JP2014105216A - Composition and temporary fixation method of a component using the same - Google Patents
Composition and temporary fixation method of a component using the same Download PDFInfo
- Publication number
- JP2014105216A JP2014105216A JP2012256572A JP2012256572A JP2014105216A JP 2014105216 A JP2014105216 A JP 2014105216A JP 2012256572 A JP2012256572 A JP 2012256572A JP 2012256572 A JP2012256572 A JP 2012256572A JP 2014105216 A JP2014105216 A JP 2014105216A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- temporary fixing
- mass
- parts
- 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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Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、色々な部材を加工するのに使用する組成物に関する。本発明は、色々な部材を加工するに際しての仮固定・剥離方法であり、又それに好適な仮固定用の(メタ)アクリル系樹脂仮固定用接着剤組成物に関する。特に表面が粗い部材や大面積の部材を加工するに際して当該部材を仮固定する方法及び剥離方法と、当該用途に好適な仮固定用接着剤組成物に関する。 The present invention relates to compositions used to process various components. The present invention relates to a temporary fixing / peeling method for processing various members, and also relates to a (meth) acrylic resin temporary fixing adhesive composition suitable for temporary fixing. In particular, the present invention relates to a method and a peeling method for temporarily fixing a member having a rough surface or a large area member, and a temporary fixing adhesive composition suitable for the application.
石英、セラミックス、ガラス、光学レンズ、プリズム、アレイ、シリコンウエハ、半導体実装部品等の仮固定用接着剤としては、両面テープやホットメルト系接着剤が使用されている。これらの接着剤にて接合又は積層した部材を、所定の形状に切削加工後、接着剤を除去し、加工部材を製造することが行われている。例えば、半導体実装部品では、これらの部品を両面テープにて基材に固定した後、所望の部品に切削加工を行い、更に両面テープに紫外線を照射することで部品からの剥離を行っている。ホットメルト系接着剤の場合には、部材を接合後、加熱により間隙に接着剤を浸透させた後、所望の部品に切削加工を行い、加熱して部品の剥離を行なうが、部材には必ず接着剤が残存するため、残存している当該接着剤は有機溶剤を使用して洗浄する必要がある。 Double-sided tapes and hot-melt adhesives are used as temporary fixing adhesives for quartz, ceramics, glass, optical lenses, prisms, arrays, silicon wafers, semiconductor mounting components, and the like. A member joined or laminated with these adhesives is cut into a predetermined shape, and then the adhesive is removed to produce a processed member. For example, in a semiconductor mounting component, these components are fixed to a base material with a double-sided tape, and then a desired part is cut, and further, the double-sided tape is irradiated with ultraviolet rays to be separated from the part. In the case of hot melt adhesives, after joining the members, the adhesive is infiltrated into the gaps by heating, and then the desired part is cut and heated to peel off the parts. Since the adhesive remains, it is necessary to wash the remaining adhesive using an organic solvent.
しかし、両面テープの場合には、寸法精度を出すのが困難であったり、接着強度が弱いため部品加工時にチッピング性が劣ったり、100℃以上の熱をかけないと剥離できなかったりするという課題があった。紫外線照射により剥離させる場合には、被着体の透過性が乏しいと剥離できないという問題があった。 However, in the case of double-sided tape, it is difficult to obtain dimensional accuracy, the chipping property is inferior when parts are processed due to low adhesive strength, and it cannot be peeled off unless heated to 100 ° C or higher. was there. In the case of peeling by ultraviolet irradiation, there is a problem that peeling is not possible if the adherend has poor permeability.
ホットメルト系接着剤の場合には、剥離後、洗浄時に有機溶剤を使用する必要があり、地球環境保護の観点から問題があり、更にはその洗浄処理工程が煩雑であるため、作業的にも問題となっていた。 In the case of a hot-melt adhesive, it is necessary to use an organic solvent at the time of cleaning after peeling, which is problematic from the viewpoint of protecting the global environment, and furthermore, the cleaning process is complicated, It was a problem.
これらの欠点を解決するために、特許文献1では、樹脂硬化体のガラス転移温度をコントロールしかつ樹脂組成物に溶解しない粒状物質を適量添加することを特徴とする光硬化型の接着剤組成物及びそれを用いた仮固定方法が提案されている。しかしながら、有機系熱膨張性粒子について記載はない。 In order to solve these drawbacks, Patent Document 1 discloses a photocurable adhesive composition characterized by adding an appropriate amount of a granular material that controls the glass transition temperature of a cured resin and does not dissolve in the resin composition. And a temporary fixing method using the same has been proposed. However, there is no description about organic heat-expandable particles.
特許文献2では、特定のエチレン性二重結合を有する炭官能モノマーと、特定の分子内に重合可能な二重結合を有せず、かつ水溶性若しくは吸水による膨潤性を有する高分子物質からなる仮固定用接着剤組成物を用いて小物品を仮固定し、次いで水に浸漬して取り外すようにする仮固定方法が提案されている。しかしながら、これらの接着剤を使用した仮固定方法では、取り外す際の接着剤の溶解、膨潤速度が遅いため、大面積の部材では作業時間が長くなってしまうという課題があった。 In Patent Document 2, a carbon-functional monomer having a specific ethylenic double bond and a polymer substance that does not have a polymerizable double bond in a specific molecule and is water-soluble or swellable by water absorption. There has been proposed a temporary fixing method in which a small article is temporarily fixed using an adhesive composition for temporary fixing and is then immersed in water and removed. However, the temporary fixing method using these adhesives has a problem that the working time becomes long with a large-area member because the dissolution and swelling speed of the adhesive when removing is slow.
特許文献3及び4には、接着剤中に有機系熱膨張性粒子を特定の割合で添加することによって接着後、加熱処理により接着力が著しく低下して容易に自己剥離できる熱剥離型接着剤が報告されている。しかしながら、これらの接着剤では接着性が強すぎるため、大面積の部材では加熱処理しても剥離できず実用化できないという課題があった。 In Patent Documents 3 and 4, a heat-peelable adhesive that can be easily self-peeled after the adhesion is significantly reduced by heat treatment after adding organic thermal expandable particles at a specific ratio in the adhesive. Has been reported. However, since these adhesives have too strong adhesiveness, there is a problem that a large-area member cannot be put into practical use because it cannot be peeled off even by heat treatment.
これら従来技術の課題を解決するために、例えば、表面が粗い部材同士や大面積の部材でも適用可能であり、更に剥離後の部材に糊残りがないといった、作業性にも環境性にも優れた仮固定用接着剤組成物が望まれていた。 In order to solve these problems of the prior art, for example, it is possible to apply even members with rough surfaces or members with a large area, and there is no adhesive residue on the member after peeling, which is excellent in workability and environment. There has been a need for a temporary fixing adhesive composition.
即ち、本発明は、(1)分子の末端又は側鎖に2個以上の(メタ)アクリロイル基を有するポリエステル系ウレタン(メタ)アクリレート、(2)ポリアルキレンオキサイド構造を有する単官能(メタ)アクリレート、(3)ラジカル重合開始剤、(4)平均粒径80〜300μmの粒状物質、(5)ブタン及び/又はイソブタンを内包する有機系熱膨張性粒子を含有する組成物である。
前記(1)が、分子量10000〜50000であるポリエステル系ウレタン(メタ)アクリレートオリゴマーであることが好ましい。
前記(2)が、ポリエチレンオキサイド構造を有する単官能(メタ)アクリレートであることが好ましい。
前記(5)ブタン及び/又はイソブタンを内包する有機系熱膨張性粒子が、ブタン及び/又はイソブタンを、塩化ビニリデン、(メタ)アクリロニトリル、(メタ)アクリル酸メチルからなる群のうちの1種又は2種以上からなる重合体又は共重合体である熱可塑性樹脂で包み込んだ熱膨張性マイクロカプセルであることが好ましい。
更に、(6)多官能アクリレートを含有する前記組成物が好ましい。
前記(6)多官能アクリレートがトリプロピレングリコールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレートからなる群のうちの1種又は2種以上からなることが好ましい。
(1)、(2)、必要に応じて使用する(6)の合計100質量部中、(1)の使用量が20〜60質量部であり、(2)の使用量が20〜60質量部であり、(6)の使用量が0〜30質量部である前記組成物が好ましい。
(1)、(2)、必要に応じて使用する(6)の合計100質量部に対して(4)の使用量が0.1〜30質量部である前記組成物が好ましい。
(1)、(2)、必要に応じて使用する(6)の合計100質量部に対して(5)の使用量が1〜30質量部である前記組成物が好ましい。
前記(3)重合開始剤が(3−1)熱ラジカル重合開始剤であることが好ましい。
前記組成物を二剤に分け、第一剤に(3−1)熱ラジカル重合開始剤を含有し、第二剤に(7)還元剤を含有する二剤型の組成物であることが好ましい。
前記(7)がバナジウムアセチルアセトネート、ナフテン酸銅及びオクチル酸コバルトからなる群のうちの1種又は2種以上からなることが好ましい。
(1)、(2)、必要に応じて使用する(6)の合計100質量部に対して(3−1)の使用量が0.1〜5質量部であり、(7)の使用量が0.1〜5質量部である前記組成物が好ましい。
前記(3)重合開始剤が(3−2)光ラジカル重合開始剤であることが好ましい。
前記(3−2)の使用量が(1)、(2)、必要に応じて使用する(6)の合計100質量部に対して0.1〜20質量部であることが好ましい。
前記(4)が架橋ポリ(メタ)アクリル酸メチル粒子、架橋ポリスチレン粒子及び架橋ポリ(メタ)アクリル酸メチルポリスチレン共重合体粒子からなる群のうちの1種又は2種以上であることが好ましい。
前記組成物を含有する接着剤組成物が好ましい。
用途が石英接着用、セラミックス接着用及びガラス接着用からなる群のうちの1種又は2種以上である前記接着剤組成物が好ましい。
用途が仮固定である前記仮固定用接着剤組成物が好ましい。
前記仮固定用接着剤組成物を用いて、部材を接着仮固定し、前記仮固定用接着剤組成物を硬化し、該仮固定された部材を加工し、加工された接着体を水に浸漬することにより、前記仮固定用接着剤組成物の硬化体を取り外す部材の仮固定方法が好ましい。
前記仮固定用接着剤組成物を用いて、部材を接着仮固定し、前記仮固定用接着剤組成物を硬化し、該仮固定された部材を加工し、加工された接着体を100〜200℃に加熱処理することにより、前記仮固定用接着剤組成物の硬化体を取り外す部材の仮固定方法が好ましい。
前記仮固定用接着剤組成物を用いて、石英基板を2〜100枚接着仮固定し、加工した後に接着体を水に浸漬することにより、石英製品を取り外す石英製品の製造方法が好ましい。
前記仮固定用接着剤組成物を用いて、石英基板を2〜100枚接着仮固定し、加工した後に接着体を100〜200℃に加熱することにより、石英製品を取り外す石英製品の製造方法が好ましい。
前記仮固定用接着剤組成物を使用して部材を接着する接合体が好ましい。
部材が石英、セラミック及びガラスからなる群のうちの1種又は2種以上である前記接合体が好ましい。
部材の表面粗さRaが0.2μm以上である前記接合体が好ましい。
加工後の部材の面積が60cm2以上である前記接合体が好ましい。
That is, the present invention includes (1) a polyester urethane (meth) acrylate having two or more (meth) acryloyl groups at the end or side chain of the molecule, and (2) a monofunctional (meth) acrylate having a polyalkylene oxide structure. (3) a radical polymerization initiator, (4) a granular material having an average particle size of 80 to 300 μm, and (5) an organic thermally expandable particle containing butane and / or isobutane.
