JP2020059831A - Adhesive for anticorrosion, adhesive layer for anticorrosion, and adhesive tape for anticorrosion - Google Patents
Adhesive for anticorrosion, adhesive layer for anticorrosion, and adhesive tape for anticorrosion Download PDFInfo
- Publication number
- JP2020059831A JP2020059831A JP2018193484A JP2018193484A JP2020059831A JP 2020059831 A JP2020059831 A JP 2020059831A JP 2018193484 A JP2018193484 A JP 2018193484A JP 2018193484 A JP2018193484 A JP 2018193484A JP 2020059831 A JP2020059831 A JP 2020059831A
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- Prior art keywords
- pressure
- sensitive adhesive
- anticorrosion
- adhesive
- meth
- 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.)
- Granted
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 75
- 239000012790 adhesive layer Substances 0.000 title claims abstract description 21
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 20
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 145
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Abstract
Description
本発明は、防食用粘着剤、防食用粘着剤層及び防食用粘着テープに関する。 The present invention relates to an anticorrosion adhesive, an anticorrosion adhesive layer, and an anticorrosion adhesive tape.
橋梁、鉄塔、高架橋、タンク、プラント、橋脚等の鋼構造物は、時間の経過と共に腐食して錆を生じる。錆が生じることで、鋼構造物の強度が低下したり、また、景観を損なうなどの不具合が生じる。このため、鋼構造物を防食するための種々の方法が検討されている。
特許文献１には、鋼構造物に、無機質ジンクリッチペイントによる塗膜を形成させて防食する技術に関する記載されている。
特許文献２には、構築物の外面に亜鉛粉末とアルキルシリケートの部分加水分解物とを含むプライマー液を塗布し乾燥させてプライマー層を形成し、次いでこのプライマー層に、支持体とこの支持体上に設けられた粘着剤層とからなる防食テープまたはシートを貼り付けて積層することを特徴とする防食被覆方法に関する発明が記載されている。
Steel structures such as bridges, steel towers, viaducts, tanks, plants, bridge piers, etc. corrode and generate rust over time. The rust causes problems such as a decrease in the strength of the steel structure and damage to the landscape. Therefore, various methods for preventing corrosion of steel structures have been investigated.
Patent Document 1 describes a technique of forming a coating film of an inorganic zinc rich paint on a steel structure to prevent corrosion.
In Patent Document 2, a primer solution containing zinc powder and a partial hydrolyzate of alkyl silicate is applied to the outer surface of the construct and dried to form a primer layer, and then the primer layer is formed on the support and the support. The invention relates to an anticorrosion coating method, which comprises sticking and laminating an anticorrosion tape or sheet comprising the adhesive layer provided on the.
このような塗膜、粘着剤層などの鋼構造物を覆っている部材は、外部からの衝撃によって部分的に傷ついて、酸素や水に対する遮断機能が低下し、その結果、鋼構造物の劣化や腐食などが生じる場合がある。このような劣化や腐食を防止する観点から、特許文献３には、自己修復材料と腐食防止剤とを含む複数のマイクロカプセルを含む自己修復系に関する発明が記載されている。具体的には、自己修復系を構成するマトリックスが損傷を受けると、マトリックス中に存在するマイクロカプセルが破裂して、自己修復剤が損傷部位に放出され、該自己修復剤が重合することにより損傷部位の修復を行うことが記載されている。 The member covering the steel structure, such as the coating film and the adhesive layer, is partially damaged by the impact from the outside, and the function of blocking oxygen and water is reduced, resulting in deterioration of the steel structure. And corrosion may occur. From the viewpoint of preventing such deterioration and corrosion, Patent Document 3 describes an invention relating to a self-repair system including a plurality of microcapsules containing a self-repair material and a corrosion inhibitor. Specifically, when the matrix that constitutes the self-repairing system is damaged, the microcapsules present in the matrix are ruptured, the self-repairing agent is released to the damaged site, and the self-repairing agent polymerizes to cause damage. It is described to perform site repair.
しかしながら、特許文献３に記載の自己修復系は、マトリックスが損傷を受けた際に、マイクロカプセルが必ずしも割れるとは限らない。そのため、錆の発生を効果的に防止することが難しく、防食性能が十分とはいえない。
本発明は、以上の事情に鑑みてなされたものであり、本発明の課題は、外部から損傷を受けた場合であっても、高い防食性能を維持できる防食用粘着剤、及びこれを用いた防食用粘着剤層並びに防食用粘着テープを提供することである。
However, the self-healing system described in Patent Document 3 does not always break the microcapsules when the matrix is damaged. Therefore, it is difficult to effectively prevent the generation of rust, and the anticorrosion performance is not sufficient.
The present invention has been made in view of the above circumstances, and an object of the present invention is to use an anticorrosion pressure-sensitive adhesive that can maintain high anticorrosion performance even when it is damaged from the outside, and the same. An object is to provide an anticorrosion adhesive layer and an anticorrosion adhesive tape.
本発明者らは、鋭意検討の結果、４０℃での貯蔵弾性率を特定範囲にした粘着剤が上記課題を解決できることを見出し、以下の発明を完成させた。本発明は、以下の［１］〜［１０］を提供する。
［１］４０℃での貯蔵弾性率Ｇ’が５万〜１００万Ｐａである、防食用粘着剤。
［２］５℃での貯蔵弾性率Ｇ’が５万〜１００万Ｐａである、上記［１］に記載の防食用粘着剤。
［３］ステンレス板に対する９０°剥離試験における粘着力が５Ｎ／２５ｍｍ以上である、上記［１］又は［２］に記載の防食用粘着剤。
［４］アクリル系粘着剤を含有する、上記［１］〜［３］のいずれかに記載の防食用粘着剤。
［５］鉄よりも電位が卑な金属を含有する、上記［１］〜［４］のいずれかに記載の防食用粘着剤。
［６］前記鉄よりも電位が卑な金属が亜鉛である、上記［５］に記載の防食用粘着剤。
［７］前記金属以外の導電性材料を含有する、上記［１］〜［６］のいずれかに記載の防食用粘着剤。
［８］上記［１］〜［７］のいずれかに記載の粘着剤からなる防食用粘着剤層。
［９］厚みが５０〜３０００μｍである、上記［８］に記載の防食用粘着剤層。
［１０］上記［８］又は［９］に記載の粘着剤層を備える、防食用粘着テープ。
As a result of earnest studies, the present inventors have found that an adhesive having a storage elastic modulus at 40 ° C. in a specific range can solve the above problems, and completed the following inventions. The present invention provides the following [1] to [10].
[1] An anticorrosive pressure-sensitive adhesive having a storage elastic modulus G ′ at 40 ° C. of 50,000 to 1,000,000 Pa.
[2] The pressure-sensitive adhesive for corrosion protection according to [1], which has a storage elastic modulus G ′ at 5 ° C. of 50,000 to 1,000,000 Pa.
[3] The anticorrosive pressure-sensitive adhesive according to the above [1] or [2], which has an adhesive strength of 5 N / 25 mm or more in a 90 ° peel test on a stainless steel plate.
[4] The anticorrosive pressure-sensitive adhesive according to any one of the above [1] to [3], which contains an acrylic pressure-sensitive adhesive.
[5] The anticorrosive pressure-sensitive adhesive according to any one of the above [1] to [4], which contains a metal having a potential lower than that of iron.
[6] The anticorrosive pressure-sensitive adhesive according to the above [5], wherein the metal having a potential lower than that of iron is zinc.
[7] The anticorrosive pressure-sensitive adhesive according to any one of the above [1] to [6], which contains a conductive material other than the metal.
[8] An anticorrosive pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to any one of [1] to [7] above.
[9] The anticorrosion pressure-sensitive adhesive layer according to the above [8], which has a thickness of 50 to 3000 μm.
[10] An anticorrosion adhesive tape comprising the adhesive layer according to [8] or [9].
本発明によれば、外部から損傷を受けた場合であっても、高い防食性能を維持できる防食用粘着剤、及びこれを用いた防食用粘着剤層並びに防食用粘着テープを提供できる。 According to the present invention, it is possible to provide an anticorrosion adhesive that can maintain high anticorrosion performance even when it is damaged from the outside, and an anticorrosion adhesive layer and an anticorrosion adhesive tape using the same.
本発明の防食用粘着剤は、４０℃での貯蔵弾性率Ｇ’が５万〜１００万Ｐａである。該防食用粘着剤は、各種金属材料からなる被着体の腐食を防止するために用いられる防食用粘着剤であり、好ましくは、後述するように防食用粘着剤からなる防食用粘着剤層、又は該粘着剤層を備えた防食用粘着テープを被着体表面に貼付して、被着体の腐食を防止する。
以下、本発明について詳細に説明する。
The anticorrosive pressure-sensitive adhesive of the present invention has a storage elastic modulus G ′ at 40 ° C. of 50,000 to 1,000,000 Pa. The anticorrosive adhesive is an anticorrosive adhesive used for preventing corrosion of adherends made of various metal materials, and preferably an anticorrosive adhesive layer made of an anticorrosive adhesive as described below. Alternatively, an anticorrosive pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer is attached to the surface of the adherend to prevent the adherend from corrosion.
Hereinafter, the present invention will be described in detail.
