JP6090566B2 - Oxygen-absorbing resin composition and oxygen-absorbing adhesive resin composition - Google Patents
Oxygen-absorbing resin composition and oxygen-absorbing adhesive resin composition Download PDFInfo
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- JP6090566B2 JP6090566B2 JP2012266419A JP2012266419A JP6090566B2 JP 6090566 B2 JP6090566 B2 JP 6090566B2 JP 2012266419 A JP2012266419 A JP 2012266419A JP 2012266419 A JP2012266419 A JP 2012266419A JP 6090566 B2 JP6090566 B2 JP 6090566B2
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- Prior art keywords
- oxygen
- acid
- absorbing
- resin composition
- derivative
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 21
- 239000000203 mixture Substances 0.000 title description 26
- 239000004840 adhesive resin Substances 0.000 title description 16
- 229920006223 adhesive resin Polymers 0.000 title description 16
- 239000002253 acid Substances 0.000 claims description 49
- 229920000728 polyester Polymers 0.000 claims description 35
- -1 alicyclic isocyanate Chemical class 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012948 isocyanate Substances 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 16
- 230000001070 adhesive effect Effects 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 50
- 239000001301 oxygen Substances 0.000 description 50
- 229910052760 oxygen Inorganic materials 0.000 description 50
- 239000010408 film Substances 0.000 description 34
- 238000010521 absorption reaction Methods 0.000 description 28
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 12
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- 238000006243 chemical reaction Methods 0.000 description 10
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- 239000000243 solution Substances 0.000 description 8
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
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- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は酸素吸収性樹脂組成物及び酸素吸収性接着剤樹脂組成物に関する。 The present invention relates to an oxygen-absorbing resin composition and an oxygen-absorbing adhesive resin composition.
飲料、食品及び医薬品の包装材料用途として種々の酸素吸収性樹脂材料が提案されている。特に、特許文献１〜３には酸化触媒としての遷移金属塩を添加することなく酸素吸収機能を発現し得る樹脂材料が提案されている。これらの材料は遷移金属触媒による過剰な酸化反応を抑えることにより分解物、脆化、着色等の抑制を実現した材料であり、包装材料用途として特に優れている。しかしながら、これらの材料は製造条件や加工条件による酸素吸収性能の変化が大きいため、安定的に優れた酸素吸収性能を発揮させることが困難であった。
また、特許文献４にはアリル水素や３級炭素に結合した水素を分子中に有する熱可塑性樹脂に酸素吸収反応開始剤として有機過酸化物を添加した酸素吸収組成物が提案されているが、機能発現のために高温長時間の熱処理が必要であり、実用性のあるものではなかった。
Various oxygen-absorbing resin materials have been proposed for use as packaging materials for beverages, foods, and pharmaceuticals. In particular, Patent Documents 1 to 3 propose resin materials that can exhibit an oxygen absorption function without adding a transition metal salt as an oxidation catalyst. These materials are materials excellent in suppressing decomposition products, embrittlement, coloring, etc. by suppressing an excessive oxidation reaction by a transition metal catalyst, and are particularly excellent as packaging materials. However, since these materials have a large change in oxygen absorption performance depending on manufacturing conditions and processing conditions, it has been difficult to stably exhibit excellent oxygen absorption performance.
Patent Document 4 proposes an oxygen-absorbing composition obtained by adding an organic peroxide as an oxygen-absorbing reaction initiator to a thermoplastic resin having hydrogen bonded to allyl hydrogen or tertiary carbon in the molecule. A heat treatment for a long time at a high temperature is necessary for the function expression, and it was not practical.
したがって、本発明は遷移金属触媒を添加することなく、実用性が高く、安定的に優れた酸素吸収性能を発揮する酸素吸収性材料を提供することを目的とする。 Accordingly, an object of the present invention is to provide an oxygen-absorbing material that has high practicality and stably exhibits excellent oxygen-absorbing performance without adding a transition metal catalyst.
本発明は、酸成分（Ａ）に由来する構造単位を含むポリエステル、いわゆる不飽和ポリエステルと過酸化水素を含有する酸素吸収性樹脂組成物を提供する。
酸成分（Ａ）：（ｉ）及び（ii）からなる群より選ばれる構造を有する酸成分；
（ｉ）下記構造（ａ）及び（ｂ）の両方の基に結合し、かつ、１個の水素原子と結合した炭素原子を有し、該炭素原子が脂環構造に含まれているジカルボン酸若しくはジカルボン酸無水物；
（ａ）炭素−炭素二重結合基、
（ｂ）カルボニル基；
（ii）不飽和脂環構造内の炭素−炭素二重結合に隣接する炭素原子が電子供与性置換基及び水素原子と結合し、かつ、該炭素原子に隣接する別の炭素原子がカルボニル基と結合しており、該電子供与性置換基と該カルボニル基とがシス位に位置しているジカルボン酸若しくはジカルボン酸無水物
また、本発明は、前記酸素吸収性樹脂組成物と、硬化剤として脂肪族及び／又は脂環族イソシアネート系硬化剤、及び溶媒として酢酸エチルを含有する酸素吸収性接着剤樹脂組成物を提供する。
The present invention provides an oxygen-absorbing resin composition containing a polyester containing a structural unit derived from an acid component (A), a so-called unsaturated polyester and hydrogen peroxide.
Acid component (A): an acid component having a structure selected from the group consisting of (i) and (ii);
(I) a dicarboxylic acid bonded to both groups of the following structures (a) and (b) and having a carbon atom bonded to one hydrogen atom, the carbon atom being contained in the alicyclic structure Or a dicarboxylic acid anhydride;
(A) a carbon-carbon double bond group,
(B) a carbonyl group;
(Ii) A carbon atom adjacent to the carbon-carbon double bond in the unsaturated alicyclic structure is bonded to an electron donating substituent and a hydrogen atom, and another carbon atom adjacent to the carbon atom is a carbonyl group. A dicarboxylic acid or a dicarboxylic acid anhydride in which the electron-donating substituent and the carbonyl group are located in the cis position. The present invention also includes the oxygen-absorbing resin composition and a fatty acid as a curing agent. An oxygen-absorbing adhesive resin composition containing an aliphatic and / or alicyclic isocyanate-based curing agent and ethyl acetate as a solvent is provided.
本発明により、遷移金属触媒を添加することなく、実用性が高く、安定的に優れた酸素吸収性能を発揮する酸素吸収性材料を提供することができる。 According to the present invention, it is possible to provide an oxygen-absorbing material that has high practicality and stably exhibits excellent oxygen-absorbing performance without adding a transition metal catalyst.
本発明の酸素吸収性樹脂組成物は、酸成分（Ａ）に由来する構造単位を含むポリエステルと過酸化水素を含有する。
酸成分（Ａ）は、（ｉ）及び（ii）からなる群より選ばれる構造を有する。
（ｉ）下記構造（ａ）及び（ｂ）の両方の基に結合し、かつ、１個の水素原子と結合した炭素原子を有し、該炭素原子が脂環構造に含まれているジカルボン酸若しくはジカルボン酸無水物；
（ａ）炭素−炭素二重結合基、
（ｂ）カルボニル基；
（ii）不飽和脂環構造内の炭素−炭素二重結合に隣接する炭素原子が電子供与性置換基及び水素原子と結合し、かつ、該炭素原子に隣接する別の炭素原子がカルボニル基と結合しており、該電子供与性置換基と該カルボニル基とがシス位に位置しているジカルボン酸若しくはジカルボン酸無水物
The oxygen-absorbing resin composition of the present invention contains a polyester containing a structural unit derived from the acid component (A) and hydrogen peroxide.
The acid component (A) has a structure selected from the group consisting of (i) and (ii).