The (1) is preferably a polyester urethane (meth) acrylate oligomer having a molecular weight of 10,000 to 50,000.
The (2) is preferably a monofunctional (meth) acrylate having a polyethylene oxide structure.
(5) The organic heat-expandable particles encapsulating butane and / or isobutane are selected from the group consisting of butane and / or isobutane selected from vinylidene chloride, (meth) acrylonitrile, methyl (meth) acrylate, or It is preferably a thermally expandable microcapsule encapsulated with a thermoplastic resin which is a polymer or copolymer comprising two or more kinds.
Furthermore, the composition containing (6) polyfunctional acrylate is preferable.
The (6) polyfunctional acrylate is one or two of the group consisting of tripropylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate It is preferable to consist of more than seeds.
Of the total 100 parts by mass of (1), (2) and (6) used as necessary, the usage of (1) is 20-60 parts by mass, and the usage of (2) is 20-60 parts by mass. The above composition in which the amount of (6) used is 0 to 30 parts by mass.
The said composition whose usage-amount of (4) is 0.1-30 mass parts with respect to a total of 100 mass parts of (1), (2) and (6) used as needed is preferable.
The said composition whose usage-amount of (5) is 1-30 mass parts is preferable with respect to a total of 100 mass parts of (1), (2) and (6) used as needed.
The (3) polymerization initiator is preferably (3-1) a thermal radical polymerization initiator.
The composition is preferably divided into two parts, and the first part contains a (3-1) thermal radical polymerization initiator and the second part contains a (7) reducing agent. .
The (7) is preferably composed of one or more of the group consisting of vanadium acetylacetonate, copper naphthenate and cobalt octylate.
(1), (2), the amount used of (3-1) is 0.1-5 parts by mass with respect to a total of 100 parts by mass of (6) used as necessary, and the amount used of (7) Is preferably 0.1 to 5 parts by mass.
The (3) polymerization initiator is preferably (3-2) a radical photopolymerization initiator.
It is preferable that the usage-amount of said (3-2) is 0.1-20 mass parts with respect to a total of 100 mass parts of (1), (2), and (6) used as needed.
It is preferable that said (4) is 1 type (s) or 2 or more types in the group which consists of bridge | crosslinking poly (meth) acrylate methyl particle, bridge | crosslinking polystyrene particle, and bridge | crosslinking poly (meth) methyl acrylate polystyrene copolymer particle.
An adhesive composition containing the composition is preferred.
The adhesive composition is preferably one or more of the group consisting of quartz bonding, ceramic bonding, and glass bonding.
The temporary fixing adhesive composition is preferably used for temporary fixing.
Using the temporary fixing adhesive composition, the member is bonded and temporarily fixed, the temporary fixing adhesive composition is cured, the temporarily fixed member is processed, and the processed adhesive is immersed in water. The temporary fixing method of the member which removes the hardening body of the said adhesive composition for temporary fixing by doing is preferable.
Using the temporary fixing adhesive composition, a member is temporarily bonded and fixed, the temporary fixing adhesive composition is cured, the temporarily fixed member is processed, and the processed adhesive body is 100 to 200. A method for temporarily fixing the member for removing the cured body of the temporary fixing adhesive composition by heat treatment at ° C is preferred.
A method for producing a quartz product in which the quartz product is removed by temporarily bonding and fixing 2 to 100 quartz substrates using the adhesive composition for temporary fixing, immersing the adhesive in water after processing, is preferable.
There is provided a method for producing a quartz product in which a quartz product is removed by temporarily bonding and processing 2 to 100 quartz substrates using the adhesive composition for temporary fixing, heating the bonded body to 100 to 200 ° C. after processing. preferable.
A bonded body in which the member is bonded using the temporary fixing adhesive composition is preferable.
The joined body is preferably one or more members selected from the group consisting of quartz, ceramic and glass.
The joined body in which the surface roughness Ra of the member is 0.2 μm or more is preferable.
The joined body in which the area of the processed member is 60 cm 2 or more is preferable.
本発明は、例えば、作業性や環境性に優れる。本発明は、例えば、表面が粗く大面積な部材であっても、仮固定用接着剤組成物の硬化体が被着物より剥離する性質(以下、単に「剥離性」という)に優れ、更に剥離後の糊残りがなく、寸法精度良く加工後の部材を得ることができる。 The present invention is excellent in workability and environmental performance, for example. The present invention, for example, is excellent in the property (hereinafter simply referred to as “peelability”) that the cured body of the temporary fixing adhesive composition is peeled off from the adherend even if the surface is rough and has a large area. There is no adhesive residue afterward, and a processed member can be obtained with high dimensional accuracy.
以下本発明を説明する。 The present invention will be described below.
本発明の組成物は、硬化性樹脂組成物として使用できる。本発明の硬化性樹脂組成物は仮固定用接着剤組成物として使用できる。二剤型の仮固定用接着剤組成物の場合、(1)、(2)、必要に応じて使用する(6)の合計100質量部とは、第一剤と第二剤を合計した(1)、(2)、必要に応じて使用する(6)の合計をいう。 The composition of the present invention can be used as a curable resin composition. The curable resin composition of the present invention can be used as a temporary fixing adhesive composition. In the case of a two-component temporary fixing adhesive composition, the total of 100 parts by mass of (1), (2), and (6) used as necessary is the sum of the first agent and the second agent ( The sum of (1), (2) and (6) used as necessary.
(1)ポリエステル系ウレタン(メタ)アクリレートは、分子の末端又は側鎖に2個以上の(メタ)アクリロイル基を有し、かつ、分子内にポリエステル構造を有する。(1)の中では、分子の末端に2個以上の(メタ)アクリロイル基を有することが好ましい。 (1) Polyester urethane (meth) acrylate has two or more (meth) acryloyl groups at the end or side chain of the molecule, and has a polyester structure in the molecule. In (1), it is preferable to have two or more (meth) acryloyl groups at the end of the molecule.
ここで、ポリエステル系ウレタン(メタ)アクリレートとは、ポリエステルポリオール化合物(以後、Xで表す)と有機ポリイソシアネート化合物(以後、Yで表す)とヒドロキシ(メタ)アクリレート(以後、Zで表す)とを反応させることにより得られる、ウレタン(メタ)アクリレートをいう。 Here, the polyester-based urethane (meth) acrylate is a polyester polyol compound (hereinafter represented by X), an organic polyisocyanate compound (hereinafter represented by Y), and a hydroxy (meth) acrylate (hereinafter represented by Z). This refers to urethane (meth) acrylate obtained by reacting.
ポリエステルポリオール化合物(X)としては、多価アルコール又はポリエーテルポリオールと、多塩基酸との縮合物であるポリエステルポリオールが挙げられる。多価アルコールとしては、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、テトラ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、ブチレングリコール、1,4−ブタンジオール、ポリブチレングリコール、1,5−ペンタンジオール、1,6−ヘキサンジオール、1,8−オクタンジオール、1,9−ノナンジオール、3−メチル−1,5−ペンタンジオール、2,4−ジエチル−1,5−ペンタンジオール、2,2−ブチルエチル−1,3−プロパンジオール、ネオペンチルグリコール、シクロヘキサンジメタノール、水素化ビスフェノールA、ポリカプロラクトン、トリメチロールエタン、トリメチロールプロパン、ポリトリメチロールプロパン、ペンタエリスリトール、ポリペンタエリスリトール、ソルビトール、マンニトール、グリセリン、ポリグリセリン、ポリテトラメチレングリコール、ポリブタジエンポリオール、水素化ポリブタジエンポリオール等が挙げられる。ポリブタジエンポリオールとは、2個以上の水酸基を有するポリブタジエンをいい、例えば、両末端に水酸基を有するポリブタジエンをいう。水素化ポリブタジエンポリオールとは、2個以上の水酸基を有する水素化ポリブタジエンをいい、例えば、両末端に水酸基を有する水素化ポリブタジエンをいう。ポリエーテルポリオールとは、ポリエチレンオキサイド、ポリプロピレンオキサイド、エチレンオキサイド/プロピレンオキサイドのブロック又はランダム共重合の少なくとも1種の構造を有するポリエーテルポリオール等が挙げられる。多価アルコール又はポリエーテルポリオールの中では、ポリエーテルポリオールが好ましく、エチレングリコール、1,4−ブタンジオール、水素化ポリブタジエンポリオールからなる群のうちの1種又は2種以上が好ましい。多塩基酸としては、無水マレイン酸、マレイン酸、フマル酸、無水イタコン酸、イタコン酸、アジピン酸、イソフタル酸等が挙げられる。多塩基酸の中では、アジピン酸が好ましい。 Examples of the polyester polyol compound (X) include a polyester polyol which is a condensate of a polyhydric alcohol or polyether polyol and a polybasic acid. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4-butanediol, polybutylene glycol, 1,5- Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2, 2-butylethyl-1,3-propanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethyl Rupuropan, pentaerythritol, poly pentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol, polybutadiene polyol, hydrogenated polybutadiene polyol, and the like. The polybutadiene polyol refers to polybutadiene having two or more hydroxyl groups, for example, polybutadiene having hydroxyl groups at both ends. The hydrogenated polybutadiene polyol refers to a hydrogenated polybutadiene having two or more hydroxyl groups, for example, a hydrogenated polybutadiene having hydroxyl groups at both ends. Examples of the polyether polyol include a polyether polyol having at least one structure of polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymerization. Among the polyhydric alcohols or polyether polyols, polyether polyols are preferred, and one or more of the group consisting of ethylene glycol, 1,4-butanediol, and hydrogenated polybutadiene polyol are preferred. Examples of the polybasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid and the like. Of the polybasic acids, adipic acid is preferred.