（貯蔵弾性率Ｇ’）
本発明の防食用粘着剤は、４０℃での貯蔵弾性率Ｇ’が５万〜１００万Ｐａである。防食用粘着剤の４０℃での貯蔵弾性率Ｇ’が５万未満であると、防食性能が低下する。４０℃での貯蔵弾性率Ｇ’が５万未満場合、防食用粘着剤を構成する樹脂の粘性が高く、樹脂は流動しやすいが、弾性が低すぎるため、防食用粘着剤が外部衝撃などにより損傷した場合に、損傷部位を元に戻すよりもむしろ広がる方向に樹脂が流動し、損傷部位を元に戻す力（以下、自己修復力ともいう）が弱い。そのため、被着体表面が露出、あるいは防食用粘着剤により形成される層（防食用粘着剤層）が部分的に薄くなるなどして、被着体の腐食を防止する機能が低下すると考えられる。
防食用粘着剤の４０℃での貯蔵弾性率Ｇ’が１００万を超える場合でも、被着体の腐食を防止する機能が低下する。４０℃での貯蔵弾性率Ｇ’が１００万を超える場合、防食用粘着剤を構成する樹脂の弾性が高く、粘性が低い。そのため、防食用粘着剤を構成する樹脂の流動性が低く、粘着剤が損傷した場合に、損傷部位を樹脂で閉塞し難く、自己修復力が弱い。その結果、上記した場合と同様に、被着体の腐食を防止する機能が低下すると考えられる。
本発明の防食用粘着剤は、４０℃での貯蔵弾性率Ｇ’が５万〜１００万Ｐａであり、粘着剤を構成する樹脂が適度な弾性及び粘性を有し、そのため、粘着剤が外部衝撃などにより損傷した場合の自己修復力が高く、高い防食性能を有すると考えられる。
防食用粘着剤の４０℃での貯蔵弾性率Ｇ’は、好ましくは２０万〜８０万Ｐａであり、より好ましくは３０万〜６０万Ｐａである。４０℃での貯蔵弾性率Ｇ’がこのような範囲であると、粘着剤の自己修復力が高まり、防食性能が向上する。
(Storage elastic modulus G ')
The anticorrosive pressure-sensitive adhesive of the present invention has a storage elastic modulus G ′ at 40 ° C. of 50,000 to 1,000,000 Pa. If the storage elastic modulus G'at 40 ° C of the anticorrosive adhesive is less than 50,000, the anticorrosive performance is deteriorated. If the storage elastic modulus G'at 40 ° C is less than 50,000, the viscosity of the resin constituting the anticorrosion adhesive is high and the resin easily flows, but since the elasticity is too low, the anticorrosion adhesive may be subject to external impact or the like. When damaged, the resin flows in a direction in which it spreads rather than restores the damaged site, and the force for restoring the damaged site (hereinafter, also referred to as self-repairing force) is weak. As a result, the surface of the adherend is exposed, or the layer formed of the anticorrosion adhesive (anticorrosion adhesive layer) is partially thinned, and the function of preventing the corrosion of the adherend is thought to deteriorate. .
Even when the storage elastic modulus G ′ of the anticorrosive adhesive at 40 ° C. exceeds 1,000,000, the function of preventing the adherend from corroding deteriorates. When the storage elastic modulus G ′ at 40 ° C. exceeds 1 million, the elasticity of the resin constituting the anticorrosive adhesive is high and the viscosity is low. Therefore, the fluidity of the resin constituting the anticorrosive pressure-sensitive adhesive is low, and when the pressure-sensitive adhesive is damaged, it is difficult for the resin to close the damaged site, and the self-repairing power is weak. As a result, as in the case described above, it is considered that the function of preventing the corrosion of the adherend deteriorates.
The anticorrosive pressure-sensitive adhesive of the present invention has a storage elastic modulus G ′ at 40 ° C. of 50,000 to 1,000,000 Pa, and the resin constituting the pressure-sensitive adhesive has appropriate elasticity and viscosity. It has a high self-repairing power when damaged by impact, and is considered to have high anticorrosion performance.
The storage elastic modulus G ′ of the anticorrosive adhesive at 40 ° C. is preferably 200,000 to 800,000 Pa, more preferably 300,000 to 600,000 Pa. When the storage elastic modulus G ′ at 40 ° C. is in such a range, the self-repairing power of the pressure-sensitive adhesive is enhanced and the anticorrosion performance is improved.
本発明の防食用粘着剤の５℃での貯蔵弾性率Ｇ’は、好ましくは５万〜１００万Ｐａである。防食用粘着剤の４０℃の貯蔵弾性率が上記のとおりであり、かつ５℃での貯蔵弾性率がこのような範囲であると、比較的広い温度範囲で、防食用粘着剤の自己修復力が高くなり、高い防食性能を有する。
防食用粘着剤の５℃での貯蔵弾性率Ｇ’は、好ましくは１０万〜９０万Ｐａであり、より好ましくは７０万〜９０万Ｐａである。５℃での貯蔵弾性率Ｇ’がこのような範囲であると、防食用粘着剤の自己修復力が高まり、防食性能が向上する。
防食用粘着剤の貯蔵弾性率Ｇ’は、後述する粘着剤の組成を調整することにより、所望の範囲に調節することができる。
貯蔵弾性率Ｇ’は、例えばＤＶＡ−２００（アイティー計測制御株式会社製）を用いて、せん断モード：１０Ｈｚ、歪み量：０．１％、温度範囲：−１００℃〜１００℃、昇温速度：１０℃/ｍｉｎの条件下で、動的粘弾性スペクトルを測定して算出することができる。
The storage modulus G ′ of the anticorrosive pressure-sensitive adhesive of the present invention at 5 ° C. is preferably 50,000 to 1,000,000 Pa. When the storage elastic modulus of the anticorrosive adhesive at 40 ° C. is as described above and the storage elastic modulus at 5 ° C. is in such a range, the self-restoring power of the anticorrosive adhesive is relatively wide. And has high anticorrosion performance.
The storage elastic modulus G ′ at 5 ° C. of the anticorrosive pressure-sensitive adhesive is preferably 100,000 to 900,000 Pa, more preferably 700,000 to 900,000 Pa. When the storage elastic modulus G ′ at 5 ° C. is in such a range, the self-repairing power of the anticorrosive pressure-sensitive adhesive is increased, and the anticorrosive performance is improved.
The storage elastic modulus G ′ of the anticorrosive pressure-sensitive adhesive can be adjusted to a desired range by adjusting the composition of the pressure-sensitive adhesive described below.
The storage elastic modulus G ′ is, for example, using DVA-200 (manufactured by IT Measurement and Control Co., Ltd.), shear mode: 10 Hz, strain amount: 0.1%, temperature range: −100 ° C. to 100 ° C., temperature rising rate. The dynamic viscoelastic spectrum can be measured and calculated under the condition of 10 ° C./min.
（粘着力）
本発明の防食用粘着剤は、ステンレス板に対する９０°剥離試験における粘着力（以下、単に粘着力ともいう）が５Ｎ／２５ｍｍ以上であることが好ましい。粘着力が５Ｎ／２５ｍｍ以上であることにより、防食用粘着剤の自己修復力が向上する。これは、粘着剤が損傷した場合に、粘着力が高いと、その粘着力により損傷部位が閉塞されやすいためと考えられる。
防食用粘着剤の粘着力は、自己修復力をより向上させる観点から、好ましくは１０Ｎ／２５ｍｍ以上であることが好ましく，２０Ｎ／２５ｍｍ以上であることがより好ましく、３０Ｎ／２５ｍｍ以上であることが更に好ましい。粘着剤の粘着力は高ければ高い方がよいが、通常は１００Ｎ／２５ｍｍ以下である。
防食用粘着剤の粘着力は、後述する粘着剤の組成を調整することにより、所望の範囲に調節することができる。
粘着剤の粘着力は、以下のとおり測定する。粘着剤からなる粘着剤層を形成させ、これを２５ｍｍ幅の短冊状に裁断して試験片を作成し、該試験片をステンレス板上に重ね合わせて２ｋｇのローラで押圧し、試験片をステンレス板上に貼着した後、温度２３℃、相対湿度５０％の雰囲気で３０分放置する。そして、該試験片をステンレス板に対して９０°方向に、剥離速度３００ｍｍ／分で、引張試験を行なったときの剥離力（Ｎ／２５ｍｍ）を測定し、これを粘着力とする。
(Adhesive force)
The anticorrosive pressure-sensitive adhesive of the present invention preferably has an adhesive force (hereinafter, also simply referred to as “adhesive force”) of 5 N / 25 mm or more in a 90 ° peel test on a stainless steel plate. When the adhesive strength is 5 N / 25 mm or more, the self-repairing power of the anticorrosive adhesive is improved. This is considered to be because if the adhesive has a high adhesive strength, the damaged area is likely to be blocked by the adhesive strength.
The adhesive strength of the anticorrosive adhesive is preferably 10 N / 25 mm or more, more preferably 20 N / 25 mm or more, and more preferably 30 N / 25 mm or more, from the viewpoint of further improving the self-repairing power. More preferable. The higher the adhesive strength of the adhesive, the better, but it is usually 100 N / 25 mm or less.
The adhesive strength of the anticorrosive adhesive can be adjusted to a desired range by adjusting the composition of the adhesive described below.
The adhesive strength of the adhesive is measured as follows. A pressure-sensitive adhesive layer made of a pressure-sensitive adhesive is formed, and this is cut into a strip of 25 mm width to prepare a test piece. The test piece is superposed on a stainless steel plate and pressed with a 2 kg roller, and the test piece is made of stainless steel. After sticking on the plate, it is left for 30 minutes in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. Then, the peeling force (N / 25 mm) when the tensile test was performed on the test piece in the 90 ° direction at a peeling speed of 300 mm / min was measured, and this was taken as the adhesive force.
（防食用粘着剤）
本発明の防食用粘着剤の粘着剤の種類は特に限定されないが、アクリル系粘着剤、ゴム系粘着剤、ウレタン系粘着剤、及びシリコーン系粘着剤などが挙げられる。これらは単独で使用してよいし、組み合わせて使用してもよい。本発明の粘着剤は、これらの中では、アクリル系粘着剤が好ましい。アクリル系粘着剤を使用すると、粘着剤の４０℃及び５℃での貯蔵弾性率並びに粘着力を所望の範囲に調整しやすくなる。
(Adhesive for anticorrosion)
The type of the pressure-sensitive adhesive of the anticorrosive pressure-sensitive adhesive of the present invention is not particularly limited, and examples thereof include an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, and a silicone pressure-sensitive adhesive. These may be used alone or in combination. Among these, the adhesive of the present invention is preferably an acrylic adhesive. Use of an acrylic pressure-sensitive adhesive makes it easier to adjust the storage elastic modulus and pressure-sensitive adhesive strength of the pressure-sensitive adhesive at 40 ° C. and 5 ° C. to desired ranges.