(I) a dicarboxylic acid bonded to both groups of the following structures (a) and (b) and having a carbon atom bonded to one hydrogen atom, the carbon atom being contained in the alicyclic structure Or a dicarboxylic acid anhydride;
(A) a carbon-carbon double bond group,
(B) a carbonyl group;
(Ii) A carbon atom adjacent to the carbon-carbon double bond in the unsaturated alicyclic structure is bonded to an electron donating substituent and a hydrogen atom, and another carbon atom adjacent to the carbon atom is a carbonyl group. A dicarboxylic acid or dicarboxylic acid anhydride which is bonded and in which the electron donating substituent and the carbonyl group are located in the cis position
上述の構造（ｉ）及び（ii）は、置換基効果により、優れた酸素との反応性を有する分子構造である。
（ｉ）の構造を有する酸成分として、Δ2−テトラヒドロフタル酸若しくはその誘導体、Δ3−テトラヒドロフタル酸若しくはその誘導体、Δ2−テトラヒドロ無水フタル酸若しくはその誘導体、Δ3−テトラヒドロ無水フタル酸若しくはその誘導体を挙げることが出来る。好ましくは、Δ3−テトラヒドロフタル酸若しくはその誘導体又はΔ3−テトラヒドロ無水フタル酸若しくはその誘導体であり、特に好ましくは４−メチル−Δ3−テトラヒドロフタル酸若しくはその誘導体又は４−メチル−Δ3−テトラヒドロ無水フタル酸若しくはその誘導体である。４−メチル−Δ3−テトラヒドロ無水フタル酸は、例えば、イソプレンを主成分とするナフサのＣ5留分を無水マレイン酸と反応させた、４−メチル−Δ4−テトラヒドロ無水フタル酸を含む異性体混合物を、構造異性化することにより得ることが出来、工業的に製造されている。
The structures (i) and (ii) described above are molecular structures having excellent reactivity with oxygen due to the substituent effect.
As the acid component having the structure (i), Δ 2 -tetrahydrophthalic acid or a derivative thereof, Δ 3 -tetrahydrophthalic acid or a derivative thereof, Δ 2 -tetrahydrophthalic anhydride or a derivative thereof, Δ 3 -tetrahydrophthalic anhydride or Derivatives thereof can be mentioned. Preferred is Δ 3 -tetrahydrophthalic acid or a derivative thereof, or Δ 3 -tetrahydrophthalic anhydride or a derivative thereof, and particularly preferred is 4-methyl-Δ 3 -tetrahydrophthalic acid or a derivative thereof or 4-methyl-Δ 3-. Tetrahydrophthalic anhydride or its derivative. For example, 4-methyl-Δ 3 -tetrahydrophthalic anhydride is an isomer containing 4-methyl-Δ 4 -tetrahydrophthalic anhydride obtained by reacting a C 5 fraction of naphtha containing isoprene as a main component with maleic anhydride. The body mixture can be obtained by structural isomerization and is industrially produced.
（ii）の構造を有する酸成分として、特に好ましくはｃｉｓ−３−メチル−Δ4−テトラヒドロフタル酸若しくはその誘導体又はｃｉｓ−３−メチル−Δ4−テトラヒドロ無水フタル酸若しくはその誘導体である。ｃｉｓ−３−メチル−Δ4−テトラヒドロ無水フタル酸は、例えば、トランス−ピペリレンを主成分とするナフサのＣ5留分を無水マレイン酸と反応させることにより得ることが出来、工業的に製造されている。 The acid component having the structure (ii) is particularly preferably cis-3-methyl-Δ 4 -tetrahydrophthalic acid or a derivative thereof, or cis-3-methyl-Δ 4 -tetrahydrophthalic anhydride or a derivative thereof. Cis-3-methyl-Δ 4 -tetrahydrophthalic anhydride can be obtained, for example, by reacting a naphtha C 5 fraction mainly composed of trans-piperylene with maleic anhydride, and is produced industrially. ing.
前述の（ｉ）の構造を有する酸成分及び（ii）の構造を有する酸成分は、酸素との反応性が非常に高い。これらの（ｉ）の構造を有する酸成分及び（ii）の構造を有する酸成分は単独で使用することも出来るが、２種類以上を組み合わせて使用することも好ましい。
前述の（ｉ）の構造として好適な４−メチル−Δ3−テトラヒドロ無水フタル酸と（ii）の構造として好適なｃｉｓ−３−メチル−Δ4−テトラヒドロ無水フタル酸の混合物は、トランス−ピペリレン及びイソプレンを主成分とするナフサのＣ5留分を無水マレイン酸と反応させた、ｃｉｓ−３−メチル−Δ4−テトラヒドロ無水フタル酸と４−メチル−Δ4−テトラヒドロ無水フタル酸の混合物を構造異性化することにより、工業品として低コストで容易に得ることが出来る。このように安価な異性体混合物を使用することは、産業応用を考えると特に好ましい。
本発明で使用するポリエステルを重合する際、ジカルボン酸及びジカルボン酸無水物はメチルエステル等にエステル化されていてもよい。
The acid component having the structure (i) and the acid component having the structure (ii) have a very high reactivity with oxygen. The acid component having the structure (i) and the acid component having the structure (ii) can be used alone, but it is also preferable to use two or more types in combination.
A mixture of 4-methyl-Δ 3 -tetrahydrophthalic anhydride suitable as the structure of (i) and cis-3-methyl-Δ 4 -tetrahydrophthalic anhydride suitable as the structure of (ii) is trans-piperylene. And a mixture of cis-3-methyl-Δ 4 -tetrahydrophthalic anhydride and 4-methyl-Δ 4 -tetrahydrophthalic anhydride obtained by reacting a C 5 fraction of naphtha containing isoprene as a main component with maleic anhydride. By structural isomerization, it can be easily obtained as an industrial product at low cost. The use of such an inexpensive isomer mixture is particularly preferable in view of industrial application.
When the polyester used in the present invention is polymerized, the dicarboxylic acid and dicarboxylic acid anhydride may be esterified to methyl ester or the like.
また、本発明の酸素吸収性樹脂組成物には、酸素吸収反応を促進させるために酸素吸収反応触媒（酸化触媒）を添加しても良い。しかしながら、前述の（ｉ）の構造を有する酸成分及び（ii）の構造を有する酸成分に由来する構造単位を含むポリエステルは、酸素との反応性が極めて高いことから、酸素吸収反応触媒の不在下において、実用的な酸素吸収性能を発現することができる。また、本発明の酸素吸収性樹脂組成物を用いて接着剤を調製する際、又は接着剤を用いた加工をする際に、酸素吸収反応触媒が原因となる過度の樹脂劣化に起因するゲル化等を防止するためにも、触媒量の酸素吸収反応触媒を含まないことが望ましい。ここで、酸素吸収反応触媒としては、マンガン、鉄、コバルト、ニッケル、銅の遷移金属と有機酸からなる遷移金属塩が挙げられる。また、「触媒量の酸素吸収反応触媒を含まない」とは、一般に酸素吸収反応触媒が遷移金属量で１０ｐｐｍ未満であることを意味し、好ましくは１ｐｐｍ未満である。 Further, an oxygen absorption reaction catalyst (oxidation catalyst) may be added to the oxygen-absorbing resin composition of the present invention in order to promote the oxygen absorption reaction. However, the polyester containing the acid component having the structure (i) and the structural unit derived from the acid component having the structure (ii) has a very high reactivity with oxygen. In the presence, practical oxygen absorption performance can be expressed. In addition, when preparing an adhesive using the oxygen-absorbing resin composition of the present invention, or when processing using an adhesive, gelation due to excessive resin deterioration caused by an oxygen absorption reaction catalyst In order to prevent the above, it is desirable not to include a catalytic amount of an oxygen absorption reaction catalyst. Here, examples of the oxygen absorption reaction catalyst include transition metal salts composed of a transition metal of manganese, iron, cobalt, nickel, and copper and an organic acid. Further, “not containing a catalytic amount of an oxygen-absorbing reaction catalyst” generally means that the oxygen-absorbing reaction catalyst is less than 10 ppm in terms of the amount of transition metal, and preferably less than 1 ppm.