有機ポリイソシアネート化合物(Y)としては、格別に限定される必要はないが、例え
ば芳香族系、脂肪族系、環式脂肪族系、脂環式系等のポリイソシアネートが使用でき、中でもトリレンジイソシアネート(TDI)、ジフェニルメタンジイソシアネート(MDI)、水添化ジフェニルメタンジイソシアネート(H−MDI)、ポリフェニルメタンポリイソシアネート(クルードMDI)、変性ジフェニルメタンジイソシアネート(変性MDI)、水添化キシリレンジイソシアネート(H−XDI)、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(HMDI)、トリメチルヘキサメチレンジイソシアネート(TMXDI)、テトラメチルキシリレンジイソシアネート(m−TMXDI)、イソホロンジイソシアネート(IPDI)、ノルボルネンジイソシアネート(NBDI)、1,3−ビス(イソシアナトメチル)シクロヘキサン(H6XDI)等のポリイソシアネート或いはこれらポリイソシアネートの三量体化合物、これらポリイソシアネートとポリオールの反応生成物等が好適に用いられる。これらの中では、水添化キシリレンジイソシアネート(H−XDI)及び/又はイソホロンジイソシアネート(IPDI)が好ましく、イソホロンジイソシアネートがより好ましい。
The organic polyisocyanate compound (Y) is not particularly limited. For example, aromatic, aliphatic, cycloaliphatic, and alicyclic polyisocyanates can be used. Isocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate (H-XDI) ), Xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), tetramethylxylylene diisocyanate (m-TMXDI), isophorone diisocyanate Polyisocyanates such as nate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), trimer compounds of these polyisocyanates, reaction products of these polyisocyanates and polyols, etc. Preferably used. In these, hydrogenated xylylene diisocyanate (H-XDI) and / or isophorone diisocyanate (IPDI) are preferable, and isophorone diisocyanate is more preferable.
ヒドロキシ(メタ)アクリレート(Z)としては、例えば、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、2−ヒドロキシブチル(メタ)アクリレート、2−ヒドロキシエチル(メタ)アクリロイルホスフェート、4−ブチルヒドロキシ(メタ)アクリレート、2−(メタ)アクリロイロキシエチル−2−ヒドロキシプロピルフタレート、グリセリンジ(メタ)アクリレート、2−ヒドロキシ−3−(メタ)アクリロイロキシプロピル(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、カプロラクトン変性2−ヒドロキシエチル(メタ)アクリレート等が挙げられる。これらの中では、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、2−ヒドロキシブチル(メタ)アクリレートからなる群のうちの1種又は2種以上が好ましい。 Examples of the hydroxy (meth) acrylate (Z) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, 4-butylhydroxy (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone-modified 2-hydroxyethyl (meth) acrylate. In these, the 1 type (s) or 2 or more types in the group which consists of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate is preferable.
(1)分子の末端又は側鎖に2個以上の(メタ)アクリロイル基を有するポリエステル系ウレタン(メタ)アクリレートの中では、分子量が10000〜50000であるポリエステル系ウレタン(メタ)アクリレートオリゴマーが好ましい。ポリエステル系ウレタン(メタ)アクリレートオリゴマーとしては、オリゴマー/ポリマー末端又は側鎖に2個以上(メタ)アクロイル化された多官能(メタ)アクリレートオリゴマー/ポリマー等が挙げられる。ここで、分子量は重量平均分子量をいう。これらの中では、効果が大きい点で、ポリエステル系ウレタン(メタ)アクリレートオリゴマーの重量平均分子量は、15000〜45000がより好ましい。重量平均分子量は、溶剤としてテトラヒドロフランを用い、GPCシステム(東ソ−社製SC−8010)等を使用し、下記条件で、市販の標準ポリスチレンで検量線を作成して求める。 (1) Among polyester urethane (meth) acrylates having two or more (meth) acryloyl groups at the molecular ends or side chains, polyester urethane (meth) acrylate oligomers having a molecular weight of 10,000 to 50,000 are preferred. Examples of the polyester-based urethane (meth) acrylate oligomer include polyfunctional (meth) acrylate oligomers / polymers that are two or more (meth) acryloylated at the oligomer / polymer terminal or side chain. Here, the molecular weight refers to the weight average molecular weight. Among these, the weight-average molecular weight of the polyester-based urethane (meth) acrylate oligomer is more preferably 15000 to 45000 in that the effect is great. The weight average molecular weight is determined by using tetrahydrofuran as a solvent, using a GPC system (SC-8010 manufactured by Tosoh Corporation), etc., and creating a calibration curve with commercially available standard polystyrene under the following conditions.
流速:1.0ml/min
設定温度:40℃
カラム構成:東ソー社製「TSK guardcolumn MP(×L)」6.0mmID×4.0cm1本、及び東ソー社製「TSK−GEL MULTIPOREHXL−M」 7.8mmID×30.0cm(理論段数16,000段)2本、計3本(全体として理論段数32,000段)、サンプル注入量:100μl(試料液濃度1mg/ml)
送液圧力:39kg/cm2
検出器:RI検出器
Flow rate: 1.0 ml / min
Set temperature: 40 ° C
Column configuration: “TSK guardcolumn MP (× L)” manufactured by Tosoh Corporation 6.0 mm ID × 4.0 cm 1 and “TSK-GEL MULTIPIOREHXL-M” manufactured by Tosoh Corporation 7.8 mm ID × 30.0 cm (theoretical plate number 16,000 plates) 2), 3 in total (32,000 theoretical plates as a whole), sample injection volume: 100 μl (sample solution concentration 1 mg / ml)
Liquid feeding pressure: 39 kg / cm 2
Detector: RI detector
このようなポリエステル系ウレタン(メタ)アクリレートオリゴマーとしては、例えば、日本合成社製「UV−2000B」(UV−2000Bの重量平均分子量:13000)、「UV−3000B」(UV−3000Bの重量平均分子量:18000)、根上工業社製「KHP−11」(KHP−11の重量平均分子量:25000)、「KHP−17」(KHP−17の重量平均分子量:40000)等が挙げられる。これらの中では、下記化学式(A)で表される構造を有するポリエステル系ウレタン(メタ)アクリレートオリゴマーが好ましい。 Examples of such a polyester urethane (meth) acrylate oligomer include “UV-2000B” (UV-2000B weight average molecular weight: 13000) and “UV-3000B” (UV-3000B weight average molecular weight) manufactured by Nihon Gosei Co., Ltd. : 18000), “KHP-11” (KHP-11 weight average molecular weight: 25000), “KHP-17” (KHP-17 weight average molecular weight: 40000), and the like manufactured by Negami Kogyo Co., Ltd. In these, the polyester-type urethane (meth) acrylate oligomer which has a structure represented by following Chemical formula (A) is preferable.
化学式(A)
P−R−P
(但し、Pは主骨格P、RはR成分)
Chemical formula (A)
P-R-P
(Where P is the main skeleton P, R is the R component)
これらの中では、下記化学式(B)で表される構造を有するポリエステル系ウレタン(メタ)アクリレートオリゴマー及び/又は化学式(C)で表される構造を有するポリエステル系ウレタン(メタ)アクリレートオリゴマーが好ましい。下記化学式(B)で表される構造を有するポリエステル系ウレタン(メタ)アクリレートオリゴマーは、ポリエステルポリオール化合物(X)が、エチレングリコールや1,4−ブタンジオールと、アジピン酸との縮合物であり、有機ポリイソシアネート化合物(Y)が、イソホロンジイソシアネートであり、ヒドロキシ(メタ)アクリレート(Z)が、2−ヒドロキシエチル(メタ)アクリレートである。下記化学式(C)で表される構造を有するポリエステル系ウレタン(メタ)アクリレートオリゴマーは、ポリエステルポリオール化合物(X)が、水素化ポリブタジエンポリオールと、アジピン酸との縮合物であり、有機ポリイソシアネート化合物(Y)が、イソホロンジイソシアネートであり、ヒドロキシ(メタ)アクリレート(Z)が、2−ヒドロキシブチル(メタ)アクリレートである。 Among these, a polyester urethane (meth) acrylate oligomer having a structure represented by the following chemical formula (B) and / or a polyester urethane (meth) acrylate oligomer having a structure represented by the chemical formula (C) are preferable. The polyester-based urethane (meth) acrylate oligomer having a structure represented by the following chemical formula (B), the polyester polyol compound (X) is a condensate of ethylene glycol or 1,4-butanediol and adipic acid, The organic polyisocyanate compound (Y) is isophorone diisocyanate, and the hydroxy (meth) acrylate (Z) is 2-hydroxyethyl (meth) acrylate. In the polyester-based urethane (meth) acrylate oligomer having a structure represented by the following chemical formula (C), the polyester polyol compound (X) is a condensate of hydrogenated polybutadiene polyol and adipic acid, and an organic polyisocyanate compound ( Y) is isophorone diisocyanate, and hydroxy (meth) acrylate (Z) is 2-hydroxybutyl (meth) acrylate.
化学式(B)で表される構造を有するポリエステル系ウレタン(メタ)アクリレートオリゴマーとしては、日本合成社製「UV−3000B」(但し、R’はH)等が挙げられる。化学式(C)で表される構造を有するポリエステル系ウレタン(メタ)アクリレートオリゴマーとしては、根上工業社製「KHP−11」、「KHP−17」(R' 'はH)等が挙げられる。 Examples of the polyester urethane (meth) acrylate oligomer having a structure represented by the chemical formula (B) include “UV-3000B” (provided that R ′ is H) manufactured by Nihon Gosei Co., Ltd. Examples of the polyester-based urethane (meth) acrylate oligomer having a structure represented by the chemical formula (C) include “KHP-11” and “KHP-17” (R ′ ′ is H) manufactured by Negami Kogyo Co., Ltd.
(1)の使用量は、(1)、(2)、必要に応じて使用する(6)の合計を100質量部中、20〜60質量部が好ましい。20質量部未満であると剥離性が得られない場合があり、60質量部を超えると仮固定用接着剤組成物が高粘度となってしまい、作業性が得られない場合がある。剥離性と作業性の観点から、30〜50質量部がより好ましく、35〜45質量部が最も好ましい。 As for the usage-amount of (1), 20-60 mass parts is preferable in 100 mass parts for the sum total of (1), (2), and (6) used as needed. If it is less than 20 parts by mass, peelability may not be obtained, and if it exceeds 60 parts by mass, the temporary fixing adhesive composition may have high viscosity and workability may not be obtained. From a viewpoint of peelability and workability, 30 to 50 parts by mass is more preferable, and 35 to 45 parts by mass is most preferable.
(2)ポリアルキレンオキサイド構造を有する単官能(メタ)アクリレートとしては、ポリエチレンオキサイド構造を有する単官能(メタ)アクリレートが好ましい。ポリエチレンオキサイド構造を有する単官能(メタ)アクリレートとしては、下記化学式(D)で表される構造を有する単官能(メタ)アクリレートが好ましい。 (2) The monofunctional (meth) acrylate having a polyalkylene oxide structure is preferably a monofunctional (meth) acrylate having a polyethylene oxide structure. The monofunctional (meth) acrylate having a polyethylene oxide structure is preferably a monofunctional (meth) acrylate having a structure represented by the following chemical formula (D).