（アクリル系粘着剤）
以下、防食用粘着剤に使用されるアクリル系粘着剤の一実施形態についてより詳細に説明する。アクリル系粘着剤は、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）を含む重合性モノマーを重合したアクリル系重合体を含有する粘着剤である。
なお、本明細書において、用語「（メタ）アクリル酸アルキルエステル」とは、アクリル酸アルキルエステル、及びメタクリル酸アルキルエステルの両方を含む概念を指すものであり、他の類似の用語も同様である。また、用語「重合性モノマー」は、繰り返し単位を有しない化合物のみならず、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）と共重合する化合物であれば、後述するオレフィン重合体（Ｃ）などのモノマー自身が繰り返し単位を有するものも含みうる概念を指す。
(Acrylic adhesive)
Hereinafter, one embodiment of the acrylic pressure-sensitive adhesive used for the anticorrosive pressure-sensitive adhesive will be described in more detail. The acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive containing an acrylic polymer obtained by polymerizing a polymerizable monomer containing a (meth) acrylic acid alkyl ester-based monomer (A).
In addition, in this specification, the term "(meth) acrylic acid alkyl ester" refers to a concept including both acrylic acid alkyl ester and methacrylic acid alkyl ester, and other similar terms are also the same. . Further, the term "polymerizable monomer" means not only a compound having no repeating unit but also an olefin polymer (C) described later as long as it is a compound copolymerizable with the (meth) acrylic acid alkyl ester-based monomer (A). Refers to a concept that the monomer itself may have a repeating unit.
［（メタ）アクリル酸アルキルエステル系モノマー（Ａ）］
（メタ）アクリル酸アルキルエステル系モノマー（Ａ）は、（メタ）アクリル酸と脂肪族アルコールとのエステルであって、脂肪族アルコールのアルキル基の炭素数が、好ましくは２〜１４、より好ましくは４〜１０である脂肪族アルコールに由来するアルキルエステルが好ましい。アルキル基の炭素数がこの範囲内であると、粘着剤の４０℃及び５℃での貯蔵弾性率並びに粘着力を上記した範囲に調整しやすくなる。
[(Meth) acrylic acid alkyl ester-based monomer (A)]
The (meth) acrylic acid alkyl ester-based monomer (A) is an ester of (meth) acrylic acid and an aliphatic alcohol, and the carbon number of the alkyl group of the aliphatic alcohol is preferably 2 to 14, and more preferably Alkyl esters derived from aliphatic alcohols of 4 to 10 are preferred. When the carbon number of the alkyl group is within this range, it becomes easy to adjust the storage elastic modulus at 40 ° C. and 5 ° C. and the adhesive strength of the adhesive within the above ranges.
具体的な（メタ）アクリル酸アルキルエステル系モノマー（Ａ）としては、例えば、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、及びテトラデシル（メタ）アクリレート等が挙げられる。
これらの中でも、ｎ−ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレートが好ましく、ｎ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート又はこれらの組み合わせがより好ましい。
（メタ）アクリル酸アルキルエステル系モノマーは、単独で使用してもよいし、２種以上を組み合わせて用いてもよい。
Specific examples of the (meth) acrylic acid alkyl ester-based monomer (A) include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) Examples thereof include acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, and tetradecyl (meth) acrylate.
Among these, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-octyl (meth) acrylate are preferable, and n-butyl (meth) acrylate, More preferred is 2-ethylhexyl (meth) acrylate or a combination thereof.
The (meth) acrylic acid alkyl ester-based monomers may be used alone or in combination of two or more kinds.
（メタ）アクリル酸アルキルエステル系モノマー（Ａ）由来の構成単位は、防食用粘着剤において主成分を構成するものであって、その含有量は、防食用粘着剤全量基準で一般的に３０質量％以上、好ましくは５０質量％以上、より好ましくは７０質量％以上である。このように、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）の含有量を多くすると、防食用粘着剤に所望の粘着力を付与することが可能になる。
なお、防食用粘着剤における（メタ）アクリル酸アルキルエステル系モノマー（Ａ）由来の構成単位の含有量は、後述する防食用粘着剤組成物における（メタ）アクリル酸アルキルエステル系モノマー（Ａ）の含有量と実質的に同じであるので、置き換えて表すことができる。以下で説明する（Ｂ）、（Ｃ）成分など、（Ａ）成分以外の成分も同様である。
The constituent unit derived from the (meth) acrylic acid alkyl ester-based monomer (A) constitutes the main component in the anticorrosive adhesive, and its content is generally 30 mass based on the total amount of the anticorrosive adhesive. % Or more, preferably 50% by mass or more, more preferably 70% by mass or more. As described above, when the content of the (meth) acrylic acid alkyl ester-based monomer (A) is increased, it becomes possible to impart a desired adhesive force to the anticorrosive adhesive.
The content of the structural unit derived from the (meth) acrylic acid alkyl ester-based monomer (A) in the anticorrosion adhesive is the same as that of the (meth) acrylic acid alkylester-based monomer (A) in the anticorrosion adhesive composition described below. Since it is substantially the same as the content, it can be expressed by being replaced. The same applies to components other than the component (A), such as the components (B) and (C) described below.
［極性基含有ビニルモノマー（Ｂ）］
重合性モノマーは、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）に加えて、極性基含有ビニルモノマー（Ｂ）を含有することが好ましい。極性基含有ビニルモノマー（Ｂ）は、極性基とビニル基を有するものである。防食用粘着剤に極性基含有モノマー（Ｂ）を用いることで、粘着剤の４０℃及び５℃での貯蔵弾性率並びに粘着力などを調整しやすくなる。
極性基含有ビニルモノマー（Ｂ）としては、例えば、酢酸ビニル等のカルボン酸ビニルエステル、（メタ）アクリル酸、及びイタコン酸等のビニル基を含有するカルボン酸、及びその無水物、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、カプロラクトン変性（メタ）アクリレート、ポリオキシエチレン（メタ）アクリレート、及びポリオキシプロピレン（メタ）アクリレート等の水酸基を有するビニルモノマー、（メタ）アクリロニトリル、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、Ｎ−ビニルラウリロラクタム、（メタ）アクリロイルモルホリン、（メタ）アクリルアミド、ジメチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、及びジメチルアミノメチル（メタ）アクリレート等の窒素含有ビニルモノマーが挙げられる。
これらの中でも、（メタ）アクリル酸、及びイタコン酸等のビニル基を含有するカルボン酸、及びその無水物が好ましく、（メタ）アクリル酸がより好ましく、アクリル酸が更に好ましい。これらの極性基含有ビニルモノマー（Ｂ）は、単独で使用してもよいし、２種以上を組み合わせて用いてもよい。
[Polar group-containing vinyl monomer (B)]
The polymerizable monomer preferably contains a polar group-containing vinyl monomer (B) in addition to the (meth) acrylic acid alkyl ester-based monomer (A). The polar group-containing vinyl monomer (B) has a polar group and a vinyl group. By using the polar group-containing monomer (B) in the anticorrosive pressure-sensitive adhesive, it becomes easy to adjust the storage elastic modulus and pressure-sensitive adhesive strength of the pressure-sensitive adhesive at 40 ° C and 5 ° C.
The polar group-containing vinyl monomer (B) includes, for example, carboxylic acid vinyl ester such as vinyl acetate, (meth) acrylic acid, and vinyl group-containing carboxylic acid such as itaconic acid, and an anhydride thereof, 2-hydroxyethyl. (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified (meth) acrylate, polyoxyethylene (meth) acrylate, and polyoxypropylene (meth) acrylate Having vinyl monomer, (meth) acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyllaurylolactam, (meth) acryloylmorpholine, (meth) acrylamide, dimethyl (meth) acrylamide, N-methylol (meth) ) Acrylamide, N- butoxymethyl (meth) acrylamide, and nitrogen-containing vinyl monomers such as dimethylaminomethyl (meth) acrylate.
Among these, carboxylic acids containing a vinyl group such as (meth) acrylic acid and itaconic acid, and anhydrides thereof are preferable, (meth) acrylic acid is more preferable, and acrylic acid is further preferable. These polar group-containing vinyl monomers (B) may be used alone or in combination of two or more.
極性基含有ビニルモノマー（Ｂ）を使用する場合、防食用粘着剤において極性基含有ビニルモノマー（Ｂ）由来の構成単位の含有量は、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）由来の構成単位１００質量部に対して、好ましくは１〜１５質量部、より好ましくは２〜１２質量部、さらに好ましくは３〜１０質量部である。極性基含有ビニルモノマー（Ｂ）の含有量をこのような範囲内とすることで、粘着剤の４０℃及び５℃での貯蔵弾性率並びに粘着力などを適切な範囲に調整しやすくなる。 When the polar group-containing vinyl monomer (B) is used, the content of the constituent unit derived from the polar group-containing vinyl monomer (B) in the anticorrosive pressure-sensitive adhesive is such that it is derived from the (meth) acrylic acid alkyl ester-based monomer (A). The amount is preferably 1 to 15 parts by mass, more preferably 2 to 12 parts by mass, and further preferably 3 to 10 parts by mass with respect to 100 parts by mass of the unit. By setting the content of the polar group-containing vinyl monomer (B) within such a range, it becomes easy to adjust the storage elastic modulus at 40 ° C. and 5 ° C., the adhesive strength, etc. of the adhesive to an appropriate range.
［オレフィン重合体（Ｃ）］
重合性モノマーは、さらに片末端に重合性結合を有するオレフィン重合体（Ｃ）を含むことが好ましい。このようなオレフィン重合体（Ｃ）を使用することで、粘着剤の４０℃及び５℃での貯蔵弾性率、並びに粘着力を上記した所望の範囲に調整しやすくなる。なお、重合性結合は、重合性モノマーと重合することが可能な不飽和の炭素−炭素結合を意味し、例えば不飽和二重結合が挙げられ、好ましくは（メタ）アクリロイル基などが挙げられる。
オレフィン重合体（Ｃ）としては、片末端に（メタ）アクリロイル基を有するポリオレフィンが挙げられる。なお、ポリオレフィンとは、エチレン、プロピレン、ブタン、ブタジエン、イソプレンなどの二重結合を有する脂肪族炭化水素化合物の重合体、又はその水素添加物である。
[Olefin polymer (C)]
The polymerizable monomer preferably further contains an olefin polymer (C) having a polymerizable bond at one end. By using such an olefin polymer (C), it becomes easy to adjust the storage elastic modulus of the pressure-sensitive adhesive at 40 ° C. and 5 ° C. and the pressure-sensitive adhesive strength within the above-mentioned desired ranges. The polymerizable bond means an unsaturated carbon-carbon bond capable of polymerizing with a polymerizable monomer, and examples thereof include an unsaturated double bond, and preferably a (meth) acryloyl group.