本発明で使用するポリエステルには、酸成分（Ａ）の他に、芳香族ジカルボン酸や脂肪族ジカルボン酸、脂肪族ヒドロキシカルボン酸など、他の酸成分（酸成分（Ｂ））及びその誘導体を原料として含んでもよい。
芳香族ジカルボン酸及びその誘導体としては、テレフタル酸、無水フタル酸、イソフタル酸などのベンゼンジカルボン酸、２，６−ナフタレンジカルボン酸などのナフタレンジカルボン酸、アントラセンジカルボン酸、スルホイソフタル酸、スルホイソフタル酸ナトリウム、又はこれらの誘導体等が挙げられる。これらの中でもベンゼンジカルボン酸が好ましく、特に好ましくはテレフタル酸である。
脂肪族ジカルボン酸及びその誘導体としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、３，３−ジメチルペンタン二酸、又はこれらの誘導体等が挙げられる。これらの中でも、アジピン酸、コハク酸が好ましく、特にコハク酸が好ましい。
脂肪族ヒドロキシカルボン酸及びその誘導体としては、グリコール酸、乳酸、ヒドロキシピバリン酸、ヒドロキシカプロン酸、ヒドロキシヘキサン酸、又はこれらの誘導体が挙げられる。
これらの酸成分は、例えばテレフタル酸ジメチルやビス−２−ヒドロキシジエチルテレフタレートのようにエステル化されていても良い。また、無水コハク酸のように酸無水物であっても良い。これらは、単独、又は、２種類以上を組み合わせて使用できる。前記酸成分を共重合させることによって、得られるポリエステルのガラス転移温度を容易に制御することができ、酸素吸収性能を向上させることが出来る。さらには、有機溶剤への溶解性を制御することも出来る。
また、酸成分（Ａ）は重合中の熱によりラジカル架橋反応を起こしやすいため、酸成分（Ｂ）によってポリエステル中に含まれる酸成分（Ａ）の組成比が減少すると、重合中のゲル化が抑制され高分子量の樹脂を安定的に得ることが出来る。
In addition to the acid component (A), the polyester used in the present invention includes other acid components (acid component (B)) and derivatives thereof such as aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and aliphatic hydroxycarboxylic acid. It may be included as a raw material.
Aromatic dicarboxylic acids and derivatives thereof include benzene dicarboxylic acids such as terephthalic acid, phthalic anhydride, and isophthalic acid, naphthalene dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, sulfoisophthalic acid, sodium sulfoisophthalate Or derivatives thereof. Among these, benzenedicarboxylic acid is preferable, and terephthalic acid is particularly preferable.
Aliphatic dicarboxylic acids and their derivatives include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethyl Pentanedioic acid or derivatives thereof may be mentioned. Among these, adipic acid and succinic acid are preferable, and succinic acid is particularly preferable.
Examples of the aliphatic hydroxycarboxylic acid and derivatives thereof include glycolic acid, lactic acid, hydroxypivalic acid, hydroxycaproic acid, hydroxyhexanoic acid, and derivatives thereof.
These acid components may be esterified such as dimethyl terephthalate or bis-2-hydroxydiethyl terephthalate. Further, it may be an acid anhydride such as succinic anhydride. These can be used alone or in combination of two or more. By copolymerizing the acid component, the glass transition temperature of the obtained polyester can be easily controlled, and the oxygen absorption performance can be improved. Furthermore, the solubility in an organic solvent can be controlled.
In addition, since the acid component (A) easily undergoes a radical crosslinking reaction due to heat during polymerization, if the composition ratio of the acid component (A) contained in the polyester is reduced by the acid component (B), gelation during polymerization may occur. Suppressed and high molecular weight resin can be obtained stably.
酸成分（Ａ）の全酸成分に対する割合は、好ましくは３５〜９５モル％であり、より好ましくは５０〜９５モル％である。
酸成分（Ｂ）に由来する構造単位の全酸成分に対する割合は１〜３０モル％である場合が好ましく、より好ましくは５〜２０モル％である。
本発明で使用するポリエステルのガラス転移温度は、十分な酸素吸収性能を得るために、好ましくは−２０〜２℃であり、より好ましくは−１５〜２℃の範囲であり、さらに好ましくは−１２〜２℃の範囲である。また、ガラス転移温度が上記の範囲より低い場合は樹脂の凝集力すなわち耐クリープ性が低下し、高い場合は他の材料への密着力すなわち接着強度が低下するため、接着剤として本発明の２液硬化型酸素吸収性樹脂組成物を適用する場合は好ましくない。
本発明で使用するポリエステルの酸価は、十分な酸素吸収性能を得るために、好ましくは５ｍｇＫＯＨ／ｇ以下であり、より好ましくは１ｍｇＫＯＨ／ｇ以下である。ポリエステルの酸価が５ｍｇＫＯＨ／ｇを超える場合には、速やかな自動酸化反応が妨げられ、安定した酸素吸収性能が得られない場合がある。
The ratio of the acid component (A) to the total acid component is preferably 35 to 95 mol%, more preferably 50 to 95 mol%.
The ratio of the structural unit derived from the acid component (B) to the total acid component is preferably 1 to 30 mol%, more preferably 5 to 20 mol%.
In order to obtain sufficient oxygen absorption performance, the glass transition temperature of the polyester used in the present invention is preferably -20 to 2 ° C, more preferably -15 to 2 ° C, and further preferably -12. It is in the range of ~ 2 ° C. Further, when the glass transition temperature is lower than the above range, the cohesive strength of the resin, that is, the creep resistance is lowered, and when it is high, the adhesion force to other materials, that is, the adhesive strength is lowered. It is not preferred when applying a liquid curable oxygen-absorbing resin composition.
The acid value of the polyester used in the present invention is preferably 5 mgKOH / g or less, more preferably 1 mgKOH / g or less in order to obtain sufficient oxygen absorption performance. When the acid value of the polyester exceeds 5 mgKOH / g, the rapid auto-oxidation reaction is hindered, and stable oxygen absorption performance may not be obtained.
本発明で使用するポリエステルは、さらにジオール成分に由来する構造単位を含む。ジオール成分としては、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、トリメチレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、３−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、１，７−ヘプタンジオール、１，８−オクタンジオール、１，９−ノナンジオール、ネオペンチルグリコール、１，４−シクロヘキサンジメタノール、２−フェニルプロパンジオール、２−（４―ヒドロキシフェニル）エチルアルコール、α，α―ジヒドロキシ−１，３−ジイソプロピルベンゼン、ｏ−キシレングリコール、ｍ−キシレングリコール、ｐ−キシレングリコール、α，α―ジヒドロキシ−１，４−ジイソプロピルベンゼン、ヒドロキノン、４，４−ジヒドロキシジフェニル、ナフタレンジオール、又はこれらの誘導体などが挙げられる。好ましくは、脂肪族ジオール、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコールであり、さらに好ましくは１，４−ブタンジオールである。１，４−ブタンジオールを用いた場合は、樹脂の酸素吸収性能が高く、更に自動酸化の過程で生じる分解物の量も少ない。これらは、単独、又は、２種類以上を組み合わせて使用できる。 The polyester used in the present invention further contains a structural unit derived from a diol component. Examples of the diol component include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2-phenyl Propanediol, 2- (4-hydroxyphenyl) ethyl alcohol, α, α-dihydroxy-1,3-diisopropylbenzene, o-xylene glycol, m-xylene glycol, p-xylene glycol, α α- dihydroxy-1,4-diisopropylbenzene, hydroquinone, 4,4-dihydroxydiphenyl, naphthalenediol or derivatives thereof. Preferred are aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and more preferred is 1,4-butanediol. When 1,4-butanediol is used, the oxygen absorption performance of the resin is high, and the amount of decomposition products generated during the auto-oxidation process is small. These can be used alone or in combination of two or more.