化学式(D)
−(−CH2−CH2−O−)n−
(但し、n=2〜4)
Chemical formula (D)
- (- CH 2 -CH 2 -O- ) n -
(However, n = 2-4)
(2)化学式(D)で表される構造を有する単官能(メタ)アクリレートとしては、メトキシ(エチレンオキサイド2モル変性)(メタ)アクリレート、メトキシ(エチレンオキサイド3モル変性)(メタ)アクリレート、メトキシ(エチレンオキサイド4モル変性)(メタ)アクリレート、フェノールエチレンオキサイド変性(メタ)アクリレート、フェノール(エチレンオキサイド2モル変性)(メタ)アクリレート、フェノール(エチレンオキサイド3モル変性)(メタ)アクリレート、フェノール(エチレンオキサイド4モル変性)(メタ)アクリレート、ノニルフェノール(エチレンオキサイド4モル変性)(メタ)アクリレート等が挙げられる。この中でもフェノール(エチレンオキサイド2モル変性)(メタ)アクリレート、フェノール(エチレンオキサイド3モル変性)(メタ)アクリレート、フェノール(エチレンオキサイド4モル変性)(メタ)アクリレート、ノニルフェノール(エチレンオキサイド4モル変性)(メタ)アクリレートからなる群のうちの1種又は2種以上が好ましく、フェノール(エチレンオキサイド2モル変性)(メタ)アクリレートがより好ましい。単官能(メタ)アクリレートとは、分子内に1個の(メタ)アクリロイル基を有する化合物をいう。 (2) Monofunctional (meth) acrylates having a structure represented by chemical formula (D) include methoxy (ethylene oxide 2 mol modified) (meth) acrylate, methoxy (ethylene oxide 3 mol modified) (meth) acrylate, methoxy (Ethylene oxide 4 mol modified) (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, phenol (ethylene oxide 2 mol modified) (meth) acrylate, phenol (ethylene oxide 3 mol modified) (meth) acrylate, phenol (ethylene Oxide 4 mol modified) (meth) acrylate, nonylphenol (ethylene oxide 4 mol modified) (meth) acrylate, and the like. Among them, phenol (ethylene oxide 2 mol modified) (meth) acrylate, phenol (ethylene oxide 3 mol modified) (meth) acrylate, phenol (ethylene oxide 4 mol modified) (meth) acrylate, nonylphenol (ethylene oxide 4 mol modified) ( 1 type or 2 or more types in the group which consists of a meth) acrylate are preferable, and a phenol (ethylene oxide 2 mol modification | denaturation) (meth) acrylate is more preferable. Monofunctional (meth) acrylate refers to a compound having one (meth) acryloyl group in the molecule.
(2)の使用量は、(1)、(2)、必要に応じて使用する(6)の合計を100質量部中、20〜60質量部が好ましい。20質量部未満であると剥離性が得られない場合があり、60質量部を超えると仮固定用接着剤組成物の硬度が低くなるため、仮固定した部材の加工時のずれが生じ、寸法精度が得られない場合がある。剥離性と寸法精度の観点から、25〜55質量部がより好ましく、30〜45質量部が最も好ましい。 As for the usage-amount of (2), 20-60 mass parts is preferable in 100 mass parts for the sum total of (1), (2), and (6) used as needed. If the amount is less than 20 parts by mass, the peelability may not be obtained. If the amount exceeds 60 parts by mass, the hardness of the temporarily fixing adhesive composition is lowered. Accuracy may not be obtained. From the viewpoint of peelability and dimensional accuracy, 25 to 55 parts by mass are more preferable, and 30 to 45 parts by mass are most preferable.
(3)重合開始剤としては、(3−1)熱ラジカル重合開始剤と(3−2)光ラジカル重合開始剤からなる群から選択される1種又は2種が好ましい。 (3) As a polymerization initiator, 1 type or 2 types selected from the group which consists of (3-1) thermal radical polymerization initiator and (3-2) radical photopolymerization initiator are preferable.
(3−1)熱ラジカル重合開始剤としては、有機又は無機の過酸化物が好ましく、有機過酸化物がより好ましい。有機過酸化物としては、t-ラウロイルパーオキサイド、ベンゾイルパーオキサイド等のジアシルパーオキサイド類、t−ブチルパーオキシ−3,5,5−トリメチルヘキサノエート、クミルパーオキシネオデカノエイト、ヘキシルパーオキシビバレート、t−ブチルパーオキシイソブチレート、t−ブチルパーオキシビバレート、t−ブチルパーオキシアセテート、t−ブチルパーオキシベンゾエート、ターシャリーブチルパーオキシ−2−エチルヘキサネート等のアルキルパーオキシエステル類、ジイソプロピルパーオキシジカーボネート、ジ−2−エチルヘキシルパーオキシジカーボネート、ジノルマルプロピルパーオキシジカーボネート、ビス(4−ターシャリーブチルシクロヘキシル)パーオキシジカーボネート、ジ−2−エトキシエチルパーオキシジカーボネート、ジメトキシイソプロピルパーオキシジカーボネート、ジ(3−メチル−3−メトキシブチル)パーオキシジカーボネート及びジアリルパーオキシジカーボネート等のパーオキシジカーボネート類、t−ブチルパーオキシイソプロピルカーボネート等のパーオキシカーボネート類、ジ−t−ブチルパーオキシシクロヘキサン、ジ−(t−ブチルパーオキシ)ブタン等のパーオキシケタール類、ジキュミルパーオキサイド、t−ブチルキュミルパーオキサイド、ジ−t−ブチルパーオキサイド等のジアルキルパーオキサイド類、クメンハイドロパーオキサイド、テトラメチルブチルハイドロパーオキサイド等のハイドロパーオキサイド類、ケトンパーオキサイド、シクロヘキサノンパーオキサイド等のケトンパーオキサイド類等が挙げられる。これらの中では、アルキルパーオキシエステル類及び/又はハイドロパーオキサイド類が好ましく、ハイドロパーオキサイド類がより好ましく、クメンハイドロパーオキサイドが最も好ましい。 (3-1) The thermal radical polymerization initiator is preferably an organic or inorganic peroxide, and more preferably an organic peroxide. Examples of organic peroxides include diacyl peroxides such as t-lauroyl peroxide and benzoyl peroxide, t-butylperoxy-3,5,5-trimethylhexanoate, cumylperoxyneodecanoate, and hexylperoxide. Alkyl pars such as oxybivalate, t-butyl peroxyisobutyrate, t-butyl peroxybivalate, t-butyl peroxyacetate, t-butyl peroxybenzoate, tertiary butyl peroxy-2-ethylhexanate Oxyesters, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, dinormalpropyl peroxydicarbonate, bis (4-tertiarybutylcyclohexyl) peroxydicarbonate, di-2-ethoxy Peroxydicarbonates such as ethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate and diallyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, etc. Peroxycarbonates, di-t-butylperoxycyclohexane, peroxyketals such as di- (t-butylperoxy) butane, dicumyl peroxide, t-butylcumyl peroxide, di-t- Dialkyl peroxides such as butyl peroxide, hydroperoxides such as cumene hydroperoxide, tetramethylbutyl hydroperoxide, ketone peroxides such as ketone peroxide and cyclohexanone peroxide Oxides, and the like. Among these, alkyl peroxyesters and / or hydroperoxides are preferable, hydroperoxides are more preferable, and cumene hydroperoxide is most preferable.
(3−1)熱ラジカル重合開始剤の使用量は、(1)、(2)及び必要に応じて使用する(6)の合計100質量部に対して、0.1〜5量部が好ましく、1〜3質量部がより好ましい。0.1質量部以上であれば、硬化性が確実に得られるし、5質量部以下であれば十分な貯蔵安定性が得られ、皮膚刺激性が低くなる。 (3-1) The usage amount of the thermal radical polymerization initiator is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight in total of (1), (2) and (6) used as necessary. 1 to 3 parts by mass is more preferable. If it is 0.1 mass part or more, sclerosis | hardenability will be acquired reliably, and if it is 5 mass parts or less, sufficient storage stability will be acquired and skin irritation will become low.
本発明の仮固定用接着剤組成物では(3−1)熱ラジカル重合開始剤を使用する場合、(7)還元剤を併用することが可能である。還元剤としてはナフテン酸銅、バナジウムアセチルアセトネート、オクチル酸コバルト等の遷移金属塩が挙げられる。これらの中では、オクチル酸コバルトが好ましい。 In the temporary fixing adhesive composition of the present invention, when (3-1) a thermal radical polymerization initiator is used, (7) a reducing agent can be used in combination. Examples of the reducing agent include transition metal salts such as copper naphthenate, vanadium acetylacetonate, and cobalt octylate. Of these, cobalt octylate is preferred.
本発明の(7)還元剤の使用量は、(1)、(2)及び必要に応じて使用する(6)の合計100質量部に対して、0.1〜5質量部が好ましく、1〜3質量部がより好ましい。0.1質量部以上であれば、硬化性が確実に得られるし、5質量部以下であれば十分な貯蔵安定性が得られる。 The amount of the (7) reducing agent used in the present invention is preferably 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of (1), (2) and (6) used as necessary. -3 mass parts is more preferable. If it is 0.1 mass part or more, sclerosis | hardenability will be obtained reliably, and if it is 5 mass parts or less, sufficient storage stability will be obtained.
本発明の仮固定用接着剤組成物は、第一剤に少なくとも(3−1)熱ラジカル重合開始剤を含有し、第二剤に少なくとも(7)還元剤を含有する二剤型の仮固定用接着剤組成物として使用することが好ましい。二剤型については、本発明の仮固定用接着剤組成物の必須成分全てを貯蔵中は混合せず、仮固定用接着剤組成物を第一剤及び第二剤に分けて貯蔵することが好ましい。この場合、両剤を同時に又は別々に部材に塗布して接触、硬化することにより、二剤型の仮固定用接着剤組成物として使用できる。この場合(4)粒状物質や(5)ブタン及び/又はイソブタンを内包する有機系熱膨張性粒子や(3−2)光ラジカル重合開始剤は、第一剤及び第二剤のいずれか一方又は両方に含有して良い。二剤型の仮固定用接着剤組成物は、二剤の混合のみによって組成物を硬化させることができる。 The adhesive composition for temporary fixing of the present invention includes a two-component type temporary fixing in which the first agent contains at least (3-1) a thermal radical polymerization initiator and the second agent contains at least (7) a reducing agent. It is preferably used as an adhesive composition. For the two-component type, all the essential components of the temporary fixing adhesive composition of the present invention may not be mixed during storage, and the temporary fixing adhesive composition may be stored separately as the first agent and the second agent. preferable. In this case, the two agents can be used as a two-component temporary fixing adhesive composition by applying them to the member simultaneously or separately, and contacting and curing them. In this case, (4) particulate matter, (5) organic heat-expandable particles encapsulating butane and / or isobutane, and (3-2) photoradical polymerization initiator are either the first agent or the second agent or It may be contained in both. The two-component temporary fixing adhesive composition can be cured only by mixing the two components.