Examples of the olefin polymer (C) include a polyolefin having a (meth) acryloyl group at one end. The polyolefin is a polymer of an aliphatic hydrocarbon compound having a double bond such as ethylene, propylene, butane, butadiene and isoprene, or a hydrogenated product thereof.
片末端に（メタ）アクリロイル基を有するポリオレフィンとしては、例えば、片末端にエポキシ基を有するポリエチレンと（メタ）アクリル酸とを反応させることにより調製された、片末端に（メタ）アクリロイル基を有するポリエチレン等が挙げられる。また、片末端に（メタ）アクリロイル基を有するポリブタジエン又はその水素添加物が挙げられ、その市販品として株式会社クラレ製の「Ｌ−１２５３」等が挙げられる。 The polyolefin having a (meth) acryloyl group at one end has, for example, a (meth) acryloyl group at one end prepared by reacting polyethylene having an epoxy group at one end with (meth) acrylic acid. Examples thereof include polyethylene. In addition, polybutadiene having a (meth) acryloyl group at one end or a hydrogenated product thereof can be mentioned, and as a commercially available product thereof, "L-1253" manufactured by Kuraray Co., Ltd. and the like can be mentioned.
オレフィン重合体（Ｃ）は、その数平均分子量が好ましくは５００〜２００００、より好ましくは１０００〜１００００である。なお、数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定し、標準ポリスチレンの検量線を用いて算出すればよい。
また、アクリル系粘着剤においてオレフィン重合体（Ｃ）由来の構成単位の含有量は、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）由来の構成単位１００質量部に対して、１〜２０質量部が好ましく、２〜１５質量部がより好ましく、４〜１２質量部がさらに好ましい。
The number average molecular weight of the olefin polymer (C) is preferably 500 to 20,000, more preferably 1,000 to 10,000. The number average molecular weight may be measured by gel permeation chromatography (GPC) and calculated using a calibration curve of standard polystyrene.
In addition, the content of the structural unit derived from the olefin polymer (C) in the acrylic pressure-sensitive adhesive is 1 to 20 parts by mass with respect to 100 parts by mass of the structural unit derived from the (meth) acrylic acid alkyl ester-based monomer (A). Is preferred, 2 to 15 parts by mass is more preferred, and 4 to 12 parts by mass is even more preferred.
［架橋剤（Ｄ）］
重合性モノマーはさらに、架橋剤を含むことが好ましい。架橋剤としては、ビニル基を２つ以上有する多官能モノマーが挙げられ、好ましくは（メタ）アクリロイル基を２つ以上有する多官能（メタ）アクリレートが挙げられる。多官能モノマーを使用すると、防食用粘着剤の４０℃及び５℃での貯蔵弾性率並びに粘着力などを適切な範囲に調整しやすくなる。
多官能（メタ）アクリレートとしては、特に限定されず、ヘキサンジオールジ（メタ）アクリレート、エトシキ化ビスフェノールＡジ（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートトリアクリレート、エトシキ化トリメチロールプロパントリアクリレート、プロキシ化トリメチロールプロパントリアクリレート、プロキシ化グリセリルトリアクリレート、ネオペンチルグリコールアジペートジアクリレートなどの他に、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、液状水素化１，２−ポリブタジエンジ（メタ）アクリレートなどの重合体が挙げられる。これら多官能（メタ）アクリレートの中でも、重合体が好ましく、液状水素化１，２−ポリブタジエンジアクリレートがより好ましい。液状水素化１，２−ポリブタジエンジアクリレートの市販品としては、日本曹達株式会社製の「ＴＥＡＩ−１０００」等が挙げられる。
また、アクリル系粘着剤において架橋剤由来の構成単位の含有量は、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）由来の構成単位１００質量部に対して、０．１〜４質量部が好ましく、０．３〜３質量部がより好ましく、０．５〜２質量部がさらに好ましい。
[Crosslinking agent (D)]
The polymerizable monomer preferably further contains a crosslinking agent. Examples of the cross-linking agent include polyfunctional monomers having two or more vinyl groups, preferably polyfunctional (meth) acrylates having two or more (meth) acryloyl groups. When a polyfunctional monomer is used, it becomes easy to adjust the storage elastic modulus at 40 ° C. and 5 ° C., the adhesive strength, etc. of the anticorrosive adhesive to an appropriate range.
The polyfunctional (meth) acrylate is not particularly limited, and hexanediol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane tri Acrylate, proxylated trimethylolpropane triacrylate, proxylated glyceryl triacrylate, neopentyl glycol adipate diacrylate, etc., as well as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, liquid hydrogenated 1,2- Examples thereof include polymers such as polybutadiene di (meth) acrylate. Among these polyfunctional (meth) acrylates, polymers are preferable, and liquid hydrogenated 1,2-polybutadiene diacrylate is more preferable. Examples of commercially available liquid hydrogenated 1,2-polybutadiene diacrylate include "TEAI-1000" manufactured by Nippon Soda Co., Ltd.
In addition, the content of the structural unit derived from the crosslinking agent in the acrylic pressure-sensitive adhesive is preferably 0.1 to 4 parts by mass with respect to 100 parts by mass of the structural unit derived from the (meth) acrylic acid alkyl ester monomer (A). , 0.3 to 3 parts by mass is more preferable, and 0.5 to 2 parts by mass is still more preferable.
［鉄よりも電位が卑な金属］
アクリル系粘着剤は、鉄よりも電位が卑な金属を含有してもよい。鉄よりも電位が卑な金属(以下、「犠牲防食用金属」ともいう)を含有することにより、犠牲防食性を有し、本発明の粘着剤からなる粘着剤層が貼付された被着体の防食性が高まる。
鉄よりも電位が卑な金属（犠牲防食用金属）としては、カドミウム、クロム、亜鉛、マンガン、アルミニウムなどが挙げられ、これらの中では亜鉛、アルミニウムが好ましく、特に亜鉛が好ましい。亜鉛を使用することで犠牲防食性が優れたものとなる。
犠牲防食用金属は、粒子形状、鱗片形状、紡錘形状等、フィラーとしていかなる形態で粘着剤に分散されていてもよいが、好ましくは粒子形状であることが好ましい。犠牲防食用金属は、粒子形状とすることで、粘着剤の粘着性を殆ど低下させることなく、粘着剤中に分散されやすくなる。
本明細書において、粒子形状とは、短軸方向の長さに対する長軸方向の長さの比（アスペクト比）が小さいものであり、例えば、アスペクト比が３以下、好ましくは２以下である。粒子形状は、特に限定されないが、球形であってもよいし、粉体等の不定形のものであってもよい。粒子形状の上記金属は、その粒径が例えば１〜５００μｍ、好ましくは１〜２００μｍである。なお、本明細書において粒径とは、レーザー回折法により測定した平均粒径を意味する。
犠牲防食用金属を用いる場合、その粘着剤における含有量は、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）由来の構成単位１００質量部に対して、好ましくは５〜３０質量部、より好ましくは１５〜２５質量部である。
[Metal whose electric potential is lower than iron]
The acrylic pressure-sensitive adhesive may contain a metal having a potential lower than that of iron. By containing a metal whose potential is lower than iron (hereinafter, also referred to as "sacrificial anticorrosion metal"), it has sacrificial anticorrosive properties, and an adherend to which an adhesive layer made of the adhesive of the present invention is attached The anticorrosion property of is increased.
Examples of metals having a lower potential than iron (sacrificial anticorrosion metals) include cadmium, chromium, zinc, manganese, and aluminum. Among these, zinc and aluminum are preferable, and zinc is particularly preferable. By using zinc, sacrificial corrosion resistance becomes excellent.
The sacrificial anticorrosion metal may be dispersed in the pressure-sensitive adhesive in any form as a filler, such as a particle shape, a scale shape, a spindle shape, or the like, but the particle shape is preferable. The sacrificial anticorrosion metal is easily dispersed in the pressure-sensitive adhesive without causing the pressure-sensitive adhesiveness of the pressure-sensitive adhesive to be reduced by forming the metal into a particle shape.
In the present specification, the particle shape has a small ratio of the length in the major axis direction to the length in the minor axis direction (aspect ratio), and for example, the aspect ratio is 3 or less, preferably 2 or less. The particle shape is not particularly limited, but may be a spherical shape or an irregular shape such as powder. The metal in particle form has a particle size of, for example, 1 to 500 μm, preferably 1 to 200 μm. In addition, in this specification, a particle diameter means the average particle diameter measured by the laser diffraction method.
When using a sacrificial anticorrosion metal, the content in the adhesive is preferably 5 to 30 parts by mass, more preferably 100 parts by mass of the structural unit derived from the (meth) acrylic acid alkyl ester monomer (A). 15 to 25 parts by mass.
［導電性材料］
アクリル系粘着剤は、犠牲防食用金属以外の導電性材料をさらに含有してもよい。粘着剤は、導電性材料を含有することで導電性が高くなる。これにより、電子を被着体に移動させやすくなり、防食性能が高まる。
導電性材料としては、カーボン系材料、金属系材料、金属酸化物系材料、イオン性ポリマー及び導電性高分子から選択される１種または２種以上が挙げられる。
カーボン系材料としては、カーボンブラック、黒鉛、グラフェン、カーボンナノチューブ、アセチレンブラックなどが挙げられる。金属系材料としては、金、銀、銅、ニッケル、又はこれらを含む合金など、鉄よりも電位が貴な金属、又は鉄などが挙げられる。金属酸化物材料としては、例えば、酸化インジウムスズ（ＩＴＯ）、三酸化アンチモン（ＡＴＯ）、フッ素ドープ酸化スズ（ＦＴＯ）、酸化亜鉛などが挙げれらる。導電性高分子としては、ポリアセチレン、ポリピロール、ＰＥＤＯＴ（ポリエチレンジオキシチオフェン）、ＰＥＤＯＴ／ＰＳＳ（ポリエチレンジオキシチオフェンとポリスチレンスルホン酸の複合物）、ポリチオフェン、ポリアニリン、ポリ（ｐ−フェニレン）、ポリフルオレン、ポリカルバゾール、ポリシランまたはこれらの誘導体等が挙げられる。イオン性ポリマーとしては、ポリアクリル酸ナトリウム、ポリアクリル酸カリウムなどが挙げられる。
導電性材料は、これらを１種単独で使用してもよいが、２種以上を併用としてもよい。
導電性材料を用いる場合、その粘着剤における含有量は、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）由来の構成単位１００質量部に対して、好ましくは１〜１０質量部、より好ましくは３〜７質量部である。
[Conductive Material]
The acrylic pressure-sensitive adhesive may further contain a conductive material other than the sacrificial anticorrosion metal. The adhesive has high conductivity by containing a conductive material. This makes it easier for the electrons to move to the adherend and enhances the anticorrosion performance.
