisisobutyronitrile as a polymerization initiator were dropped in 2 hours, and then reacted at 83 ° C. for 4 hours. Next, after adding 600 parts of ammonia water containing ammonia equivalent to the carboxyl group in the reaction product, isopropyl alcohol was distilled off under reduced pressure to produce a water-soluble acrylic copolymer (c) having a solid content of 25%, (d), (e), (f), (g), (h), (i) were obtained.
〔実施例１〜９〕表２に示す実施例１〜９の組成の混合物をサンドミルおよびディソルバーを用いて連肉、混合し、本発明の酸素インジケーター組成物を製造した。
〔比較例１〜８〕表２に示す比較例１〜９の組成の混合物をサンドミルおよびディソルバーを用いて連肉、混合し、酸素インジケーター組成物を製造した。
[Examples 1 to 9] Mixtures of the compositions of Examples 1 to 9 shown in Table 2 were mixed and mixed using a sand mill and a dissolver to produce an oxygen indicator composition of the present invention.
[Comparative Examples 1 to 8] Mixtures of the compositions of Comparative Examples 1 to 9 shown in Table 2 were mixed and mixed using a sand mill and a dissolver to produce an oxygen indicator composition.
刃先の厚みが６０μｍのセラミックメッキドクターブレード、東洋プリプレス株式会社製のクロム硬度１０５０Ｈｖの電子彫刻版(２００線／ｉｎｃｈ、スタイラス角度１２０度)および実施例１〜９および比較例１〜９で得られた酸素インジケーター組成物を富士機械工業株式会社製グラビア印刷機にセットし、ドクター圧０．２ＭＰａ、１００ｍ/分の印刷速度で厚さ１５μｍのコロナ放電処理延伸ガスバリア性ナイロンフィルム(ＭＸＤ系フィルム)に印刷した。 Obtained in ceramic plated doctor blade with blade thickness of 60 μm, electronic engraving plate with chrome hardness of 1050 Hv (200 lines / inch, stylus angle 120 degrees) manufactured by Toyo Prepress Co., Ltd. and Examples 1-9 and Comparative Examples 1-9 The oxygen indicator composition was set on a gravure printing machine manufactured by Fuji Machine Industry Co., Ltd., and a corona discharge treatment stretched gas barrier nylon film (MXD film) having a doctor pressure of 0.2 MPa and a printing speed of 100 m / min and a thickness of 15 μm. Printed.
次に、得られた印刷物を用いて、版深度８５μｍの腐蝕版を備えたドライラミネーターで、印刷面にエーテル系ドライラミネート接着剤を約２ｇ／ｍ2塗布し、直鎖状低密度ポリエチレンと貼り合わせを行なった後、４０℃で２日間エージングを行ない、積層物を得た。 Next, using the obtained printed matter, with a dry laminator equipped with a corrosive plate having a plate depth of 85 μm, an ether-based dry laminate adhesive was applied to the printing surface at about 2 g / m 2 and pasted with linear low-density polyethylene. After combining, aging was performed at 40 ° C. for 2 days to obtain a laminate.
実施例１〜９および比較例１〜８で得られた酸素インジケーター組成物を、以下の通り性能評価した。
流動性、レベリング性；回転粘度計(ＢＭ型粘度計)を用いて２５℃下における酸素インジケーターの粘度を測定した。また、得られた印刷物の以下の基準で目視評価した。
○ ；酸素インジケーター組成物の粘度が１０〜５００ｍＰａ・ｓの範囲にあり、印刷物泳ぎの発生が全くなかった。
○△；酸素インジケーター組成物の粘度が１０〜１０００ｍＰａ・ｓの範囲にあり、印刷物泳ぎの発生が全くなかった。
△ ；酸素インジケーター組成物の粘度が１０００ｍＰａ・ｓを超え、印刷物泳ぎがやや発生した。
△×；酸素インジケーター組成物の粘度が１０００ｍＰａ・ｓを超え、印刷物泳ぎが発生した。
× ；酸素インジケーター組成物の粘度が１０００ｍＰａ・ｓを超え、著しい印刷物泳ぎが発生した。
溶解性、版かぶり性；印刷物を黒色の紙の上に貼り、余白部分(非画線部)に付着したインキの量を以下の基準で目視評価した。
○ ；非画像部にインキの転移が全く認められなかった。
○△；非画像部にインキの転移が僅かに認められた。
△ ；非画像部の小面積にインキの転移が認められた。
△×；非画像部の大面積にインキの転移が認められた。
× ；非画像部全面にインキの転移が認められた。
耐ブロッキング性；印刷フィルムの印刷面と非印刷面とを重ね合わせ、荷重２０Ｎ／ｃｍ2、４０℃、相対湿度８０％の条件下で２４時間保存した後に、剥離させて以下の基準で評価した。
○ ；剥離抵抗がなく、インキの転移も全く認められなかった。
○△；剥離抵抗はあったが、インキの転移は全く認められなかった。