二剤型の仮固定用接着剤組成物の使用方法は以下の通りである。 The method of using the two-component temporary fixing adhesive composition is as follows.
二剤型の仮固定用接着剤組成物の使用方法としては、固定する一方の部材の接着面に接着剤を適量塗布し、続いてもう一方の部材を重ね合わせるという方法や、予め仮固定する部材を多数積層しておき、接着剤を隙間に浸透させて塗布させる方法等により接着剤を塗布し、仮固定用接着剤組成物を硬化させ、部材同士を仮固定する方法等が挙げられる。 As a method of using the two-component temporary fixing adhesive composition, an appropriate amount of adhesive is applied to the bonding surface of one member to be fixed, and then the other member is superposed, or temporarily fixed. Examples include a method in which a large number of members are stacked, an adhesive is applied by infiltrating an adhesive into a gap, and the like, the adhesive composition for temporary fixing is cured, and members are temporarily fixed.
本発明の仮固定用接着剤組成物は、二剤の正確な計量を必要とせず、不完全な計量や混合、時には二剤の接触だけでも、常温で硬化する。本発明の仮固定用接着剤組成物は、作業性に優れる。 The adhesive composition for temporary fixing according to the present invention does not require accurate metering of the two agents, and is cured at room temperature even by incomplete metering or mixing, or sometimes only by contact of the two agents. The temporary fixing adhesive composition of the present invention is excellent in workability.
両剤を同時に又は別々に部材に塗布して接触、硬化させ、部材同士を仮固定する際は、二剤を混合して部材に塗布した後、例えば、常温で0.5〜500時間静置することにより部材同士を接着することが好ましい。0.5時間以上であれば仮固定用接着剤組成物が硬化し、十分な接着強度が得られるし、500時間以下であれば十分な接着力が得られる。部材同士を仮固定する際の静置時間は、4〜300時間がより好ましく、24〜200時間が更に好ましく、50〜100時間が最も好ましい。常温とは、例えば、10〜40℃をいう。 When both agents are applied to the members simultaneously or separately to contact and cure and the members are temporarily fixed, after mixing the two agents and applying them to the members, for example, leave at room temperature for 0.5 to 500 hours It is preferable to bond the members together. If it is 0.5 hours or more, the adhesive composition for temporary fixing is cured and sufficient adhesive strength is obtained, and if it is 500 hours or less, sufficient adhesive strength is obtained. The standing time when the members are temporarily fixed is more preferably 4 to 300 hours, further preferably 24 to 200 hours, and most preferably 50 to 100 hours. Room temperature refers to 10 to 40 ° C., for example.
本発明の仮固定用接着剤組成物を使用した仮固定方法としては、上述した二剤の混合による仮固定方法を用いた後、水に接着体を浸漬することにより、仮固定用接着剤組成物の硬化体が軟化し、それにより容易にブタン及び/又はイソブタンを内包する有機系熱膨張性粒子が膨張し、硬化体(接着基材)と仮固定用接着剤組成物との界面に水が侵入し、硬化体をより容易に剥離できる。水の温度は高温である方が、ブタン及び/又はイソブタンを内包する有機系熱膨張性粒子の膨張が大きいため、水が侵入しやすくなり、容易に硬化体を剥離することができる。硬化体を取り外す際の水の温度は、剥離性と温水による接着基材の劣化の点で、40℃を超えることが好ましく、60℃以上がより好ましく、80〜100℃が最も好ましく、90〜100℃が一層好ましい。浸漬時間は、1〜240分が好ましく、2〜200分がより好ましく、5〜180分が最も好ましい。 As a temporary fixing method using the temporary fixing adhesive composition of the present invention, the temporary fixing adhesive composition is prepared by immersing the adhesive in water after using the above-described temporary fixing method by mixing the two components. The hardened body of the product is softened, so that the organic thermally expandable particles containing butane and / or isobutane easily expand, and water is formed at the interface between the cured body (adhesive substrate) and the temporary fixing adhesive composition. Penetrates and the cured body can be peeled off more easily. The higher the temperature of the water, the greater the expansion of the organic thermally expandable particles encapsulating butane and / or isobutane, so that water easily enters and the cured product can be easily peeled off. The temperature of water when removing the cured body is preferably higher than 40 ° C., more preferably 60 ° C. or higher, and most preferably 80 to 100 ° C. in terms of peelability and deterioration of the adhesive substrate due to warm water. 100 ° C. is more preferable. The immersion time is preferably 1 to 240 minutes, more preferably 2 to 200 minutes, and most preferably 5 to 180 minutes.
本発明の仮固定用接着剤組成物を使用した仮固定方法としては、上述した二剤の混合による仮固定方法を用いた後、100〜200℃に接着体を加熱することにより、仮固定用接着剤組成物の硬化体が軟化し、それにより容易にブタン及び/又はイソブタンを内包する有機系熱膨張性粒子が膨張し、硬化体(接着基材)と仮固定用接着剤組成物との界面に空隙が生じ、硬化体をより容易に剥離できる。加熱温度は高温である方が、ブタン及び/又はイソブタンを内包する有機系熱膨張性粒子の膨張が大きいため、容易に硬化体を剥離することができる。硬化体を取り外す際の加熱温度は、剥離性と接着基材の劣化の点で、130〜200℃がより好ましく、150〜260℃が最も好ましい。加熱時間は、1〜240分が好ましく、10〜120分がより好ましく、15〜60分が最も好ましい。 As a temporary fixing method using the temporary fixing adhesive composition of the present invention, the temporary fixing method by mixing the two agents described above is used, and then the adhesive is heated to 100 to 200 ° C. for temporary fixing. The cured body of the adhesive composition is softened, whereby the organic thermally expandable particles containing butane and / or isobutane easily expand, and the cured body (adhesive base material) and the temporary fixing adhesive composition A space is generated at the interface, and the cured body can be more easily peeled off. When the heating temperature is higher, the organic thermally expandable particles encapsulating butane and / or isobutane have a larger expansion, so that the cured product can be easily peeled off. The heating temperature when removing the cured body is more preferably 130 to 200 ° C, and most preferably 150 to 260 ° C, in terms of peelability and deterioration of the adhesive substrate. The heating time is preferably 1 to 240 minutes, more preferably 10 to 120 minutes, and most preferably 15 to 60 minutes.
積層は、例えば、一方の貼り合わせ面又は両方の貼り合わせ面に仮固定用接着剤組成物が塗布された各部材を貼り合わせた後に、両部材に挟まれて広がっている仮固定用接着剤組成物を硬化させるために、常温で静置することによって実施することができる。これを所望の回数だけ繰り返すことにより、所望の枚数の部材が積層された積層体を作製することができる。常温における静置は、部材を1枚積層する度に実施してもよく、複数枚を積層した後にまとめて実施してもよい。積層枚数は作業性の点から2〜100枚が好ましく、3〜50枚がより好ましく、4〜20枚が最も好ましい。 Lamination is, for example, a temporary fixing adhesive that is sandwiched between both members and then spread after bonding each member coated with the temporary fixing adhesive composition to one bonding surface or both bonding surfaces. In order to cure the composition, it can be carried out by standing at room temperature. By repeating this a desired number of times, a laminate in which a desired number of members are laminated can be produced. The standing at normal temperature may be performed every time one member is stacked, or may be performed collectively after stacking a plurality of members. The number of stacked layers is preferably 2 to 100, more preferably 3 to 50, and most preferably 4 to 20 from the viewpoint of workability.
(3−2)光ラジカル重合開始剤は、可視光線や紫外線の活性光線により増感させて樹脂組成物の光硬化を促進するために使用するものである。光ラジカル重合開始剤としては、ベンゾフェノン及びその誘導体、ベンジル及びその誘導体、アントラキノン及びその誘導体、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール等のベンゾイン誘導体、ジエトキシアセトフェノン、4−t−ブチルトリクロロアセトフェノン等のアセトフェノン誘導体、2−ジメチルアミノエチルベンゾエート、p−ジメチルアミノエチルベンゾエート、ジフェニルジスルフィド、チオキサントン及びその誘導体、カンファーキノン、7,7−メチル−2,3−ジオキソビシクロ[2.2.1]ヘプタン−1−カルボン酸、7,7−ジメチル−2,3−ジオキソビシクロ[2.2.1]ヘプタン−1−カルボキシ−2−ブロモエチルエステル、7,7−ジメチル−2,3−ジオキソビシクロ[2.2.1]ヘプタン−1−カルボキシ−2−メチルエステル、7,7−ジメチル−2,3−ジオキソビシクロ[2.2.1]ヘプタン−1−カルボン酸クロライド等のカンファーキノン誘導体、2−メチル−1−[4-(メチルチオ)フェニル]−2−モルフォリノプロパン−1−オン、2−ベンジル−2−ジメチルアミノ−1−(4−モルフォリノフェニル)−ブタノン−1、2−ジメチルアミノ−2−(4−メチルーベンジル)−1−(4−モルフォリン−4−イルーフェニル)−ブタン−1−オン等のα−アミノアルキルフェノン誘導体、ベンゾイルジフェニルホスフィンオキサイド、2,4,6−トリメチルベンゾイルジフェニルホスフィンオキサイド、ベンゾイルジエトキシポスフィンオキサイド、2,4,6−トリメチルベンゾイルジメトキシフェニルホスフィンオキサイド、2,4,6−トリメチルベンゾイルジエトキシフェニルホスフィンオキサイド等のアシルホスフィンオキサイド誘導体、オキシ−フェニル−アセチックアシッド2−[2−オキソ−2−フェニル−アセトキシ−エトキシ]−エチルエステル及びオキシ−フェニル−アセチックアシッド2−[2−ヒドロキシ−エトキシ]−エチルエステル等が挙げられる。光ラジカル重合開始剤は1種又は2種以上を組み合わせて用いることができる。これらの中では、効果が大きい点で、ベンジルジメチルケタール、2−ジメチルアミノ−2−(4−メチルーベンジル)−1−(4−モルフォリン−4−イルーフェニル)−ブタン−1−オンからなる群のうちの1種又は2種が好ましい。 (3-2) The radical photopolymerization initiator is used for sensitization with visible light or ultraviolet actinic light to promote photocuring of the resin composition. Examples of radical photopolymerization initiators include benzophenone and derivatives thereof, benzyl and derivatives thereof, anthraquinone and derivatives thereof, benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal. Acetophenone derivatives such as ethoxyacetophenone and 4-t-butyltrichloroacetophenone, 2-dimethylaminoethylbenzoate, p-dimethylaminoethylbenzoate, diphenyldisulfide, thioxanthone and derivatives thereof, camphorquinone, 7,7-methyl-2,3- Dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane- -Carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3- Camphorquinone derivatives such as dioxobicyclo [2.2.1] heptane-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl)- Α-Aminoalkylphenone derivatives such as butan-1-one, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Acylphosphine oxide derivatives such as benzoyldioxyphosphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, oxy-phenyl-acetic acid Examples include 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester. A radical photopolymerization initiator can be used alone or in combination of two or more. Among these, benzyldimethyl ketal and 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one are particularly effective. One or two of the groups are preferred.