Examples of the conductive material include one or more selected from carbon-based materials, metal-based materials, metal oxide-based materials, ionic polymers and conductive polymers.
Examples of carbon materials include carbon black, graphite, graphene, carbon nanotubes, and acetylene black. Examples of the metal-based material include metals such as gold, silver, copper, nickel, and alloys containing these, which have a higher potential than iron, or iron. Examples of the metal oxide material include indium tin oxide (ITO), antimony trioxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, and the like. As the conductive polymer, polyacetylene, polypyrrole, PEDOT (polyethylenedioxythiophene), PEDOT / PSS (composite of polyethylenedioxythiophene and polystyrenesulfonic acid), polythiophene, polyaniline, poly (p-phenylene), polyfluorene, Examples include polycarbazole, polysilane, and derivatives thereof. Examples of the ionic polymer include sodium polyacrylate and potassium polyacrylate.
These conductive materials may be used alone or in combination of two or more.
When a conductive material is used, its content in the adhesive is preferably 1 to 10 parts by mass, more preferably 3 parts by mass with respect to 100 parts by mass of the structural unit derived from the (meth) acrylic acid alkyl ester monomer (A). ~ 7 parts by mass.
［粘着付与樹脂］
アクリル系粘着剤は、粘着力を向上させる観点から、粘着付与樹脂を含有してもよい。粘着付与樹脂としては、水添テルペン樹脂、水添ロジン、不均化ロジン樹脂、石油樹脂等の重合阻害性の低い粘着付与樹脂が好ましい。これらの中でも、粘着付与樹脂が二重結合を多く有していると重合反応を阻害することから、水添系のものが好ましく、中でも水添石油樹脂が好ましい。
粘着付与樹脂の軟化点は、粘着剤の凝集力及び粘着力を向上させる観点から、９５℃以上程度であればよいが、１２０℃以上のものを含むことが好ましく、例えば、９５℃以上１２０℃未満のものと、１２０℃以上１５０℃以下のものとを併用してもよい。なお、軟化点は、ＪＩＳＫ２２０７に規定される環球法により測定すればよい。
アクリル系粘着剤における粘着付与樹脂の含有量は、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）由来の構成単位１００質量部に対して、好ましくは５〜４０質量部、より好ましくは７〜３５質量部、さらに好ましくは１０〜２５質量部である。
[Tackifying resin]
The acrylic pressure-sensitive adhesive may contain a tackifying resin from the viewpoint of improving the adhesive strength. The tackifying resin is preferably a tackifying resin having a low polymerization inhibitory property such as hydrogenated terpene resin, hydrogenated rosin, disproportionated rosin resin and petroleum resin. Among these, hydrogenated type resins are preferable, and hydrogenated petroleum resins are preferable, because the tackifying resin has a large number of double bonds to inhibit the polymerization reaction.
The softening point of the tackifying resin may be about 95 ° C. or higher from the viewpoint of improving the cohesive force and adhesive force of the pressure-sensitive adhesive, but it is preferable that the softening point include 120 ° C. or higher, for example, 95 ° C. or higher and 120 ° C. You may use together what is less than 120 degreeC and below 150 degreeC. The softening point may be measured by the ring and ball method specified in JIS K2207.
The content of the tackifying resin in the acrylic pressure-sensitive adhesive is preferably 5 to 40 parts by mass, and more preferably 7 to 35 parts by mass, relative to 100 parts by mass of the structural unit derived from the (meth) acrylic acid alkyl ester monomer (A). Parts by mass, more preferably 10 to 25 parts by mass.
［微粒子］
アクリル系粘着剤は、微粒子を含有してもよい。微粒子を含有させることで、粘着力を向上させることができる。
微粒子としては、ガラスバルーン、シラスバルーン、及びフライアッシュバルーン等の無機質中空粒子、ポリメタクリル酸メチル、アクリロニトリル−塩化ビニリデン共重合体、ポリスチレン、及びフェノール樹脂等からなる有機質中空粒子、ガラスビーズ、シリカビーズ、及び合成雲母等の無機質微粒子、ポリアクリル酸エチル、ポリウレタン、ポリエチレン、及びポリプロピレン等の有機質微粒子が挙げられる。
アクリル系粘着剤における微粒子の含有量は、（メタ）アクリル酸アルキルエステル系モノマー（Ａ）由来の構成単位１００質量部に対して、好ましくは０．１〜１５質量部、より好ましくは０．５〜１０質量部、さらに好ましくは０．７〜５質量部である。
[Fine particles]
The acrylic pressure-sensitive adhesive may contain fine particles. By containing fine particles, the adhesive strength can be improved.
As the fine particles, glass balloons, shirasu balloons, inorganic hollow particles such as fly ash balloons, polymethyl methacrylate, acrylonitrile-vinylidene chloride copolymer, polystyrene, and organic hollow particles made of phenolic resin, glass beads, silica beads. , And inorganic fine particles such as synthetic mica, and organic fine particles such as polyethyl acrylate, polyurethane, polyethylene, and polypropylene.
The content of fine particles in the acrylic pressure-sensitive adhesive is preferably 0.1 to 15 parts by mass, more preferably 0.5 parts by mass, relative to 100 parts by mass of the structural unit derived from the (meth) acrylic acid alkyl ester monomer (A). 10 to 10 parts by mass, more preferably 0.7 to 5 parts by mass.
［その他の成分］
本発明において用いるアクリル系粘着剤は、前述した成分以外にも、可塑剤、軟化剤、顔料、染料、光重合開始剤、難燃剤等の粘着剤に従来使用されている各種の添加剤を含有してもよい。
[Other ingredients]
The acrylic pressure-sensitive adhesive used in the present invention contains various additives conventionally used for pressure-sensitive adhesives such as a plasticizer, a softening agent, a pigment, a dye, a photopolymerization initiator, and a flame retardant, in addition to the components described above. You may.
（アクリル系粘着剤及び粘着剤層の製造方法）
アクリル系粘着剤は、上記した重合性モノマーを含む粘着剤組成物に光を照射して、重合性モノマーを重合させることで得ることが可能である。また、粘着剤組成物は、必要に応じて上記した粘着付与樹脂、犠牲防食用金属、導電性材料、微粒子、及びその他の成分の少なくとも１種を含んでいてもよい。
より具体的に説明すると、まず、重合性モノマー、さらに必要に応じて配合される粘着付与樹脂、犠牲防食用金属、導電性材料、微粒子、その他の成分を、ガラス容器等の反応容器に投入して混合して、粘着剤組成物を得る。
次いで、粘着剤組成物中の溶存酸素を除去するために、一般に窒素ガス等の不活性ガスを供給して酸素をパージする。そして、粘着剤組成物を剥離シート上に塗布するか、又は、樹脂フィルム、織布、不織布等の支持体などに塗布した後、光を照射し重合性モノマーを重合することにより防食用粘着剤層を得ることができる。
前記粘着剤組成物の塗布もしくは含浸から光を照射する工程までは、不活性ガス雰囲気下、又はフィルム等により酸素が遮断された状態で行うことが好ましい。
なお、本製造方法では、各成分を混合して得た粘着剤組成物は、粘度を高くするために、剥離シート又は支持体などに塗布する前に予備重合をしてもよい。
(Method for producing acrylic pressure-sensitive adhesive and pressure-sensitive adhesive layer)
The acrylic pressure-sensitive adhesive can be obtained by irradiating the pressure-sensitive adhesive composition containing the above-mentioned polymerizable monomer with light to polymerize the polymerizable monomer. In addition, the pressure-sensitive adhesive composition may contain at least one of the above-mentioned tackifying resin, sacrificial anticorrosive metal, conductive material, fine particles, and other components, if necessary.
More specifically, first, a polymerizable monomer, a tackifying resin that is further compounded as necessary, a sacrificial anticorrosion metal, a conductive material, fine particles, and other components are charged into a reaction container such as a glass container. And mixed to obtain an adhesive composition.
Then, in order to remove dissolved oxygen in the pressure-sensitive adhesive composition, generally, an inert gas such as nitrogen gas is supplied to purge oxygen. Then, the pressure-sensitive adhesive composition is applied on a release sheet, or after being applied to a support such as a resin film, a woven fabric, a non-woven fabric, etc., it is irradiated with light to polymerize a polymerizable monomer, and thus an anticorrosive pressure-sensitive adhesive. Layers can be obtained.
The steps from coating or impregnation of the pressure-sensitive adhesive composition to the step of irradiating light are preferably performed in an inert gas atmosphere or in a state where oxygen is blocked by a film or the like.
In this production method, the pressure-sensitive adhesive composition obtained by mixing the components may be prepolymerized before being applied to a release sheet, a support or the like in order to increase the viscosity.
粘着剤組成物に光を照射する際に用いることができるランプとしては、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウエーブ励起水銀灯、及びメタルハライドランプ等が挙げられる。これらの中でも、ケミカルランプが好ましい。粘着剤組成物に対して光を照射する際の光照射強度は、光重合開始剤の有無等によっても異なるが、０．１〜１００ｍＷ／ｃｍ2程度が好ましい。 Examples of the lamp that can be used when irradiating the pressure-sensitive adhesive composition with light include, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp. Etc. Of these, chemical lamps are preferable. The light irradiation intensity when the pressure-sensitive adhesive composition is irradiated with light varies depending on the presence or absence of a photopolymerization initiator and the like, but is preferably about 0.1 to 100 mW / cm 2 .