本発明で使用するポリエステルは、さらに多価アルコール、多価カルボン酸、又はそれらの誘導体等に由来する構造単位を含んでもよい。多価アルコール及び多価カルボン酸を導入し分岐構造を制御することにより、溶融粘度特性や溶媒に溶解したポリエステルの溶液粘度特性を調整できる。
多価アルコール及びその誘導体としては、１，２，３−プロパントリオール、ソルビトール、１，３，５−ペンタントリオール、１，５，８−ヘプタントリオール、トリメチロールプロパン、ペンタエリスリトール、３，５−ジヒドロキシベンジルアルコール、グリセリン又はこれらの誘導体が挙げられる。
多価カルボン酸及びその誘導体としては、１，２，３−プロパントリカルボン酸、メソ−ブタン−１，２，３，４−テトラカルボン酸、クエン酸、トリメリット酸、ピロメリット酸、又はこれらの誘導体が挙げられる。
また、多価アルコールや多価カルボン酸等の３官能以上の官能基を有する成分を共重合させる場合は全酸成分に対し５モル％以内にすることが好ましい。
The polyester used in the present invention may further contain a structural unit derived from a polyhydric alcohol, a polyvalent carboxylic acid, or a derivative thereof. By introducing a polyhydric alcohol and a polycarboxylic acid and controlling the branched structure, the melt viscosity characteristic and the solution viscosity characteristic of the polyester dissolved in the solvent can be adjusted.
Examples of polyhydric alcohols and derivatives thereof include 1,2,3-propanetriol, sorbitol, 1,3,5-pentanetriol, 1,5,8-heptanetriol, trimethylolpropane, pentaerythritol, 3,5-dihydroxy Examples include benzyl alcohol, glycerin, and derivatives thereof.
Examples of the polyvalent carboxylic acid and its derivatives include 1,2,3-propanetricarboxylic acid, meso-butane-1,2,3,4-tetracarboxylic acid, citric acid, trimellitic acid, pyromellitic acid, and these Derivatives.
Moreover, when copolymerizing the component which has trifunctional or more functional groups, such as a polyhydric alcohol and polyhydric carboxylic acid, it is preferable to make it into 5 mol% or less with respect to all the acid components.
本発明で使用するポリエステルは当業者に公知の任意のポリエステルの重縮合方法により得ることが出来る。例えば、界面重縮合、溶液重縮合、溶融重縮合及び固相重縮合である。
本発明で使用するポリエステルを合成する場合に、重合触媒は必ずとも必要としないが、例えばチタン系、ゲルマニウム系、アンチモン系、スズ系、アルミニウム系等の通常のポリエステル重合触媒が使用可能である。また、含窒素塩基性化合物、ホウ酸及びホウ酸エステル、有機スルホン酸系化合物等の公知の重合触媒を使用することもできる。
さらに、重合の際にはリン化合物等の着色防止剤や酸化防止剤等の各種添加剤を添加することもできる。酸化防止剤を添加することにより、重合中やその後の加工中の酸素吸収を抑制できるため、酸素吸収性樹脂の性能低下やゲル化を抑えることができる。
本発明で使用するポリエステルの数平均分子量は、好ましくは５００〜１０００００であり、より好ましくは２０００〜１００００である。また好ましい重量平均分子量は５０００〜２０００００、より好ましくは１００００〜１０００００であり、さらに好ましくは２００００〜７００００である。分子量が上記の範囲より低い場合は樹脂の凝集力すなわち耐クリープ性が低下し、高い場合は有機溶剤への溶解性の低下や溶液粘度の上昇による塗工性の低下が生じるため、接着剤として本発明の２液硬化型酸素吸収性樹脂組成物を適用する場合に好ましくない。上記範囲内の分子量の場合には、凝集力、接着性及び有機溶剤への溶解性に優れ、接着剤溶液として好適な粘度特性を有する酸素吸収性接着剤樹脂組成物を得ることが出来る。
本発明で使用するポリエステルは、合成の際、重縮合反応とラジカルによる熱重合反応の両反応により分子量が増大し、その結果比較的分子量分布の広い樹脂となる。特に重縮合反応効率が悪い重合条件においては、分子量分布の広がりが増し、この場合該ポリエステルの酸素吸収性能、特に初期酸素吸収性能が低下する傾向にある。本発明の酸素吸収性樹脂組成物および酸素吸収性接着剤樹脂組成物においては、過酸化水素による酸素吸収反応促進効果により、重合条件によってばらついた該ポリエステルの酸素吸収性能を安定化させ、実用的で安定的な酸素吸収性能を発現するのである。
The polyester used in the present invention can be obtained by any polycondensation method of polyester known to those skilled in the art. For example, interfacial polycondensation, solution polycondensation, melt polycondensation and solid phase polycondensation.
When synthesizing the polyester used in the present invention, a polymerization catalyst is not necessarily required. For example, a normal polyester polymerization catalyst such as titanium, germanium, antimony, tin, and aluminum can be used. Further, known polymerization catalysts such as nitrogen-containing basic compounds, boric acid and boric acid esters, and organic sulfonic acid compounds can also be used.
Furthermore, various additives, such as coloring inhibitors, such as a phosphorus compound, and antioxidant, can also be added in the case of superposition | polymerization. By adding an antioxidant, it is possible to suppress oxygen absorption during polymerization and subsequent processing, and therefore, it is possible to suppress performance degradation and gelation of the oxygen-absorbing resin.
The number average molecular weight of the polyester used in the present invention is preferably 500 to 100,000, more preferably 2000 to 10,000. Moreover, a preferable weight average molecular weight is 5000-200000, More preferably, it is 10,000-100000, More preferably, it is 20000-70000. When the molecular weight is lower than the above range, the cohesive strength of the resin, that is, the creep resistance is lowered, and when it is high, the solubility in an organic solvent is lowered and the coating property is lowered due to an increase in the solution viscosity. This is not preferable when the two-part curable oxygen-absorbing resin composition of the present invention is applied. When the molecular weight is within the above range, an oxygen-absorbing adhesive resin composition having excellent cohesive strength, adhesiveness and solubility in an organic solvent and having viscosity characteristics suitable as an adhesive solution can be obtained.
The polyester used in the present invention has a molecular weight increased by both the polycondensation reaction and the thermal polymerization reaction by radicals during synthesis, and as a result, becomes a resin having a relatively wide molecular weight distribution. In particular, under polymerization conditions with poor polycondensation reaction efficiency, the molecular weight distribution increases, and in this case, the oxygen absorption performance, particularly the initial oxygen absorption performance, of the polyester tends to decrease. In the oxygen-absorbing resin composition and the oxygen-absorbing adhesive resin composition of the present invention, the oxygen-absorbing performance of the polyester, which varies depending on the polymerization conditions, is stabilized by the effect of promoting the oxygen-absorbing reaction by hydrogen peroxide. It exhibits stable oxygen absorption performance.