(3−2)光ラジカル重合開始剤の使用量は、(1)、(2)及び必要に応じて使用する(6)の合計100質量部に対して、0.1〜20質量部が好ましく、1〜10質量部がより好ましい。0.1質量部以上であれば、硬化促進の効果が確実に得られるし、20質量部以下で充分な剥離性を得ることができる。 (3-2) The amount of the radical photopolymerization initiator used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of (1), (2) and (6) used as necessary. 1-10 mass parts is more preferable. If it is 0.1 mass part or more, the effect of hardening acceleration will be acquired reliably, and sufficient peelability can be obtained if it is 20 mass parts or less.
(3−2)光ラジカル重合開始剤を使用した場合は可視光線又は紫外線を照射して、組成物を硬化させる。部材同士を接着する方法としては、仮固定用接着剤組成物に可視光線又は紫外線の少なくとも一方を照射して接着力を高める接着方法等が挙げられる。このような可視光線又は紫外線を照射するためのエネルギー照射源としては、重水素ランプ、高圧水銀ランプ、超高圧水銀ランプ、低圧水銀ランプ、キセノンランプ、キセノン−水銀混成ランプ、ハロゲンランプ、エキシマランプ、インジュームランプ、タリウムランプ、LEDランプ、無電極放電ランプ等のエネルギー照射源が挙げられる。 (3-2) When a radical photopolymerization initiator is used, the composition is cured by irradiation with visible light or ultraviolet rays. Examples of a method for adhering members include an adhesion method for increasing adhesive strength by irradiating at least one of visible light or ultraviolet light to the temporary fixing adhesive composition. As an energy irradiation source for irradiating such visible light or ultraviolet light, a deuterium lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a xenon-mercury hybrid lamp, a halogen lamp, an excimer lamp, Examples of the energy irradiation source include an indium lamp, a thallium lamp, an LED lamp, and an electrodeless discharge lamp.
光ラジカル重合開始剤を含有する仮固定用接着剤組成物(一剤型の仮固定用接着剤組成物)の使用方法は以下の通りである。 The method of using the temporary fixing adhesive composition (one-component temporary fixing adhesive composition) containing a photoradical polymerization initiator is as follows.
可視光線又は紫外線を照射して、仮固定用接着剤組成物を硬化させ、部材を仮固定する際は、波長365nmにおいて1〜10000mJ/cm2のエネルギーを仮固定用接着剤組成物に照射し接着基材同士を接着することが好ましい。1〜10000mJ/cm2であれば仮固定用接着剤組成物が硬化し、十分な接着強度が得られる。1mJ/cm2以上であれば仮固定用接着剤組成物が十分に硬化し、10000mJ/cm2以下であれば硬化歪みがなく、接着強度が向上する。部材同士を仮固定する際のエネルギー量は、接着強度の点で、10〜5000mJ/cm2がより好ましく、1500〜3000mJ/cm2が最も好ましい。 When the adhesive composition for temporary fixing is cured by irradiating visible light or ultraviolet rays, and the member is temporarily fixed, the adhesive composition for temporary fixing is irradiated with energy of 1 to 10,000 mJ / cm 2 at a wavelength of 365 nm. It is preferable to bond the adhesive substrates together. If it is 1-10000mJ / cm < 2 >, the adhesive composition for temporary fixing will harden | cure and sufficient adhesive strength will be obtained. If it is 1 mJ / cm 2 or more, the adhesive composition for temporary fixing is sufficiently cured, and if it is 10000 mJ / cm 2 or less, there is no curing distortion and the adhesive strength is improved. Energy at the time of temporarily fixed member each other in terms of bond strength, more preferably 10~5000mJ / cm 2, 1500~3000mJ / cm 2 being most preferred.
本発明の仮固定用接着剤組成物を使用した仮固定方法としては、上述した光エネルギーによる仮固定方法を用いた後、水に接着体を浸漬することにより、仮固定用接着剤組成物の硬化体が軟化し、それにより容易にブタン及び/又はイソブタンを内包する有機系熱膨張性粒子が膨張し、硬化体(接着基材)と仮固定用接着剤組成物との界面に水が侵入し、硬化体をより容易に剥離できる。水の温度は高温である方が、ブタン及び/又はイソブタンを内包する有機系熱膨張性粒子の膨張が大きいため、水が侵入しやすくなり、容易に硬化体を剥離することができる。硬化体を取り外す際の水の温度は、剥離性と温水による接着基材の劣化の点で、40℃を超えることが好ましく、60℃以上がより好ましく、80〜100℃が最も好ましく、90〜100℃が一層好ましい。浸漬時間は、1〜240分が好ましく、2〜200分がより好ましく、5〜180分が最も好ましい。 As a temporary fixing method using the temporary fixing adhesive composition of the present invention, after using the above-described temporary fixing method by light energy, the adhesive composition for temporary fixing is immersed in water. The hardened body is softened, so that the organic thermally expandable particles containing butane and / or isobutane easily expand, and water enters the interface between the hardened body (adhesive substrate) and the temporary fixing adhesive composition. In addition, the cured body can be peeled off more easily. The higher the temperature of the water, the greater the expansion of the organic thermally expandable particles encapsulating butane and / or isobutane, so that water easily enters and the cured product can be easily peeled off. The temperature of water when removing the cured body is preferably higher than 40 ° C., more preferably 60 ° C. or higher, and most preferably 80 to 100 ° C. in terms of peelability and deterioration of the adhesive substrate due to warm water. 100 ° C. is more preferable. The immersion time is preferably 1 to 240 minutes, more preferably 2 to 200 minutes, and most preferably 5 to 180 minutes.
本発明の仮固定用接着剤組成物を使用した仮固定方法としては、上述した光エネルギーによる仮固定方法を用いた後、100〜200℃に接着体を加熱することにより、仮固定用接着剤組成物の硬化体が軟化し、それにより容易にブタン及び/又はイソブタンを内包する有機系熱膨張性粒子が膨張し、硬化体(接着基材)と仮固定用接着剤組成物との界面に空隙が生じ、硬化体をより容易に剥離できる。加熱温度は高温である方が、ブタン及び/又はイソブタンを内包する有機系熱膨張性粒子の膨張が大きい点で、容易に硬化体を剥離することができる。硬化体を取り外す際の加熱温度は、剥離性と接着基材の劣化の点で、130〜200℃がより好ましく、150〜260℃が最も好ましい。加熱時間は、1〜240分が好ましく、10〜120分がより好ましく、15〜60分が最も好ましい。 As a temporary fixing method using the temporary fixing adhesive composition of the present invention, the temporary fixing method using light energy described above is used, and then the adhesive body is heated to 100 to 200 ° C., thereby temporarily fixing the adhesive. The hardened body of the composition is softened, so that the organic thermally expandable particles encapsulating butane and / or isobutane easily expand, and at the interface between the hardened body (adhesive base material) and the temporary fixing adhesive composition. A space | gap arises and it can peel a hardening body more easily. When the heating temperature is higher, the cured body can be peeled off more easily because the expansion of the organic thermally expandable particles containing butane and / or isobutane is larger. The heating temperature when removing the cured body is more preferably 130 to 200 ° C, and most preferably 150 to 260 ° C, in terms of peelability and deterioration of the adhesive substrate. The heating time is preferably 1 to 240 minutes, more preferably 10 to 120 minutes, and most preferably 15 to 60 minutes.
仮固定用接着剤組成物の硬化体を取り外す際は、仮固定用接着剤組成物に可視光線又は紫外線を波長365nmにおいて好ましくは40000mJ/cm2以下のエネルギーを照射することにより、未反応の(3−2)からラジカルが発生し、大きな硬化歪みが発生し、硬化体自体が大きくうねりを生じ、接着面積が減少し、接着強度が低下するので、容易に硬化体を取り外すことができる。 When removing the cured product of the temporary fixing adhesive composition, the temporary fixing adhesive composition is irradiated with visible light or ultraviolet light at an energy of preferably 40,000 mJ / cm 2 at a wavelength of 365 nm. Since the radical is generated from 3-2), a large curing strain is generated, the cured body itself is greatly swelled, the adhesion area is reduced, and the adhesive strength is lowered, so that the cured body can be easily removed.
積層は、例えば、一方の貼り合わせ面又は両方の貼り合わせ面に仮固定用接着剤組成物が塗布された各部材を貼り合わせた後に、両部材に挟まれて広がっている仮固定用接着剤組成物を硬化させるために、光を照射することによって実施することができる。これを所望の回数だけ繰り返すことにより、所望の枚数の部材が積層された積層体を作製することができる。光照射は、部材を1枚積層する度に実施してもよく、仮固定用接着剤組成物へ光が到達する限りにおいて、複数枚を積層した後にまとめて実施してもよい。積層枚数は作業性の点から2〜100枚が好ましく、3〜50枚がより一層好ましく、4〜20枚が最も好ましい。 Lamination is, for example, a temporary fixing adhesive that is sandwiched between both members and then spread after bonding each member coated with the temporary fixing adhesive composition to one bonding surface or both bonding surfaces. In order to cure the composition, it can be carried out by irradiating with light. By repeating this a desired number of times, a laminate in which a desired number of members are laminated can be produced. The light irradiation may be performed every time one member is stacked, or may be performed collectively after stacking a plurality of sheets as long as light reaches the temporary fixing adhesive composition. The number of stacked layers is preferably 2 to 100, more preferably 3 to 50, and most preferably 4 to 20 from the viewpoint of workability.
(4)平均粒径80〜300μmの粒状物質は、レーザー法によって測定された平均粒径80〜300μmの粒状物質が好ましい。レーザー法によって測定された平均粒径80〜300μmの粒状物質(以下粒状物質ということもある)を使用することにより、硬化体が一定の厚みを保持することが容易となり、寸法精度が向上したまま接着でき、硬化体の厚みを制御でき、安定した剥離性を得ることができる。 (4) The granular material having an average particle size of 80 to 300 μm is preferably a granular material having an average particle size of 80 to 300 μm measured by a laser method. By using a granular material having an average particle size of 80 to 300 μm measured by the laser method (hereinafter sometimes referred to as a granular material), it becomes easy for the cured body to maintain a constant thickness, and dimensional accuracy is improved. It can adhere | attach, can control the thickness of a hardening body, and can obtain the stable peelability.