（ゴム系粘着剤）
次に、粘着剤に使用するゴム系粘着剤について説明する。ゴム系粘着剤は、ゴム成分と、粘着付与樹脂を含有するものであり、ゴム成分としては、スチレン−イソプレンブロック共重合体を使用することが好ましい。スチレン−イソプレンブロック共重合体は、ジブロック率が好ましくは２５〜７０質量％、より好ましくは３０〜６５質量％、さらに好ましくは４５〜６０重量％である。ここでジブロックとは、スチレンとイソプレンとからなるジブロックのことをいう。ジブロック率を上記の範囲とすることにより、粘着力を高めやすくなる。なお、スチレン−イソプレンブロック共重合体は、ジブロック以外にも、スチレン、イソプレン、スチレンブロックからなるトリブロックなどブロックを３つ以上有するものも含有する。
(Rubber adhesive)
Next, the rubber-based pressure-sensitive adhesive used for the pressure-sensitive adhesive will be described. The rubber-based pressure-sensitive adhesive contains a rubber component and a tackifying resin, and it is preferable to use a styrene-isoprene block copolymer as the rubber component. The styrene-isoprene block copolymer has a diblock ratio of preferably 25 to 70% by mass, more preferably 30 to 65% by mass, and further preferably 45 to 60% by mass. Here, the diblock means a diblock composed of styrene and isoprene. By setting the diblock ratio within the above range, it becomes easy to increase the adhesive strength. In addition to the diblock, the styrene-isoprene block copolymer also includes one having three or more blocks such as a triblock composed of styrene, isoprene, and a styrene block.
スチレン−イソプレンブロック共重合体におけるスチレン量は、特に限定されないが、１４〜２４質量％であることが好ましく、より好ましくは１５〜１８質量％である。スチレン量が１４質量％以上であると、凝集性の高い粘着剤となりやすくなる。また、２４質量％以下とすると、凝集力が適度な大きさとなり粘着力を発現しやすくなる。
スチレン−イソプレンブロック共重合体の分子量は、特に限定されないが、質量平均分子量で１００，０００〜４００，０００が好ましく、１５０，０００〜２５０，０００がより好ましい。なお、ここでいう質量平均分子量とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法によりポリスチレン換算分子量として測定されるものをいう。
The amount of styrene in the styrene-isoprene block copolymer is not particularly limited, but is preferably 14 to 24% by mass, more preferably 15 to 18% by mass. When the amount of styrene is 14% by mass or more, the adhesive tends to be highly cohesive. Further, when the content is 24% by mass or less, the cohesive force becomes an appropriate amount and the adhesive force is easily exhibited.
The molecular weight of the styrene-isoprene block copolymer is not particularly limited, but the weight average molecular weight is preferably 100,000 to 400,000, more preferably 150,000 to 250,000. The term "mass average molecular weight" as used herein refers to that measured as a polystyrene-equivalent molecular weight by GPC (gel permeation chromatography) method.
ゴム系粘着剤に使用される粘着付与樹脂は、各種の粘着付与樹脂が使用可能であるが、好ましくは石油系樹脂、テルペン樹脂、クマロン樹脂を使用する。粘着付与樹脂は、１種単独で使用してもよいし、２種以上を併用してもよいが、石油系樹脂と、テルペン樹脂及びクマロン樹脂から選択される少なくとも１種とを併用することが好ましい。このような粘着付与樹脂の組み合わせにより粘着力を良好にしやすくなる。
石油系樹脂としては、脂肪族系石油樹脂（Ｃ５系石油樹脂）、脂環族系石油樹脂、芳香族系石油樹脂等が挙げられ、スチレン−イソプレンブロック共重合体との相溶性の観点から脂肪族系石油樹脂が好ましい。また、石油系樹脂は、軟化点が９０〜１２０℃程度のものを使用することが好ましい。
また、テルペン樹脂としては、軟化点が８０〜１２０℃程度のものが使用可能であるが、粘着力確保の観点から１００℃未満のものが好ましい。また、クマロン樹脂としては、凝集力確保のために、軟化点が好ましくは１１０〜１３０℃、より好ましくは１１５〜１２５℃のものを使用する。
As the tackifying resin used for the rubber-based pressure-sensitive adhesive, various tackifying resins can be used, but petroleum-based resin, terpene resin, and coumarone resin are preferably used. The tackifier resins may be used alone or in combination of two or more, but it is preferable to use a petroleum resin and at least one selected from a terpene resin and a coumarone resin in combination. preferable. The combination of such tackifying resins makes it easy to improve the adhesive strength.
Examples of the petroleum-based resin include an aliphatic petroleum resin (C5 petroleum resin), an alicyclic petroleum resin, an aromatic petroleum resin, and the like. From the viewpoint of compatibility with a styrene-isoprene block copolymer, Group petroleum resins are preferred. Further, it is preferable to use a petroleum-based resin having a softening point of about 90 to 120 ° C.
As the terpene resin, those having a softening point of about 80 to 120 ° C. can be used, but those having a softening point of less than 100 ° C. are preferable from the viewpoint of securing the adhesive strength. Further, as the coumarone resin, one having a softening point of preferably 110 to 130 ° C., more preferably 115 to 125 ° C. is used in order to secure cohesive force.
粘着付与樹脂はゴム成分１００質量部に対して６０〜２５０質量部が好ましく、１００〜２００質量部がより好ましく、１１０〜１８０質量部がさらに好ましい。粘着付与樹脂の配合量を上記範囲内とすることで、凝集力を良好にして適度な粘着力を付与できるようになる。
また、石油系樹脂と、テルペン樹脂及びクマロン樹脂から選択される少なくとも１種とを併用する場合、石油系樹脂は、ゴム成分１００質量部に対して、５０〜２００質量部が好ましく、６０〜１５０質量部が好ましく、６０〜１１０質量部がより好ましい。一方で、テルペン樹脂は、ゴム成分１００質量部に対して、１０〜７０質量部が好ましく、２０〜６０質量部がより好ましく、３０〜５０質量部がさらに好ましい。さらに、クマロン樹脂は、ゴム成分１００質量部に対して、１０〜６０質量部が好ましく、１５〜５０質量部がより好ましく、２０〜４０質量部がさらに好ましい。
ゴム系粘着剤は、アクリル系粘着剤と同様に上記した微粒子を含有してもよく、また、ゴム系粘着剤は、必要に応じて、犠牲防食用金属、導電性材料、軟化剤、酸化防止剤、充填剤等を含有してもよい。
The tackifying resin is preferably 60 to 250 parts by mass, more preferably 100 to 200 parts by mass, still more preferably 110 to 180 parts by mass with respect to 100 parts by mass of the rubber component. By setting the blending amount of the tackifying resin within the above range, it becomes possible to improve the cohesive force and impart an appropriate tackiness.
When the petroleum-based resin and at least one selected from the terpene resin and the coumarone resin are used in combination, the petroleum-based resin is preferably 50 to 200 parts by mass, and 60 to 150 parts by mass with respect to 100 parts by mass of the rubber component. A mass part is preferable and a 60-110 mass part is more preferable. On the other hand, the terpene resin is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and still more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the rubber component. Further, the coumarone resin is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass, still more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the rubber component.
The rubber-based pressure-sensitive adhesive may contain the above-mentioned fine particles like the acrylic-based pressure-sensitive adhesive, and the rubber-based pressure-sensitive adhesive may, if necessary, be a sacrificial anticorrosion metal, a conductive material, a softening agent, an antioxidant. It may also contain agents, fillers and the like.
（ウレタン系粘着剤）
上記したウレタン系粘着剤は特に限定されず、例えば、少なくともポリオールとポリイソシアネート化合物とを反応させて得られるウレタン樹脂等が挙げられる。上記ポリオールとして、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリカプロラクトンポリオール等が挙げられる。上記ポリイソシアネート化合物として、例えば、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート等が挙げられる。これらのウレタン粘着剤は、単独で用いてもよく、２種以上を併用してもよい。
また、ウレタン系粘着剤としては、ポリウレタンポリオールと多官能イソシアネート系硬化剤とを反応させて得られるウレタン樹脂を使用してもよい。ポリウレタンポリオールは、上記したポリオールとポリイソシアネート化合物とを反応したもの、又はポリオールとポリイソシアネート化合物とジアミンなどの鎖延長剤とを反応させたものが挙げられる。多官能イソシアネート系硬化剤としては、２以上のイソシアネート基を有する化合物であればよく、上記したイソシアネート化合物を使用可能である。
ウレタン系粘着剤は、ウレタン樹脂に加えて、上記した微粒子を含有してもよく、また、ウレタン系粘着剤は、必要に応じて、粘着付与樹脂、犠牲防食用金属、導電性材料、軟化剤、酸化防止剤、充填剤等を含有してもよい。
(Urethane adhesive)
The urethane-based pressure-sensitive adhesive described above is not particularly limited, and examples thereof include a urethane resin obtained by reacting at least a polyol and a polyisocyanate compound. Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, and the like. Examples of the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate. These urethane adhesives may be used alone or in combination of two or more.
Further, as the urethane-based pressure-sensitive adhesive, a urethane resin obtained by reacting a polyurethane polyol with a polyfunctional isocyanate-based curing agent may be used. Examples of the polyurethane polyol include those obtained by reacting the above-mentioned polyol and polyisocyanate compound, or those obtained by reacting the polyol, polyisocyanate compound and a chain extender such as diamine. The polyfunctional isocyanate curing agent may be a compound having two or more isocyanate groups, and the above-mentioned isocyanate compounds can be used.
The urethane-based pressure-sensitive adhesive may contain the above-mentioned fine particles in addition to the urethane resin, and the urethane-based pressure-sensitive adhesive may be a tackifying resin, a sacrificial anticorrosive metal, a conductive material, a softening agent, if necessary. , An antioxidant, a filler and the like may be contained.