過酸化水素は、前記ポリエステルに対して、０．０１〜２０ｐｈｒ（ｐａｒｔｓ ｐｅｒ ｈｕｎｄｒｅｄ ｒｅｓｉｎ）添加することが好ましく、より好ましくは０．０２〜１０ｐｈｒ、さらに好ましくは０．０５〜１ｐｈｒである。添加量が少なすぎると、実用性が高く安定的した酸素吸収性能を発揮することが困難であり、多すぎると、急激で過剰なラジカル反応によりゲル化等の不具合を来すため好ましくない。なお、高濃度過酸化水素は危険なため、水溶液としてポリエステルに添加する方が好ましい。過酸化水素水溶液の濃度は好ましくは３〜８０ｗｔ％であり、より好ましくは２０〜６０ｗｔ％である。 Hydrogen peroxide is preferably added to the polyester in an amount of 0.01 to 20 phr (parts per hundred resin), more preferably 0.02 to 10 phr, and still more preferably 0.05 to 1 phr. If the amount added is too small, it is difficult to exhibit a practical and stable oxygen absorption performance, and if it is too large, problems such as gelation due to a rapid and excessive radical reaction are not preferable. Since high-concentration hydrogen peroxide is dangerous, it is preferable to add it to the polyester as an aqueous solution. The concentration of the aqueous hydrogen peroxide solution is preferably 3 to 80 wt%, more preferably 20 to 60 wt%.
本発明の酸素吸収性樹脂組成物は、脂肪族及び／又は脂環族イソシアネート系硬化剤と共に酸素吸収性接着剤樹脂組成物として使用することができる。イソシアネート系硬化剤を用いた場合、接着強度及び凝集力が高くなり、また、室温付近の低温でキュアが可能となる。脂肪族イソシアネート系硬化剤としては、例えば、キシリレンジイソシアネート（ＸＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、リジンジイソシアネート、リジンメチルエステルジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ｎ−ペンタン−１，４−ジイソシアネート等が挙げられる。脂環族イソシアネート系硬化剤としては、例えば、イソホロンジイソシアネート（ＩＰＤＩ）、シクロヘキサン−１，４−ジイソシアネート、メチルシクロヘキシルジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート等が挙げられる。これらの中でも、脂肪族イソシアネート系硬化剤としては、ＸＤＩ及びＨＤＩが好ましく、脂環族イソシアネート系硬化剤としては、ＩＰＤＩが好ましい。特に好ましくは、ＸＤＩ及びＩＰＤＩであり、最も好ましくはＸＤＩである。ＸＤＩを使用することにより、本発明の酸素吸収性接着剤樹脂組成物は最も優れた酸素吸収性能を発揮する。ＩＰＤＩとＸＤＩを組み合わせて使用することも好ましい。一方、芳香族イソシアネート系硬化剤は、樹脂の接着性及び凝集力を向上させるものの、酸素吸収性能を著しく低下させるため、好ましくない。この理由として、芳香族イソシアネート系硬化剤が、主剤であるポリエステル末端の水酸基と反応して形成された芳香族ウレタン部位が、酸化防止剤である芳香族アミンと同様の働きで、ラジカルを失活／安定化させるためであることが考えられる。
これらの脂肪族及び／又は脂環族イソシアネート系硬化剤は、アダクトやイソシアヌレート、ビュレット体等、分子量を増大させたポリイソシアネート化合物として使用されることが好ましい。
また、これらの脂肪族及び／又は脂環族イソシアネート系硬化剤は単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The oxygen-absorbing resin composition of the present invention can be used as an oxygen-absorbing adhesive resin composition together with an aliphatic and / or alicyclic isocyanate curing agent. When an isocyanate curing agent is used, the adhesive strength and cohesive force are increased, and curing is possible at a low temperature around room temperature. Examples of the aliphatic isocyanate curing agent include xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), lysine diisocyanate, lysine methyl ester diisocyanate, trimethylhexamethylene diisocyanate, and n-pentane-1,4-diisocyanate. It is done. Examples of the alicyclic isocyanate-based curing agent include isophorone diisocyanate (IPDI), cyclohexane-1,4-diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate. Among these, XDI and HDI are preferable as the aliphatic isocyanate-based curing agent, and IPDI is preferable as the alicyclic isocyanate-based curing agent. Particularly preferred are XDI and IPDI, and most preferred is XDI. By using XDI, the oxygen-absorbing adhesive resin composition of the present invention exhibits the most excellent oxygen-absorbing performance. It is also preferable to use a combination of IPDI and XDI. On the other hand, an aromatic isocyanate curing agent improves the adhesion and cohesion of the resin, but is not preferable because it significantly reduces the oxygen absorption performance. The reason for this is that the aromatic urethane part formed by the reaction of the aromatic isocyanate curing agent with the hydroxyl group at the polyester terminal, which is the main agent, deactivates radicals in the same manner as the aromatic amine, which is an antioxidant. / It is conceivable that it is for stabilization.
These aliphatic and / or alicyclic isocyanate curing agents are preferably used as polyisocyanate compounds having an increased molecular weight, such as adducts, isocyanurates, and burettes.
These aliphatic and / or alicyclic isocyanate curing agents may be used alone or in combination of two or more.
脂肪族及び／又は脂環族イソシアネート系硬化剤成分は、主剤であるポリエステルに対して、固形分重量部で３ｐｈｒ〜３０ｐｈｒ添加することが好ましく、より好ましくは５ｐｈｒ〜２０ｐｈｒ、さらに好ましくは７ｐｈｒ〜１５ｐｈｒである。添加量が少なすぎると、接着性及び凝集力が不十分となり、多すぎると、樹脂単位重量中に含まれる酸素吸収成分の配合量が少なくなり、酸素吸収性能が不十分となる。また、硬化により樹脂の運動性が著しく低下した場合、酸素吸収反応が進行しにくくなり、酸素吸収性能は低下する。
また、上記の脂肪族及び／又は脂環族イソシアネート系硬化剤は、鎖延長剤として主剤であるポリエステルを高分子量化する目的で使用することも出来る。これらのイソシアネート系硬化剤は単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The aliphatic and / or alicyclic isocyanate-based curing agent component is preferably added in an amount of 3 phr to 30 phr, more preferably 5 phr to 20 phr, and even more preferably 7 phr to 15 phr, based on the weight of the solid content, with respect to the main polyester. It is. If the amount added is too small, the adhesiveness and cohesive force will be insufficient, and if it is too large, the amount of the oxygen-absorbing component contained in the resin unit weight will be small and the oxygen-absorbing performance will be insufficient. In addition, when the mobility of the resin is remarkably lowered by curing, the oxygen absorption reaction is difficult to proceed, and the oxygen absorption performance is lowered.
In addition, the aliphatic and / or alicyclic isocyanate-based curing agent described above can also be used for the purpose of increasing the molecular weight of a polyester as a main component as a chain extender. These isocyanate curing agents may be used alone or in combination of two or more.
本発明の酸素吸収性接着剤樹脂組成物は、有機溶剤等の溶媒を含有することが好ましい。溶媒としては、酢酸エチル、アセトン、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、イソプロパノールなどが挙げられる。特に、酢酸エチルは残留溶剤を原因とする異臭トラブルが比較的少ないことから、軟包装のドライラミネート用接着剤の溶媒として一般的であり、産業応用を考慮するとトルエンやキシレン等を含有しない酢酸エチル単一溶剤を本発明の溶媒として用いることが好ましい。
本発明の酸素吸収性接着剤樹脂組成物には、本発明の目的を損なわない範囲で必要に応じてシランカップリング剤、酸化防止剤、紫外線吸収剤、加水分解防止剤、防カビ剤、硬化触媒、増粘剤、可塑剤、顔料、充填剤、ポリエステル樹脂、エポキシ樹脂等の各種添加剤を添加することができる。
The oxygen-absorbing adhesive resin composition of the present invention preferably contains a solvent such as an organic solvent. Examples of the solvent include ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, isopropanol and the like. In particular, ethyl acetate is a common solvent for soft packaging dry laminate adhesives because it has relatively few off-flavor problems caused by residual solvents. Considering industrial applications, ethyl acetate does not contain toluene or xylene. A single solvent is preferably used as the solvent of the present invention.
The oxygen-absorbing adhesive resin composition of the present invention includes a silane coupling agent, an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, an antifungal agent, and a curing agent as necessary without departing from the object of the present invention. Various additives such as a catalyst, a thickener, a plasticizer, a pigment, a filler, a polyester resin, and an epoxy resin can be added.