(4)粒状物質としては、有機粒子、無機粒子いずれでもかまわない。粒状物質は、後述する(5)有機系熱膨張性粒子を除くものをいう。有機粒子としては、ポリエチレン粒子、ポリプロピレン粒子、架橋ポリ(メタ)アクリル酸メチル粒子、架橋ポリスチレン粒子、架橋ポリ(メタ)アクリル酸メチルポリスチレン共重合体粒子等挙げられる。無機粒子としては、ガラス、シリカ、アルミナ、チタン等といった、セラミック粒子が挙げられる。 (4) The particulate material may be either organic particles or inorganic particles. The particulate material means a material excluding (5) organic heat-expandable particles described later. Examples of the organic particles include polyethylene particles, polypropylene particles, crosslinked poly (meth) methyl acrylate particles, crosslinked polystyrene particles, and crosslinked poly (meth) methyl polystyrene polystyrene copolymer particles. Inorganic particles include ceramic particles such as glass, silica, alumina, titanium and the like.
(4)粒状物質としては、加工精度の向上、つまり接着剤の膜厚の制御の点で、球状が好ましい。有機粒子の中では、粒子の変形が少なく、粒径のバラツキによる硬化体の膜厚のバラツキが少ない点で、架橋ポリ(メタ)アクリル酸メチル粒子、架橋ポリスチレン粒子及び架橋ポリ(メタ)アクリル酸メチルポリスチレン共重合体粒子からなる群のうちの1種又は2種以上が好ましい。架橋ポリ(メタ)アクリル酸メチル粒子、架橋ポリスチレン粒子及び架橋ポリ(メタ)アクリル酸メチルポリスチレン共重合体粒子は、例えば、(メタ)アクリル酸メチルモノマーやスチレンモノマーと、架橋性モノマーとを、公知の乳化重合法により重合することにより、単分散粒子として得られる。無機粒子としては、粒子の変形が少なく、粒径のバラツキによる硬化体の膜厚のバラツキが少ない点で、球状シリカが好ましい。これらの中では、粒子の沈降等に因る貯蔵安定性や組成物の反応性の点で、有機粒子が好ましい。 (4) The granular material is preferably spherical in terms of improving processing accuracy, that is, controlling the thickness of the adhesive. Among the organic particles, crosslinked poly (meth) acrylate particles, crosslinked polystyrene particles, and crosslinked poly (meth) acrylic acid are small in that the deformation of the particles is small and the variation in the thickness of the cured product due to the variation in particle size is small. One or more of the group consisting of methylpolystyrene copolymer particles are preferred. Cross-linked poly (meth) acrylate methyl particles, cross-linked polystyrene particles, and cross-linked poly (meth) methyl acrylate polystyrene copolymer particles include, for example, (meth) methyl acrylate monomers and styrene monomers, and cross-linkable monomers. It is obtained as monodisperse particles by polymerizing by the emulsion polymerization method. As the inorganic particles, spherical silica is preferable in that the deformation of the particles is small and the variation in the thickness of the cured product due to the variation in the particle size is small. Among these, organic particles are preferable from the viewpoint of storage stability due to particle sedimentation and the reactivity of the composition.
本発明における粒子径は、例えば、島津製作所製「レーザー回折式粒度分布測定装置SALD−2200」により測定することができる。 The particle diameter in the present invention can be measured by, for example, “Laser diffraction particle size distribution analyzer SALD-2200” manufactured by Shimadzu Corporation.
(4)粒状物質の使用量は、接着強度、加工精度、剥離性の点で、(1)、(2)及び必要に応じて使用する(6)の合計100質量部に対して、0.1〜30質量部が好ましく、0.5〜20質量部がより好ましく、1〜5質量部が最も好ましい。 (4) The amount of the granular material used is 0. 0 in terms of adhesive strength, processing accuracy, and peelability with respect to 100 parts by mass in total of (1), (2) and (6) used as necessary. 1-30 mass parts is preferable, 0.5-20 mass parts is more preferable, and 1-5 mass parts is the most preferable.
(5)ブタン及び/又はイソブタンを内包する有機系熱膨張性粒子(以下有機系熱膨張性粒子ということもある)としては、マイクロカプセル内に、外殻の有機材料(ポリマー)によりブタン及び/又はイソブタンが封入された熱膨張性のマイクロカプセルが挙げられる。(5)有機系熱膨張性粒子は、外殻の有機材料が加熱により軟化すると共に内殻のブタン及び/又はイソブタンが膨張する粒子である。(5)有機系熱膨張性粒子の外殻としては、塩化ビニリデン、(メタ)アクリロニトリル、(メタ)アクリル酸メチルからなる重合体又は共重合体を含有する熱可塑性樹脂が好ましい。本発明では、ブタン及び/又はイソブタンを外殻で包み込んだ熱膨張性マイクロカプセルを好ましく使用できる。 (5) Organic heat-expandable particles encapsulating butane and / or isobutane (hereinafter sometimes referred to as organic heat-expandable particles) include butane and / or a microcapsule depending on the organic material (polymer) of the outer shell. Alternatively, thermally expandable microcapsules encapsulating isobutane can be given. (5) The organic heat-expandable particles are particles in which the outer shell organic material is softened by heating and the inner shell butane and / or isobutane is expanded. (5) The outer shell of the organic thermally expandable particles is preferably a thermoplastic resin containing a polymer or copolymer composed of vinylidene chloride, (meth) acrylonitrile, methyl (meth) acrylate. In the present invention, a thermally expandable microcapsule in which butane and / or isobutane is wrapped with an outer shell can be preferably used.
(5)ブタン及び/又はイソブタンを内包する有機系熱膨張性粒子の平均粒径は、2〜50μmが好ましく、5〜30μmが好ましく、8〜20μmが最も好ましい。2μm以上であれば、組成物の剥離性に優れるし、100μm以下であれは、剥離前の組成物の接着性が低下しない。 (5) The average particle diameter of the organic thermally expandable particles containing butane and / or isobutane is preferably 2 to 50 μm, more preferably 5 to 30 μm, and most preferably 8 to 20 μm. If it is 2 micrometers or more, it is excellent in the peelability of a composition, and if it is 100 micrometers or less, the adhesiveness of the composition before peeling does not fall.
(5)有機系熱膨張性粒子の使用量は、剥離促進の効果と接着力の点から、(1)、(2)及び必要に応じて使用する(6)の合計100質量部に対して、1〜30質量部が好ましく、5〜29.9質量部がより好ましく、10〜25質量部が最も好ましい。1質量部以上であれば、剥離促進の効果が確実に得られるし、30質量部以下で充分な接着力を得ることができる。 (5) The amount of organic thermally expandable particles used is based on 100 parts by mass in total of (1), (2) and (6) used as needed from the viewpoint of peeling promotion effect and adhesive strength. 1-30 parts by mass, more preferably 5-29.9 parts by mass, and most preferably 10-25 parts by mass. If it is 1 part by mass or more, the effect of promoting peeling can be reliably obtained, and if it is 30 parts by mass or less, sufficient adhesive force can be obtained.
本発明は、更に、(6)多官能(メタ)アクリレートを使用することが好ましい。(6)多官能(メタ)アクリレートとは、分子内に2個以上の(メタ)アクリロイル基を有する化合物をいい、(1)以外の多官能(メタ)アクリレートをいう。(6)多官能(メタ)アクリレートとしては、2官能(メタ)アクリレートモノマー、3官能(メタ)アクリレートモノマー、4官能以上の(メタ)アクリレートモノマー等が挙げられる。多官能(メタ)アクリレートの中では、2官能(メタ)アクリレートモノマーが好ましい。 In the present invention, it is further preferable to use (6) polyfunctional (meth) acrylate. (6) The polyfunctional (meth) acrylate refers to a compound having two or more (meth) acryloyl groups in the molecule, and refers to a polyfunctional (meth) acrylate other than (1). (6) Examples of polyfunctional (meth) acrylates include bifunctional (meth) acrylate monomers, trifunctional (meth) acrylate monomers, and tetrafunctional or higher (meth) acrylate monomers. Among polyfunctional (meth) acrylates, bifunctional (meth) acrylate monomers are preferred.
2官能(メタ)アクリレートモノマーとしては、1,3−ブチレングリコールジ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサジオールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ジシクロペンタニルジ(メタ)アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ(メタ)アクリレート、ステアリン酸変性ペンタエリストールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、2,2−ビス(4−(メタ)アクリロキシジエトキシフェニル)プロパン、2,2−ビス(4−(メタ)アクリロキシプロポキシフェニル)プロパン、2,2−ビス(4−(メタ)アクリロキシテトラエトキシフェニル)プロパン、ジメチロール−トリシクロデカンジ(メタ)アクリレート、1,10−デカンジオールジ(メタ)アクリレート、イソシアヌル酸エチレンオキサイド変成ジ(メタ)アクリレート等が挙げられる。これらの中では、効果が大きい点で、1,9−ノナンジオールジ(メタ)アクリレート、1,6−ヘキサジオールジ(メタ)アクリレート及びトリプロピレングリコールジ(メタ)アクリレートからなる群のうちの1種又は2種以上が好ましく、トリプロピレングリコールジ(メタ)アクリレートがより好ましい。 Examples of the bifunctional (meth) acrylate monomer include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, and 1,9- Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, stearic acid modified pentaerythrodi (meth) Acrylate, tripropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2, 2-bis (4- (meth) acryl Alkoxy tetra ethoxyphenyl) propane, dimethylol - tricyclodecane (meth) acrylate, 1,10-decanediol di (meth) acrylate, and the like isocyanuric acid ethylene oxide-modified di (meth) acrylate. Among these, one of the group consisting of 1,9-nonanediol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate and tripropylene glycol di (meth) acrylate is highly effective. Two or more species are preferred, and tripropylene glycol di (meth) acrylate is more preferred.
3官能(メタ)アクリレートモノマーとしては、トリメチロールプロパントリ(メタ)アクリレート、トリス[(メタ)アクリロイキシエチル]イソシアヌレート等が挙げられる。 Examples of the trifunctional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate and tris [(meth) acryloxyethyl] isocyanurate.
4官能以上の(メタ)アクリレートモノマーとしては、ジメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールエトキシテトラ(メタ)アクリレート、ジペンタエリストールペンタ(メタ)アクリレート、ジペンタエリストールヘキサ(メタ)アクリレート等が挙げられる。 As tetrafunctional or higher (meth) acrylate monomers, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerystol penta (meth) acrylate, dipenta Examples include erythrole hexa (meth) acrylate.