（シリコーン系粘着剤）
また、シリコーン系粘着剤としては、例えば、付加反応型、過酸化物硬化型又は縮合反応型のシリコーン系粘着剤等が挙げられる。中でも、低温短時間で硬化可能という観点から、付加反応型シリコーン系粘着剤が好ましく用いられる。なお、付加反応型シリコーン系粘着剤は粘着剤層の形成時に硬化するものである。シリコーン系粘着剤として、付加反応型シリコーン系粘着剤を用いる場合、上記シリコーン系粘着剤は白金触媒等の触媒を含んでいてもよい。
また、シリコーン系粘着剤は、微粒子を含有してもよく、また、架橋剤、粘着力を制御するための各種添加剤を加えたりしてもよい。
(Silicone adhesive)
Examples of the silicone-based pressure-sensitive adhesive include addition reaction-type, peroxide-curable or condensation-reaction-type silicone-based pressure-sensitive adhesives. Above all, an addition reaction type silicone-based pressure-sensitive adhesive is preferably used from the viewpoint of curing at low temperature in a short time. The addition reaction type silicone-based pressure-sensitive adhesive cures when the pressure-sensitive adhesive layer is formed. When an addition reaction type silicone adhesive is used as the silicone adhesive, the silicone adhesive may contain a catalyst such as a platinum catalyst.
Further, the silicone-based pressure-sensitive adhesive may contain fine particles, and may further contain a crosslinking agent and various additives for controlling the adhesive strength.
（自己修復機能）
本発明の防食用粘着剤は自己修復機能を有する。ここで、自己修復機能とは、例えば、粘着剤からなる粘着剤層を、刃厚０．３８ｍｍのカッターで、長さ５０ｍｍ、深さ６００μｍの傷を付けた場合に、その傷を５時間以内に修復できる機能をいう。粘着剤が自己修復機能を有することで、外部衝撃などにより、損傷した場合でも、損傷部位を自己修復でき、腐食の原因となる空気、水分などを再遮断することができる。
(Self-repair function)
The anticorrosive adhesive of the present invention has a self-repairing function. Here, the self-healing function means, for example, when an adhesive layer made of an adhesive is scratched with a cutter having a blade thickness of 0.38 mm and a length of 50 mm and a depth of 600 μm, the scratch is within 5 hours. A function that can be restored to. Since the pressure-sensitive adhesive has a self-repairing function, even if it is damaged by an external impact or the like, the damaged part can be self-repaired, and air, moisture, etc. that cause corrosion can be blocked again.
（防食用粘着剤層）
本発明の防食用粘着剤層は、上記した防食用粘着剤からなるものである。防食用粘着剤層の厚さは、好ましくは５０〜３０００μｍである。厚さが５０μｍ以上であると、防食用粘着剤層を金属材料からなる被着体に貼付した場合の防食性能が高まる。一方、厚さが３０００μｍ以下であると、厚さに応じた防食性能の向上効果が期待できる。防食用粘着剤層の厚さは、より好ましくは２００〜１５００μｍであり、更に好ましくは３００〜１０００μｍである。
(Adhesive layer for anticorrosion)
The anticorrosion pressure-sensitive adhesive layer of the present invention comprises the above-mentioned anticorrosion pressure-sensitive adhesive. The thickness of the anticorrosive pressure-sensitive adhesive layer is preferably 50 to 3000 μm. When the thickness is 50 μm or more, the anticorrosion performance is improved when the anticorrosion pressure-sensitive adhesive layer is attached to an adherend made of a metal material. On the other hand, when the thickness is 3000 μm or less, the effect of improving the anticorrosion performance depending on the thickness can be expected. The thickness of the anticorrosive pressure-sensitive adhesive layer is more preferably 200 to 1500 μm, further preferably 300 to 1000 μm.
（防食用粘着テープ）
本発明の防食用粘着テープは、上記した防食用粘着剤層を備えるものである。防食用粘着テープは、支持体の片面に防食用粘着剤層が設けられた防食用片面粘着テープであってもよいし、支持体の両面に防食用粘着剤層が設けられた防食用両面粘着テープであってもよいし、いわゆる基材レスの防食用両面粘着テープと呼ばれる、防食用粘着剤層単体からなるものであってもよいが、防食用粘着剤層単体からなるものが好ましい。
なお、防食用粘着テープの粘着剤層の表面には、一般的に、剥離シートが貼付されており、その剥離シートを剥離した後に被着体に貼着されるものである。剥離シートとしては、樹脂フィルムの一方の面にシリコーン剥離剤等の剥離剤により剥離処理したものなどが使用され、剥離シートは剥離処理面が粘着剤層に接触するように貼付される。
(Adhesive tape for anticorrosion)
The anticorrosion pressure-sensitive adhesive tape of the present invention comprises the above-mentioned anticorrosion pressure-sensitive adhesive layer. The anticorrosion adhesive tape may be an anticorrosion single-sided adhesive tape in which an anticorrosion adhesive layer is provided on one side of a support, or an anticorrosion double-sided adhesive in which an anticorrosion adhesive layer is provided on both sides of a support. The tape may be a tape or a so-called double-sided adhesive tape for anticorrosion without base material, which may be composed of a single layer of the anticorrosion adhesive layer, but is preferably composed of a single layer of the anticorrosion adhesive layer.
A release sheet is generally attached to the surface of the pressure-sensitive adhesive layer of the anticorrosion pressure-sensitive adhesive tape, and the release sheet is peeled off and then attached to the adherend. As the release sheet, one obtained by subjecting one surface of the resin film to release treatment with a release agent such as a silicone release agent is used, and the release sheet is attached so that the release-treated surface contacts the pressure-sensitive adhesive layer.
防食用片面粘着テープ及び防食用両面粘着テープの支持体としては、不織布、和紙等の紙、天然繊維、合成繊維等からなる織布、ポリエステル、ポリオレフィン、軟質ポリ塩化ビニル、硬質ポリ塩化ビニル、アセテート等からなる樹脂フィルム、フラットヤーンクロスなどが挙げられる。フラットヤーンクロスは、ポリオレフィン樹脂などの合成樹脂製のフラットヤーンを、２軸、３軸、又は４軸などの格子目状に配置させ交点を接着させたものである。 As the support for the anticorrosion single-sided adhesive tape and the anticorrosion double-sided adhesive tape, non-woven fabric, paper such as Japanese paper, woven fabric made of natural fiber, synthetic fiber, etc., polyester, polyolefin, soft polyvinyl chloride, hard polyvinyl chloride, acetate And the like, a resin film, a flat yarn cloth, and the like. The flat yarn cloth is a flat yarn made of a synthetic resin such as a polyolefin resin arranged in a biaxial, triaxial, or quasiaxial lattice pattern and bonding the intersections.
本発明の防食用粘着剤、及び該防食用粘着剤からなる粘着剤層並びに該粘着剤層を備えた防食用粘着テープは、各種金属材料からなる被着体表面に対して貼付して使用することが好ましい。金属材料としては好ましくは、鉄、及び鉄を含む合金からなる群から選択される少なくとも１種を含有する金属材料である。鉄を含む合金としては、具体的には、ニッケルクロム鋼、ニッケルクロムモリブデン鋼、クロム鋼、クロムモリブデン鋼、マンガン鋼などの合金鋼、炭素鋼などの各種の鋼材が挙げられる。
鋼材は、橋梁、鉄塔、高架橋、タンク、プラント、橋脚等の鋼構造物に用いられているため、本発明の防食用粘着剤、及び該防食用粘着剤からなる粘着剤層並びに該粘着剤層を備えた防食用粘着テープは、鋼構造物の防食用途として使用することが好ましい。
本発明の防食用粘着剤、及び該防食用粘着剤からなる粘着剤層並びに該粘着剤層を備えた防食用粘着テープは、上記したように自己修復機能を有しているため、外部衝撃などにより損傷した場合でも、その損傷部位が自己修復され、腐食因子である酸素や水分を再遮断することができる。そのため、特に、鋼構造物を構成する鋼材を高く防食することができる。
The anticorrosive pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive layer made of the anticorrosive pressure-sensitive adhesive, and the anticorrosive pressure-sensitive adhesive tape provided with the pressure-sensitive adhesive layer are used by being attached to the surface of an adherend made of various metal materials. It is preferable. The metal material is preferably a metal material containing at least one selected from the group consisting of iron and iron-containing alloys. Specific examples of the iron-containing alloy include various steel materials such as nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, alloy steels such as manganese steel, and carbon steel.
Since the steel material is used for steel structures such as bridges, steel towers, viaducts, tanks, plants, bridge piers, etc., the anticorrosive pressure-sensitive adhesive of the present invention, and a pressure-sensitive adhesive layer comprising the anti-corrosion pressure-sensitive adhesive and the pressure-sensitive adhesive layer. The anticorrosion adhesive tape provided with is preferably used for anticorrosion of steel structures.
The anticorrosive pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive layer made of the anticorrosive pressure-sensitive adhesive, and the anticorrosive pressure-sensitive adhesive tape provided with the pressure-sensitive adhesive layer have the self-repairing function as described above, and thus external impact, etc. Even if it is damaged by, the damaged part can be self-repaired and oxygen and water which are corrosion factors can be blocked again. Therefore, in particular, the steel material forming the steel structure can be highly corrosion-protected.
以下に実施例を用いて本発明を更に詳しく説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
防食用両面粘着テープの貯蔵弾性率、粘着力、防食性能の評価は、以下の方法で実施した。 The storage elastic modulus, adhesive strength, and anticorrosion performance of the double-sided adhesive tape for anticorrosion were evaluated by the following methods.