△ ；一部分に小面積のインキ取られを生じた。
△×；ブロッキングが多くの箇所で発生した。
× ；ブロッキングが全面に発生した。
接着性；ニチバン社製粘着テープ(12mm幅)を印刷面に貼りつけ親指で５回強く擦った後、粘着テープを急激に引離してインキ皮膜の剥離程度を以下の基準で評価した。
○ ；印刷直後よりインキが全く剥離しなかった。
○△；印刷直後はインキが部分的に剥離したが、印刷１日後ではインキが全く剥離しなかった。
△ ；印刷直後はインキがほとんど剥離したが、印刷１日後ではインキが剥離しなかった。
△×；印刷１日後でもインキがやや剥離した。
× ；印刷１日後でもインキが完全に剥離した。
発色、色相変化；積層物を有酸素状態にて２５℃、１２時間保管後の酸素インジケーター組成物の発色を確認した。その後、積層物に脱酸素剤を封入して四方シールし、脱酸素状態にて２５℃、１２時間保管後の酸素インジケーター組成物の発色を確認した。次に積層物を再び有酸素状態に移し、２５℃、１２時間保管後の酸素インジケーター組成物の発色を確認した。有酸素状態→無酸素状態→有酸素状態のサイクルを５回繰り返した。
酸素インジケーター組成物の発色を以下の基準で評価した。
○ ；有酸素状態と脱酸素状態の色相の差が極めて大きく、容易に見分ける事ができた。
○△；有酸素状態と脱酸素状態の色相の差が大きく、見分ける事ができた。
△ ；見分ける事はできたが、有酸素状態と脱酸素状態の色相の差が小さかった。
△×；有酸素状態と脱酸素状態の色相の差が小さく、見分ける事が困難であった。
× ；有酸素状態と脱酸素状態の色相の差がなく、見分ける事が全く困難であった。
酸素インジケーター組成物の発色、色相変化を以下の基準で評価した。
○ ；５サイクル終了時でも完全な色相変化が確認できた。
○△；４サイクル終了までは完全な色相変化が確認できた。
△ ；２〜３サイクル終了までは完全な色相変化が確認できた。
△×；１サイクル終了までは完全な色相変化が確認できた。
× ；全く色相変化が起こらなかった。
The performance of the oxygen indicator compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 8 was evaluated as follows.
Flowability, leveling property: The viscosity of an oxygen indicator at 25 ° C. was measured using a rotational viscometer (BM type viscometer). Further, the obtained printed matter was visually evaluated according to the following criteria.
○: The viscosity of the oxygen indicator composition was in the range of 10 to 500 mPa · s, and there was no occurrence of printed matter swimming.
B: The viscosity of the oxygen indicator composition was in the range of 10 to 1000 mPa · s, and there was no occurrence of print swim.
Δ: The viscosity of the oxygen indicator composition exceeded 1000 mPa · s, and printed matter swimming slightly occurred.
Δ ×: The viscosity of the oxygen indicator composition exceeded 1000 mPa · s, and printed matter swimming occurred.
X: Viscosity of the oxygen indicator composition exceeded 1000 mPa · s, and remarkable print swimming occurred.
Solubility, plate fogging property: The printed matter was pasted on black paper, and the amount of ink adhered to the blank portion (non-image area) was visually evaluated according to the following criteria.
○: No ink transfer was observed in the non-image area.
◯: Slight ink transfer was observed in the non-image area.
Δ: Ink transfer was observed in a small area of the non-image area.
Δ ×: Ink transfer was observed in a large area of the non-image area.
X: Ink transfer was observed over the entire non-image area.
Blocking resistance: The printed surface and the non-printed surface of the printed film were overlapped, stored for 24 hours under the conditions of a load of 20 N / cm 2 , 40 ° C. and a relative humidity of 80%, and then peeled and evaluated according to the following criteria. .
○: There was no peeling resistance, and no ink transfer was observed.
◯: There was peeling resistance, but no ink transfer was observed.
Δ: A small area of ink was partially removed.
Δ ×: Blocking occurred in many places.