本発明の酸素吸収性接着剤樹脂組成物は、通常のドライラミネート用接着剤と同様に複数のフィルムを積層する目的で使用することが出来る。特に、酸素バリア性を有するフィルム基材と、ヒートシール性及び酸素ガス透過性を有するシーラントフィルムの積層に好適に使用できる。この場合、外層側から酸素バリア基材層/酸素吸収性接着剤層/シーラント層の積層構成となり、外部から透過進入する酸素を酸素バリア基材により遮断することにより、容器外酸素による酸素吸収性能の低下を抑えると共に、酸素吸収性接着剤が酸素透過性シーラントフィルムを介して容器内部の酸素を速やかに吸収できるため好ましい。
酸素バリア性を有するフィルム基材及びシーラントフィルムはそれぞれ単層でも積層体でもよい。酸素バリア性を有するフィルム基材としては、バリア層としてシリカ、アルミナ等の金属酸化物或いは金属の蒸着薄膜や、ポリビニルアルコール系樹脂、エチレン−ビニルアルコール共重合体、ポリアクリル酸系樹脂或いは塩化ビニリデン系樹脂等のガスバリア性有機材料を主剤とするバリアコーティング層を有する、二軸延伸ＰＥＴフィルム、二軸延伸ポリアミドフィルム或いは二軸延伸ポリプロピレンフィルム等を好適に使用できる。また、エチレン−ビニルアルコール共重合体フィルム、ポリメタキシリレンアジパミドフィルム、ポリ塩化ビニリデン系フィルムやアルミ箔等の金属箔も好ましい。これらの酸素バリア性を有するフィルム基材は、同種基材や２種以上の異種基材を積層して使用することも出来、また、二軸延伸ＰＥＴフィルム、二軸延伸ポリアミドフィルム、二軸延伸ポリプロピレンフィルム、セロファン、紙等を積層して使用することも好ましい。
The oxygen-absorbing adhesive resin composition of the present invention can be used for the purpose of laminating a plurality of films in the same manner as usual dry laminating adhesives. In particular, it can be suitably used for laminating a film substrate having oxygen barrier properties and a sealant film having heat sealability and oxygen gas permeability. In this case, the oxygen barrier base material layer / oxygen-absorbing adhesive layer / sealant layer are laminated from the outer layer side, and the oxygen permeation from the outside is blocked by the oxygen barrier base material. This is preferable because an oxygen-absorbing adhesive can quickly absorb oxygen inside the container through the oxygen-permeable sealant film.
Each of the film base material and the sealant film having oxygen barrier properties may be a single layer or a laminate. As a film substrate having an oxygen barrier property, as a barrier layer, a metal oxide such as silica or alumina or a deposited thin film of metal, a polyvinyl alcohol resin, an ethylene-vinyl alcohol copolymer, a polyacrylic acid resin, or vinylidene chloride is used. A biaxially stretched PET film, a biaxially stretched polyamide film, a biaxially stretched polypropylene film or the like having a barrier coating layer mainly composed of a gas barrier organic material such as a resin can be suitably used. Also preferred are metal foils such as ethylene-vinyl alcohol copolymer films, polymetaxylylene adipamide films, polyvinylidene chloride films and aluminum foils. These film base materials having oxygen barrier properties can be used by laminating the same kind of base material or two or more kinds of different base materials, and also biaxially stretched PET film, biaxially stretched polyamide film, biaxially stretched It is also preferable to use a laminate of polypropylene film, cellophane, paper or the like.
シーラントフィルムの材料としては低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、線状低密度ポリエチレン、線状超低密度ポリエチレン、ポリプロピレン、ポリ−１−ブテン、ポリ−４−メチル−１−ペンテン、環状オレフィン重合体、環状オレフィン共重合体、或いはエチレン、プロピレン、１−ブテン、４−メチル−１−ペンテン等のα−オレフィン同士のランダム又はブロック共重合体等のポリオレフィン、エチレン−酢酸ビニル共重合体、エチレン−（メタ）アクリル酸共重合体やそのイオン架橋物（アイオノマー）、エチレン−メタクリル酸メチル共重合体等のエチレン−ビニル化合物共重合体、ヒートシール性を有するＰＥＴ、Ａ−ＰＥＴ、ＰＥＴＧ、ＰＢＴ等のポリエステルやアモルファスナイロン等を好適に使用できる。これらは二種以上の材料をブレンドして使用することも出来、同種材料や異種材料を積層して用いることも出来る。 The material of the sealant film is low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, cyclic Polyolefins such as olefin polymers, cyclic olefin copolymers, or random or block copolymers of α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, and ethylene-vinyl acetate copolymers , Ethylene- (meth) acrylic acid copolymers and their ionic cross-linked products (ionomers), ethylene-vinyl compound copolymers such as ethylene-methyl methacrylate copolymer, heat-sealable PET, A-PET, PETG PBT and other polyesters and amorphous nylon are preferred It can be used for. These can be used by blending two or more kinds of materials, or can be used by laminating the same kind of materials or different kinds of materials.
本発明の酸素吸収性接着剤樹脂組成物を用いて複数のフィルム基材をラミネートする際、公知のドライラミネーターを使用することが出来る。ドライラミネーターにより、酸素吸収性接着剤樹脂組成物のバリアフィルム基材への塗布、乾燥オーブンによる溶剤揮散、５０〜１２０℃に加温したニップロールでのシーラントフィルムとの貼り合わせの一連のラミネート工程を実施することが出来る。酸素吸収性接着剤樹脂組成物の塗布量は、固形分で０．１〜３０ｇ／ｍ2、好ましくは１〜１５ｇ／ｍ2であり、さらに好ましくは２〜１０ｇ／ｍ2である。酸素吸収性接着剤樹脂組成物を用いてラミネートされた酸素吸収性積層フィルムは、室温付近の温度、例えば１０〜６０℃で硬化反応を進めるためにエージング（キュア）することも好ましい。硬化は主にイソシアネート系硬化剤による架橋反応によるものであり、硬化により接着強度や凝集力が向上するため好ましい。なお、エージングは、酸素吸収性積層フィルムを、例えば酸素不透過性の袋等で密封することにより、酸素不在下若しくは酸素遮断下で行うのが好ましい。このようにすることにより、エージング中における空気中の酸素による酸素吸収性能の低下を抑制することが出来る。
また、本発明の酸素吸収性樹脂組成物は、溶剤に溶解させることなく、無溶剤型接着剤として使用することもできる。この場合、公知のノンソルラミネーターを用いて酸素吸収性積層フィルムを得ることが出来る。
さらに、本発明の酸素吸収性樹脂組成物は、接着剤用途に限らず塗料用途にも使用することができ、各種フィルム等のコーティング膜として塗工することができる。
本発明の酸素吸収性樹脂組成物は、熱履歴や光により過酸化水素が分解、すなわちラジカルが発生し、そのラジカルが本発明で使用するポリエステルの水素引き抜きに伴うラジカル発生を促進することにより、安定したラジカル自動酸化反応が生じ、実用的かつ安定的な酸素吸収性能を発揮する。本発明の酸素吸収性接着剤樹脂組成物においては、ラミネート工程中の乾燥オーブンやニップロールの熱、およびキュア中の熱により過酸化水素からのラジカル発生が起こる。
When laminating a plurality of film substrates using the oxygen-absorbing adhesive resin composition of the present invention, a known dry laminator can be used. With a dry laminator, a series of laminating steps of applying the oxygen-absorbing adhesive resin composition to the barrier film substrate, evaporating the solvent with a drying oven, and laminating with a sealant film with a nip roll heated to 50 to 120 ° C. Can be implemented. The coating amount of the oxygen-absorbing adhesive resin composition, 0.1 to 30 g / m 2 in solid content is preferably 1 to 15 g / m 2, more preferably from 2 to 10 g / m 2. The oxygen-absorbing laminated film laminated using the oxygen-absorbing adhesive resin composition is also preferably aged (cured) to advance the curing reaction at a temperature near room temperature, for example, 10 to 60 ° C. Curing is mainly due to a crosslinking reaction with an isocyanate curing agent, and is preferable because the adhesive strength and cohesive force are improved by curing. In addition, it is preferable to perform aging in oxygen absence or oxygen interruption | blocking by sealing an oxygen absorptive laminated | multilayer film with an oxygen-impermeable bag etc., for example. By doing in this way, the fall of the oxygen absorption performance by the oxygen in the air during aging can be suppressed.