［貯蔵弾性率］
各実施例、比較例の防食用両面粘着テープから、剥離シートを剥がして、これを試験片として貯蔵弾性率を測定した。貯蔵弾性率は、動的粘弾性測定装置（アイティー計測制御株式会社社製、商品名「ＤＶＡ−２００」）を用いて、せん断モード：１０Ｈｚ、歪み量：０．１％、温度範囲：−１００℃〜１００℃、昇温速度：１０℃/ｍｉｎの条件下で、動的粘弾性スペクトルを測定して算出した。
［粘着力］
各実施例、比較例の防食用両面粘着テープを２５ｍｍ幅の短冊状に裁断してから、剥離シートを剥がして試験片とした。試験片の剥離シートを剥がした面を、ステンレス板上に重ね合わせて２ｋｇのローラで押圧し、試験片をステンレス板上に貼着した。そして、温度２３℃、相対湿度５０％の雰囲気で３０分放置した後、引張試験機（株式会社エー・アンド・デイ社製、商品名「テンシロン万能材料試験機」）を用いて、ＪＩＳ Ｚ ０２３７に準拠して９０°引き剥がし粘着力（Ｎ／２５ｍｍ）を測定した。
［防食性能の評価］
１．マイクロスコープ観察
被着体としての鋼板ＳＳ４００（ＴＰ技研株式会社製、１５０ｍｍ×７０ｍｍ）に、各実施例、比較例で得られた防食用両面粘着テープを、剥離シートを剥がして貼り付けた。鋼板に貼り付けた防食用両面粘着テープの表面から、鋼板まで届くように、刃厚０．３８ｍｍのカッターで長さ５０ｍｍ傷を付け、マイクロスコープで傷口の変化を観察した。以下の基準で評価した。◎又は〇の場合は、自己修復機能を有することを示しており、特に◎の場合は、自己修復機能に優れることを示している。
◎：カッターで傷を付けた後、１時間以内に修復した
〇：カッターで傷を付けた後、１時間超５時間以下で修復した
×：カッターで傷を付けた後、５時間以下で修復しない
２．傷下の錆の有無
被着体としての鋼板ＳＳ４００（ＴＰ技研株式会社製、１５０ｍｍ×７０ｍｍ）に、各実施例、比較例で得られた防食用両面粘着テープを、剥離シートを剥がして貼り付けた。鋼板に貼り付けた防食用両面粘着テープの表面から、鋼板まで届くように、刃厚０．３８ｍｍのカッターで、互いに交差する各線の長さが８０ｍｍであるＸ印状の傷を付けた。その後、防食用両面粘着テープを表面に備えた鋼板を水道水に浸漬し、１カ月後に両面粘着テープの傷下の鋼板表面の錆の有無を以下のように評価した。
〇：傷下に錆が確認された
×：傷下に錆が確認されなかった
[Storage modulus]
The release sheet was peeled off from the anticorrosion double-sided pressure-sensitive adhesive tapes of Examples and Comparative Examples, and the storage elastic modulus was measured using the release sheet as a test piece. The storage elastic modulus was measured using a dynamic viscoelasticity measuring device (trade name “DVA-200” manufactured by IT Measurement and Control Co., Ltd.), shear mode: 10 Hz, strain amount: 0.1%, temperature range: −. The dynamic viscoelastic spectrum was measured and calculated under the conditions of 100 ° C. to 100 ° C. and a temperature rising rate of 10 ° C./min.
[Adhesive force]
The anticorrosion double-sided pressure-sensitive adhesive tapes of Examples and Comparative Examples were cut into strips having a width of 25 mm, and the release sheet was peeled off to obtain test pieces. The surface of the test piece from which the release sheet had been peeled off was placed on the stainless steel plate and pressed with a 2 kg roller to bond the test piece onto the stainless steel plate. Then, after standing for 30 minutes in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%, a tensile tester (manufactured by A & D Co., Ltd., trade name “Tensilon universal material tester”) is used to carry out JIS Z 0237. The 90 ° peeling adhesive strength (N / 25 mm) was measured in accordance with.
[Evaluation of anticorrosion performance]
1. Observation with Microscope On the steel plate SS400 (150 mm × 70 mm, manufactured by TP Giken Co., Ltd.) as an adherend, the anticorrosion double-sided adhesive tape obtained in each of Examples and Comparative Examples was attached by peeling off the release sheet. A 50 mm long scratch was made with a cutter having a blade thickness of 0.38 mm so as to reach the steel sheet from the surface of the anticorrosive double-sided adhesive tape attached to the steel sheet, and changes in the wound were observed with a microscope. The following criteria were evaluated. The case of ⊚ or ◯ indicates that the film has a self-repairing function, and the case of ⊚ indicates that the self-repairing function is excellent.
◎: Repaired within 1 hour after scratching with a cutter ◯: Repaired within 1 hour but less than 5 hours after scratched with a cutter ×: Repaired within 5 hours after scratching with a cutter Not 2. Presence or absence of rust under scratches The anticorrosion double-sided adhesive tape obtained in each of the examples and comparative examples is attached to a steel plate SS400 (150 mm × 70 mm, manufactured by TP Giken Co., Ltd.) as an adherend by peeling off the release sheet. It was From the surface of the anticorrosion double-sided adhesive tape attached to the steel plate, an X mark-shaped scratch having a length of each wire intersecting with each other of 80 mm was made with a cutter having a blade thickness of 0.38 mm so as to reach the steel plate. Then, the steel plate provided with the double-sided pressure-sensitive adhesive tape for corrosion prevention was immersed in tap water, and one month later, the presence or absence of rust on the surface of the steel plate under scratches on the double-sided pressure-sensitive adhesive tape was evaluated as follows.
◯: Rust was confirmed under the scratch ×: No rust was confirmed under the scratch
［実施例１］
表１に記載の配合にしたがって、防食用粘着剤組成物を調製した。この粘着剤組成物に窒素をパージして溶存酸素を除去した。次いで、剥離シートの剥離処理面上に厚さ６００μｍのスペーサーを設置し、粘着剤組成物を剥離シートの剥離処理面上に塗布した。次いで、塗布した粘着剤組成物の上に、剥離処理面が粘着剤組成物に接するように、別の剥離シートを被覆した。なお、剥離シートとしては、シリコーン離型処理されたＰＥＴフィルム（厚み５０μｍ）を使用した。
この状態で被覆側の剥離シートにおける紫外線照射強度が５ｍＷ／ｃｍ2となるようにケミカルランプのランプ強度を調整し、１５分間紫外線を照射し、粘着剤層単体からなり、両面に剥離シートが貼付された防食用両面粘着テープを得た。粘着剤層（すなわち、両面粘着テープ）の厚さは６００μｍであった。結果を表１に示した。
[Example 1]
According to the formulation shown in Table 1, an anticorrosive pressure-sensitive adhesive composition was prepared. The pressure-sensitive adhesive composition was purged with nitrogen to remove dissolved oxygen. Then, a 600 μm thick spacer was placed on the release-treated surface of the release sheet, and the pressure-sensitive adhesive composition was applied onto the release-treated surface of the release sheet. Next, another release sheet was coated on the applied pressure-sensitive adhesive composition so that the release-treated surface was in contact with the pressure-sensitive adhesive composition. As the release sheet, a PET film (thickness 50 μm) subjected to silicone release treatment was used.
In this state, adjust the lamp intensity of the chemical lamp so that the UV irradiation intensity of the release sheet on the coated side is 5 mW / cm 2 , irradiate it with UV rays for 15 minutes, and consist of the adhesive layer alone, with the release sheet attached on both sides. A double-sided pressure-sensitive adhesive tape for corrosion protection was obtained. The thickness of the pressure-sensitive adhesive layer (that is, the double-sided pressure-sensitive adhesive tape) was 600 μm. The results are shown in Table 1.
［実施例２〜６、比較例１〜２］
表１に記載の配合にしたがって粘着剤組成物を調製した以外は、実施例１と同様にして防食用両面粘着テープを得た。結果を表１に示した。
[Examples 2-6, Comparative Examples 1-2]
A double-sided pressure-sensitive adhesive tape for corrosion protection was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition was prepared according to the formulation shown in Table 1. The results are shown in Table 1.
表１における各成分は、以下のとおりである。
オレフィン重合体：商品名「Ｌ−１２５３」、株式会社クラレ製、（メタ）アクリロイル基を片末端に有する水素化ポリブタジエン
架橋剤：商品名「ＴＥＡＩ−１０００」、日本曹達株式会社製
粘着付与樹脂１：商品名「アルコンＰ１４０」、荒川化学工業株式会社製、水添石油樹脂、軟化点１４０℃
粘着付与樹脂２：商品名「アルコンＰ１００」、荒川化学工業株式会社製、水添石油樹脂、軟化点１００℃
微粒子：商品名「セルスターＺ−２７」、東海工業株式会社製、ガラスバルーン
亜鉛粒子：堺化学工業株式会社製、商品名「亜鉛末＃４０」、平均粒径：５０μｍ
カーボン系材料：人造黒鉛粉、オリエンタル産業株式会社、商品名「ＡＴ−ＮＯ．１５Ｓ」、平均粒径１３μｍ
重合開始剤：２，２−ジメトキシ−２−フェニルアセトフェノン
Each component in Table 1 is as follows.
Olefin polymer: trade name "L-1253", manufactured by Kuraray Co., Ltd., hydrogenated polybutadiene cross-linking agent having a (meth) acryloyl group at one end: trade name "TEAI-1000", tackifier resin 1 manufactured by Nippon Soda Co., Ltd. : Trade name "Arcon P140", manufactured by Arakawa Chemical Industry Co., Ltd., hydrogenated petroleum resin, softening point 140 ° C
Tackifying resin 2: trade name "ALCON P100", manufactured by Arakawa Chemical Industry Co., Ltd., hydrogenated petroleum resin, softening point 100 ° C
Fine particles: trade name "CELSTAR Z-27", manufactured by Tokai Kogyo Co., Ltd., glass balloon zinc particles: manufactured by Sakai Chemical Industry Co., Ltd., trade name "zinc dust # 40", average particle size: 50 μm
Carbon-based material: artificial graphite powder, Oriental Sangyo Co., Ltd., trade name “AT-NO.15S”, average particle size 13 μm
Polymerization initiator: 2,2-dimethoxy-2-phenylacetophenone
本実施例１〜６では、４０℃における貯蔵弾性率が特定の範囲内にある粘着剤を備える両面粘着テープを用いており、防食性能の評価が良好であった。これに対して、比較例１〜２では、４０℃における貯蔵弾性率が特定の範囲外にある粘着剤を備える両面粘着テープを用いており、防食性能の評価が悪かった。 In Examples 1 to 6, the double-sided pressure-sensitive adhesive tape including the pressure-sensitive adhesive having a storage elastic modulus at 40 ° C. within a specific range was used, and the anticorrosion performance was evaluated well. On the other hand, in Comparative Examples 1 and 2, the double-sided pressure-sensitive adhesive tape including the pressure-sensitive adhesive having a storage elastic modulus at 40 ° C. outside the specific range was used, and the evaluation of the anticorrosion performance was poor.
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