X: Blocking occurred on the entire surface.
Adhesiveness: Nichiban adhesive tape (12 mm width) was affixed to the printing surface and rubbed strongly with the thumb five times, and then the adhesive tape was abruptly peeled to evaluate the degree of peeling of the ink film according to the following criteria.
○: Ink did not peel off immediately after printing.
◯: The ink partially peeled immediately after printing, but the ink did not peel at all after 1 day of printing.
Δ: The ink was almost peeled off immediately after printing, but the ink was not peeled off after 1 day of printing.
Δ: The ink peeled slightly even after 1 day of printing.
X: The ink was completely peeled even after one day of printing.
Color development, hue change: The color development of the oxygen indicator composition was confirmed after storing the laminate in an aerobic state at 25 ° C. for 12 hours. Thereafter, an oxygen scavenger was sealed in the laminate and sealed in four directions, and color development of the oxygen indicator composition after storage for 12 hours at 25 ° C. in a deoxygenated state was confirmed. Next, the laminate was again transferred to an aerobic state, and the color development of the oxygen indicator composition after storage at 25 ° C. for 12 hours was confirmed. The cycle of aerobic state → anoxic state → aerobic state was repeated 5 times.
The color development of the oxygen indicator composition was evaluated according to the following criteria.
○: The difference in the hue between the aerobic state and the deoxygenated state was extremely large and could be easily distinguished.
◯: The difference in hue between the aerobic state and the deoxygenated state was large and could be distinguished.
Δ: Although it was possible to distinguish, the difference in hue between the aerobic state and the deoxygenated state was small.
Δ ×: The difference in hue between the aerobic state and the deoxygenated state was small, and it was difficult to distinguish.
X: There was no difference in hue between the aerobic state and the deoxygenated state, and it was quite difficult to distinguish.
The color development and hue change of the oxygen indicator composition were evaluated according to the following criteria.
○: Complete hue change was confirmed even at the end of 5 cycles.
A: Complete hue change was confirmed until the end of 4 cycles.
Δ: Complete hue change was confirmed until the end of 2-3 cycles.
Δ ×: Complete hue change was confirmed until the end of one cycle.
X: No hue change occurred.
Claims (3)
酸化還元色素であるメチレンブルーと、
還元剤であるＤ−グルコースと、
酸価が５０〜３００ｍｇＫＯＨ／ｇであるとともにガラス転移点が１０〜７０℃であり、アクリル酸、スチレン、及び、（メタ）アクリル酸エステルを重合してなる
アルカリ可溶型水溶性アクリル系重合体またはエマルジョン型アクリル系共重合体
とからなることを特徴とする酸素インジケーター組成物。 At least with water,
Methylene blue, which is a redox dye,
D-glucose as a reducing agent;
10 to 70 ° C. Der glass transition point with an acid value of from 50 to 300 / g is, acrylic acid, styrene, and (meth) obtained by polymerizing an acrylic acid ester <br/> alkali-soluble water An oxygen indicator composition comprising a water-soluble acrylic polymer or an emulsion-type acrylic copolymer.
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| JP2003066024A (en) * | 2001-08-30 | 2003-03-05 | Toppan Forms Co Ltd | Discoloring pigment composition containing super absorbent polymer microspheres carrying discoloring pigments, method for producing the same, and antiforgery sheet using the same |
| JP2004254684A (en) * | 2003-02-07 | 2004-09-16 | Powdertech Co Ltd | Method for controlling quality of product and oxygen detecting agent used for the same |
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| JP3217823B2 (en) * | 1991-11-28 | 2001-10-15 | 大日本印刷株式会社 | Packaging material with oxygen detection function |
| JPH0634619A (en) * | 1992-07-15 | 1994-02-10 | Nippon Kayaku Co Ltd | Oxygen detecting sheet |
| JPH06230004A (en) * | 1993-02-05 | 1994-08-19 | Freunt Ind Co Ltd | Oxygen detecting agent composite |
| JP3502192B2 (en) * | 1995-06-27 | 2004-03-02 | 三井化学株式会社 | Powder coating composition |
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| JP2003066024A (en) * | 2001-08-30 | 2003-03-05 | Toppan Forms Co Ltd | Discoloring pigment composition containing super absorbent polymer microspheres carrying discoloring pigments, method for producing the same, and antiforgery sheet using the same |
| JP2004254684A (en) * | 2003-02-07 | 2004-09-16 | Powdertech Co Ltd | Method for controlling quality of product and oxygen detecting agent used for the same |
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