Moreover, the oxygen-absorbing resin composition of the present invention can be used as a solventless adhesive without being dissolved in a solvent. In this case, an oxygen-absorbing laminated film can be obtained using a known non-sol laminator.
Furthermore, the oxygen-absorbing resin composition of the present invention can be used not only for adhesives but also for coatings, and can be applied as coating films such as various films.
In the oxygen-absorbing resin composition of the present invention, hydrogen peroxide is decomposed by heat history and light, that is, radicals are generated, and the radicals promote radical generation accompanying hydrogen abstraction of the polyester used in the present invention. A stable radical auto-oxidation reaction occurs, and practical and stable oxygen absorption performance is exhibited. In the oxygen-absorbing adhesive resin composition of the present invention, radical generation from hydrogen peroxide occurs due to the heat of the drying oven or nip roll during the laminating process and the heat during curing.
本発明の酸素吸収性接着剤樹脂組成物を用いてラミネートされた酸素吸収性積層フィルムは、種々の形態の袋状容器や、カップ・トレイ容器の蓋材に好適に使用できる。袋状容器としては、三方又は四方シールの平パウチ類、ガセット付パウチ類、スタンディングパウチ類、ピロー包装袋等が挙げられる。
酸素吸収性積層フィルムを少なくとも一部に用いた酸素吸収性容器は、容器外部から透過する酸素を有効に遮断し、容器内に残存した酸素を吸収する。そのため、容器内の酸素濃度を長期間低いレベルに保ち、内容物の酸素が係わる品質低下を防止し、シェルフライフを向上させる容器として有用である。
特に、酸素存在下で劣化しやすい内容品として、例えば、食品ではコーヒー豆、茶葉、スナック類、米菓、生・半生菓子、果物、ナッツ、野菜、魚・肉製品、練り製品、干物、薫製、佃煮、生米、米飯類、幼児食品、ジャム、マヨネーズ、ケチャップ、食用油、ドレッシング、ソース類、乳製品等、飲料ではビール、ワイン、フルーツジュース、緑茶、コーヒー等、その他では医薬品、化粧品、電子部品等が挙げられるが、これらの例に限定されない。
The oxygen-absorbing laminated film laminated using the oxygen-absorbing adhesive resin composition of the present invention can be suitably used for various forms of bag-like containers and cup / tray container lids. Examples of the bag-like container include three-way or four-side sealed flat pouches, gusseted pouches, standing pouches, pillow packaging bags, and the like.
An oxygen-absorbing container using at least a part of the oxygen-absorbing laminated film effectively blocks oxygen permeating from the outside of the container and absorbs oxygen remaining in the container. Therefore, it is useful as a container that keeps the oxygen concentration in the container at a low level for a long period of time, prevents the quality deterioration related to the oxygen in the contents, and improves the shelf life.
In particular, as content that easily deteriorates in the presence of oxygen, for example, coffee beans, tea leaves, snacks, rice confectionery, raw and semi-fresh confectionery, fruits, nuts, vegetables, fish and meat products, kneaded products, dried fish, smoked products, Boiled rice, raw rice, cooked rice, infant food, jam, mayonnaise, ketchup, cooking oil, dressing, sauces, dairy products, beverages such as beer, wine, fruit juice, green tea, coffee, etc., pharmaceuticals, cosmetics, electronics Although parts etc. are mentioned, it is not limited to these examples.
以下、本発明を実施例により具体的に説明する。各値は以下の方法により測定した。
（１）数平均分子量（Ｍｎ）及び重量平均分子量（Ｍｗ）
ゲルパーミエーションクロマトグラフィー（ＧＰＣ、東ソー社製；ＨＬＣ−８１２０型ＧＰＣ）により、ポリスチレン換算で測定した。溶媒にはクロロホルムを使用した。
（２）酸成分（Ａ）に由来する構造単位を含むポリエステル中の各モノマー単位の組成比
核磁気共鳴分光法（１Ｈ−ＮＭＲ、日本電子データム社製；ＥＸ２７０）により、コハク酸由来のメチレンプロトン（２．６ｐｐｍ）、メチルテトラヒドロ無水フタル酸及びコハク酸から誘導されたエステル基に隣接するメチレンプロトン（４．１〜４．２ｐｐｍ）のシグナルの面積比から樹脂中の酸成分の組成比をそれぞれ算出した。溶媒には基準物質としてテトラメチルシランを含む重クロロホルムを使用した。
このとき、樹脂中の酸成分の組成比は、重合に使用した各モノマーの仕込み量（モル比）とほぼ同等であった。
（３）ガラス転移温度；Ｔｇ
示差走査熱量測定器（セイコーインスツルメンツ社製ＤＳＣ６２２０）を用いて、窒素気流中、昇温速度１０℃／分で測定した。
（４）酸価
ＪＩＳＫ００７０：１９９２に準じて測定した。
（５）酸素吸収量
２ｃｍ×１０ｃｍに切り出した積層フィルム試験片を、内容積８５ｃｍ3の酸素不透過性のスチール箔積層カップに仕込んでアルミ箔積層フィルム蓋でヒートシール密封し、２２℃雰囲気下にて保存した。３日及び１４日間保存後のカップ内酸素濃度をマイクロガスクロマトグラフ装置（アジレント・テクノロジー社製；Ｍ２００）にて測定し、フィルム１ｍ2当たりの酸素吸収量を算出した。３日区で５０ｍｌ／ｍ2以上且つ１４日区で３００ｍｌ／ｍ2以上の酸素吸収量を満足するものを良好（○）、それ以外を不良（×）とした。
Hereinafter, the present invention will be specifically described by way of examples. Each value was measured by the following method.
(1) Number average molecular weight (Mn) and weight average molecular weight (Mw)
It was measured in terms of polystyrene by gel permeation chromatography (GPC, manufactured by Tosoh Corporation; HLC-8120 GPC). Chloroform was used as the solvent.
(2) Composition ratio of each monomer unit in the polyester containing the structural unit derived from the acid component (A) Methylene proton derived from succinic acid by nuclear magnetic resonance spectroscopy (1H-NMR, manufactured by JEOL Datum; EX270) (2.6 ppm), the composition ratio of the acid component in the resin from the area ratio of the signals of methylene protons (4.1 to 4.2 ppm) adjacent to the ester group derived from methyltetrahydrophthalic anhydride and succinic acid, respectively. Calculated. The solvent used was deuterated chloroform containing tetramethylsilane as a reference substance.
At this time, the composition ratio of the acid component in the resin was substantially equal to the charged amount (molar ratio) of each monomer used for the polymerization.
(3) Glass transition temperature; Tg
Using a differential scanning calorimeter (DSC 6220 manufactured by Seiko Instruments Inc.), the measurement was performed in a nitrogen stream at a heating rate of 10 ° C./min.
(4) Acid value It measured according to JISK0070: 1992.
(5) Oxygen absorption amount A laminated film test piece cut out to 2 cm × 10 cm was charged into an oxygen-impermeable steel foil laminated cup having an internal volume of 85 cm 3 and heat-sealed with an aluminum foil laminated film lid, and the atmosphere was 22 ° C. Saved at. The oxygen concentration in the cup after storage for 3 days and 14 days was measured with a micro gas chromatograph (manufactured by Agilent Technologies; M200), and the amount of oxygen absorbed per 1 m 2 of film was calculated. Those satisfying an oxygen absorption amount of 50 ml / m 2 or more in the 3rd day and 300 ml / m 2 or more in the 14th day were judged as good (◯), and others were judged as bad (x).
（実施例１）
攪拌装置、窒素導入管、コンデンサー、真空装置、及び温度調節装置等を備えた１５０Ｌの重縮合反応槽に、酸成分（Ａ）として４−メチル−Δ3−テトラヒドロ無水フタル酸を４５モル％及びｃｉｓ−３−メチル−Δ4−テトラヒドロ無水フタル酸を２１モル％含有するメチルテトラヒドロ無水フタル酸異性体混合物（日立化成社製；ＨＮ−２２００）を３１．４ｋｇ、その他の酸成分として無水コハク酸を２．１ｋｇ、ジオール成分として１，４−ブタンジオールを２０．８ｋｇ、重合触媒としてイソプロピルチタナート（キシダ化学社製）を３００ｐｐｍ仕込み、窒素雰囲気中１５０℃〜２００℃で生成する水を除きながら約７時間反応させた。引き続いて０．７ｋＰａの減圧下、２００〜２２０℃で約５時間重合を行い、酸素吸収性ポリエステルを得た。さらに重合後反応槽を冷却しながら酢酸エチルにて重合物を希釈し、固形分濃度６０ｗｔ％の酸素吸収性ポリエステル溶液を得た。得られたポリエステル樹脂の、Ｍｗは６０２００、Ｔｇは−４．９℃、酸価は０．５ｍｇＫＯＨ／ｇであった。
得られた酸素吸収性ポリエステル溶液に３０ｗｔ％過酸化水素水溶液をポリエステル樹脂に対して過酸化水素が１０００ｐｐｍになるように添加した。
これにイソシアネート系硬化剤（三井化学社製；Ａ−５０、脂環族・脂肪族混合イソシアネート系硬化剤、固形分濃度７５％）をポリエステル樹脂に対し固形分換算で１０ｐｈｒになるように添加し、さらに固形分濃度が２０ｗｔ％になるように酢酸エチルで希釈して酸素吸収性接着剤溶液を調製した。
調製した接着剤溶液を、１２μｍ透明蒸着ＰＥＴフィルム（凸版印刷社製ＧＬ−ＡＥ）の蒸着面側に、＃１６のバーコーターにて塗布した。１００℃の電気オーブンにて１分間処理して接着剤に含まれる溶剤を飛ばした後、透明蒸着ＰＥＴフィルムの接着剤塗布面と、３０μｍＬＤＰＥフィルム（タマポリ製；ＡＪ−３）のコロナ処理面を対向させて７０℃の熱ロールで圧着し、透明蒸着ＰＥＴフィルム／酸素吸収性樹脂組成物（接着剤）（膜厚４μｍ）／ＬＤＰＥからなる酸素吸収性積層フィルムを得た。
得られた酸素吸収性積層フィルムを、３５℃窒素雰囲気下で５日間キュアした後、酸素吸収性能評価に供した。結果を表１に示す。
Example 1
In a 150 L polycondensation reaction tank equipped with a stirrer, a nitrogen inlet tube, a condenser, a vacuum device, a temperature controller, etc., 45 mol% 4-methyl-Δ 3 -tetrahydrophthalic anhydride as an acid component (A) and 31.4 kg of methyltetrahydrophthalic anhydride isomer mixture (Hitachi Chemical Co., Ltd .; HN-2200) containing 21 mol% of cis-3-methyl-Δ 4 -tetrahydrophthalic anhydride, and succinic anhydride as other acid component 2.1 kg, 20.8 kg of 1,4-butanediol as a diol component, 300 ppm of isopropyl titanate (manufactured by Kishida Chemical Co., Ltd.) as a polymerization catalyst, while removing water produced at 150 ° C. to 200 ° C. in a nitrogen atmosphere The reaction was performed for about 7 hours. Subsequently, polymerization was carried out at 200 to 220 ° C. under a reduced pressure of 0.7 kPa for about 5 hours to obtain an oxygen-absorbing polyester. Further, after the polymerization, the polymer was diluted with ethyl acetate while cooling the reaction vessel to obtain an oxygen-absorbing polyester solution having a solid concentration of 60 wt%. Mw of the obtained polyester resin was 60200, Tg was -4.9 ° C, and the acid value was 0.5 mgKOH / g.
A 30 wt% aqueous hydrogen peroxide solution was added to the obtained oxygen-absorbing polyester solution so that the hydrogen peroxide was 1000 ppm with respect to the polyester resin.
To this was added an isocyanate curing agent (Mitsui Chemicals Co., Ltd .; A-50, alicyclic / aliphatic mixed isocyanate curing agent, solid content concentration 75%) to a polyester resin in a solid content conversion of 10 phr. Further, an oxygen-absorbing adhesive solution was prepared by diluting with ethyl acetate so that the solid content concentration was 20 wt%.
The prepared adhesive solution was applied to the vapor deposition surface side of a 12 μm transparent vapor-deposited PET film (GL-AE manufactured by Toppan Printing Co., Ltd.) with a # 16 bar coater. After processing in an electric oven at 100 ° C. for 1 minute to drive off the solvent contained in the adhesive, the adhesive-coated surface of the transparent vapor-deposited PET film and the corona-treated surface of the 30 μmL DPE film (Tamapoly; AJ-3) face each other Then, pressure bonding was performed with a hot roll at 70 ° C. to obtain an oxygen-absorbing laminated film composed of transparent vapor-deposited PET film / oxygen-absorbing resin composition (adhesive) (film thickness 4 μm) / LDPE.
The obtained oxygen-absorbing laminated film was cured in a nitrogen atmosphere at 35 ° C. for 5 days and then subjected to oxygen absorption performance evaluation. The results are shown in Table 1.
（比較例１）
過酸化水素を添加しなかったこと以外は実施例１と同様にして酸素吸収性積層フィルムを作製し、酸素吸収性能評価に供した。結果を表１に示す。
(Comparative Example 1)
Except that hydrogen peroxide was not added, an oxygen-absorbing laminated film was produced in the same manner as in Example 1, and subjected to oxygen absorption performance evaluation. The results are shown in Table 1.
Claims (5)
酸成分（Ａ）：（ｉ）及び（ii）からなる群より選ばれる構造を有する酸成分；
（ｉ）Δ 2 −テトラヒドロフタル酸若しくはその誘導体、Δ 3 −テトラヒドロフタル酸若しくはその誘導体、Δ 2 −テトラヒドロ無水フタル酸若しくはその誘導体、又はΔ 3 −テトラヒドロ無水フタル酸若しくはその誘導体；
（ii）ｃｉｓ−３−メチル−Δ 4 −テトラヒドロフタル酸若しくはその誘導体又はｃｉｓ−３−メチル−Δ 4 −テトラヒドロ無水フタル酸若しくはその誘導体 An oxygen-absorbing resin composition comprising a polyester containing a structural unit derived from an acid component (A) and hydrogen peroxide.
Acid component (A): an acid component having a structure selected from the group consisting of (i) and (ii);
(I) Δ 2 -tetrahydrophthalic acid or a derivative thereof, Δ 3 -tetrahydrophthalic acid or a derivative thereof, Δ 2 -tetrahydrophthalic anhydride or a derivative thereof, or Δ 3 -tetrahydrophthalic anhydride or a derivative thereof ;
(Ii) cis-3-methyl-Δ 4 -tetrahydrophthalic acid or a derivative thereof or cis-3-methyl-Δ 4 -tetrahydrophthalic anhydride or a derivative thereof
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