(6)の使用量としては(1)、(2)、必要に応じて使用する(6)の合計100質量部中、0〜30質量部が好ましい。(6)の使用量がこの範囲にあると仮固定用接着剤組成物の硬度が高くなるため仮固定した部材の加工時のずれが生じ難く、寸法精度が優れる。30質量部を超えると剥離性が得られない場合がある。寸法精度と剥離性の観点から、5〜25質量部がより好ましく、10〜20質量部が最も好ましい。 As a usage-amount of (6), 0-30 mass parts is preferable in a total of 100 mass parts of (1), (2), and (6) used as needed. When the amount of use of (6) is within this range, the temporarily fixing adhesive composition has a high hardness, so that the temporarily fixed member is hardly displaced during processing, and the dimensional accuracy is excellent. If it exceeds 30 parts by mass, peelability may not be obtained. From a viewpoint of dimensional accuracy and peelability, 5 to 25 parts by mass is more preferable, and 10 to 20 parts by mass is most preferable.
本発明の組成物は、貯蔵安定性向上のために、重合禁止剤を使用できる。重合禁止剤としては、メチルハイドロキノン、ハイドロキノン、2,2−メチレン−ビス(4−メチル−6−ターシャリーブチルフェノール)、カテコール、ハイドロキノンモノメチルエーテル、モノターシャリーブチルハイドロキノン、2,5−ジターシャリーブチルハイドロキノン、p−ベンゾキノン、2,5−ジフェニル−p−ベンゾキノン、2,5−ジターシャリーブチル−p−ベンゾキノン、ピクリン酸、クエン酸、フェノチアジン、ターシャリーブチルカテコール、2−ブチル−4−ヒドロキシアニソール及び2,6−ジターシャリーブチル−p−クレゾール等が挙げられる。これらの中では、効果が大きい点で、2,2−メチレン−ビス(4−メチル−6−ターシャリーブチルフェノール)及び/又はクエン酸が好ましい。 In the composition of the present invention, a polymerization inhibitor can be used to improve the storage stability. Polymerization inhibitors include methyl hydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol), catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone. P-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcatechol, 2-butyl-4-hydroxyanisole and 2 , 6-ditertiary butyl-p-cresol and the like. Among these, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) and / or citric acid are preferable because of their great effects.
重合禁止剤の使用量は、(1)、(2)及び(6)の合計100質量部に対して、0.001〜3質量部が好ましく、0.05〜2質量部がより好ましく、0.1〜0.3質量部が最も好ましい。0.001質量部以上であれば貯蔵安定性が確保されるし、3質量部以下であれば良好な接着性が得られ、未硬化になることもない。 The amount of the polymerization inhibitor used is preferably 0.001 to 3 parts by mass, more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass in total of (1), (2) and (6). 0.1 to 0.3 parts by mass is most preferable. If it is 0.001 mass part or more, storage stability will be ensured, and if it is 3 mass parts or less, favorable adhesiveness will be obtained and it will not become uncured.
本発明の組成物は、本発明の目的を損なわない範囲で、一般に使用されているアクリルゴム、ウレタンゴム、アクリロニトリル−ブタジエン−スチレンゴム等の各種エラストマー、極性有機溶媒等の溶剤、増量材、補強材、可塑剤、増粘剤、染料、顔料、難燃剤、シランカップリング剤及び界面活性剤等の添加剤を使用してもよい。 The composition of the present invention is a generally used acrylic rubber, urethane rubber, various elastomers such as acrylonitrile-butadiene-styrene rubber, solvents such as polar organic solvents, fillers, reinforcements, etc., as long as the object of the present invention is not impaired. Additives such as materials, plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.
本発明において、仮固定する際に用いられる部材の材質に特に制限はないが、例えば、石英部材、セラミックス部材、水晶部材、ガラス部材、プラスチック部材が挙げられる。このような部材は、部材の表面粗さRaが0.2μm以上であったり、加工後の部材の接着面積が60cm2以上であったりしても、本発明の仮固定方法により加工及び剥離が可能であり、適用可能である。部材の表面粗さRaは、50μm以下が好ましい。 In the present invention, the material of the member used for temporary fixing is not particularly limited, and examples thereof include a quartz member, a ceramic member, a crystal member, a glass member, and a plastic member. Such a member can be processed and peeled by the temporary fixing method of the present invention even if the surface roughness Ra of the member is 0.2 μm or more or the bonded area of the processed member is 60 cm 2 or more. It is possible and applicable. The surface roughness Ra of the member is preferably 50 μm or less.
仮固定された部材は、所望の形状にするために、切断、研削、研磨、孔開け等の加工を施した後、該部材を水、好ましくは温水に浸漬することにより、仮固定用接着剤組成物の硬化体を部材から剥離することができる。 The temporarily fixed member is subjected to processing such as cutting, grinding, polishing, and punching in order to obtain a desired shape, and then the member is immersed in water, preferably warm water, to temporarily fix the adhesive. The cured product of the composition can be peeled from the member.
以下に実施例及び比較例を挙げて本発明を更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
(実施例1〜9、比較例1〜5)
以下の方法により評価した。
(Examples 1-9, Comparative Examples 1-5)
Evaluation was made by the following method.
(仮固定用接着剤組成物の作製)
表1の使用材料を用いた。表2、表4、表6、表8の組成で各使用材料を混合して、第一剤と第二剤からなる仮固定用接着剤組成物(二剤を二液ということもある)若しくは一剤の仮固定用接着剤組成物(一剤を一液ということもある)を調製した。得られた接着剤組成物を使用して、以下に示す評価方法にてD硬度、引張せん断接着強さ測定、接着・剥離試験(A)〜(F)を行った。結果を表3、表5、表7、表9に示す。表2、表4、表6、表8の組成物名には、表1に示す略号を用いた。
(Preparation of temporary fixing adhesive composition)
The materials used in Table 1 were used. Each material used is mixed in the composition of Table 2, Table 4, Table 6, and Table 8, and an adhesive composition for temporary fixing composed of a first agent and a second agent (the two agents are sometimes referred to as two liquids) or An adhesive composition for temporary fixing (one agent may be referred to as one liquid) was prepared. Using the obtained adhesive composition, D hardness, tensile shear bond strength measurement, and adhesion / peeling tests (A) to (F) were performed by the following evaluation methods. The results are shown in Table 3, Table 5, Table 7, and Table 9. The abbreviations shown in Table 1 were used for the composition names in Table 2, Table 4, Table 6, and Table 8.
(評価方法) (Evaluation method)
積算光量:積算光量は紫外線積算照度計(アイグラフィック社製:EYE UVMETER UVPF-A1(365nm受光器使用))により測定した。 Integrated light amount: The integrated light amount was measured with an ultraviolet integrated illuminometer (manufactured by Eye Graphic: EYE UVMETER UVPF-A1 (using 365 nm light receiver)).
2液硬化による仮固定用接着剤硬化体のD硬度(表の「D硬度(2液硬化)」):第一剤と第二剤を等量混合した仮固定用接着剤組成物を、5mm厚のシリコンシートを型枠とし、PETフィルムに挟み込んだ。仮固定用接着剤組成物を、5mm厚のシリコンシートを型枠とし、PETフィルムに挟み込んだ。仮固定用接着剤組成物を、23℃で24時間養生し、厚さ5mmの仮固定用接着剤組成物の硬化体を作製した。作製した硬化体をカッターにて直径30mmの円柱状に切断し、ショアD硬度測定用硬化体とした。得られた硬化体を、D型ショア硬度計を用いてASTM D−2240により値を測定した。 D hardness of cured adhesive body for temporary fixing by two-component curing (“D hardness (two-component curing)” in the table): 5 mm of an adhesive composition for temporary fixing in which equal amounts of the first agent and the second agent are mixed A thick silicon sheet was used as a mold and sandwiched between PET films. The temporary fixing adhesive composition was sandwiched between PET films using a 5 mm thick silicon sheet as a mold. The temporary fixing adhesive composition was cured at 23 ° C. for 24 hours to prepare a cured body of the temporary fixing adhesive composition having a thickness of 5 mm. The produced cured body was cut into a cylindrical shape having a diameter of 30 mm with a cutter to obtain a cured body for Shore D hardness measurement. The value of the obtained cured product was measured by ASTM D-2240 using a D-type Shore hardness meter.
UV照射による仮固定用接着剤硬化体のD硬度(表の「D硬度(UV照射)」):仮固定用接着剤組成物を、ベルトコンベア式メタルハライドランプを使用し、365nmの波長の積算光量2000mJ/cm2の条件にて光を上面から照射、硬化させた後、更に下面から365nmの波長の積算光量2000mJ/cm2の条件にて光を下面から照射、硬化させ、厚さ5mmの硬化体を作製した。作製した硬化体をカッターにて直径30mmの円柱状に切断し、ショアD硬度測定用硬化体とした。得られた硬化体を、D型ショア硬度計を用いてASTM D−2240により値を測定した。 D hardness of cured adhesive body for temporary fixing by UV irradiation ("D hardness (UV irradiation)" in the table): Using a belt conveyor type metal halide lamp, the temporary fixing adhesive composition is an integrated light quantity at a wavelength of 365 nm. After irradiating and curing light from the upper surface under the condition of 2000 mJ / cm 2 , and further irradiating and curing light from the lower surface under the condition of an integrated light amount of 2000 mJ / cm 2 with a wavelength of 365 nm from the lower surface, curing with a thickness of 5 mm The body was made. The produced cured body was cut into a cylindrical shape having a diameter of 30 mm with a cutter to obtain a cured body for Shore D hardness measurement. The value of the obtained cured product was measured by ASTM D-2240 using a D-type Shore hardness meter.
2液硬化による引張せん断接着強さ(表の「接着強さ(2液硬化)」):JIS K 6850に従い測定した。具体的には被着材とした耐熱ガラス(商品名「耐熱パイレックス(登録商標)ガラス」、長さ25mm×幅25mm×厚さ2.0mm)を用いて、接着部位を直径8mmの円形として、第一剤と第二剤を等量混合した仮固定用接着剤組成物にて、2枚の耐熱ガラスを貼り合わせ、23℃で24時間養生して硬化させた後に、引張せん断接着強さ試験片を作製した。作製した試験片は、万能試験機を使用して、温度23℃、湿度50%の環境下、引張速度10mm/minで引張せん断接着強さを測定した。 Tensile shear adhesive strength by two-component curing (“Adhesive strength (two-component curing)” in the table): Measured according to JIS K 6850. Specifically, using the heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, length 25 mm × width 25 mm × thickness 2.0 mm) as the adherend, the bonding site is a circle with a diameter of 8 mm, Adhesive composition for temporary fixing in which equal amounts of the first agent and the second agent are mixed, two heat-resistant glasses are bonded together, cured at 23 ° C. for 24 hours, and then subjected to a tensile shear bond strength test. A piece was made. The prepared test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.
UV照射による引張せん断接着強さ(表の「接着強さ(UV照射)」):JIS K 6850に従い測定した。被着材とした耐熱ガラス(商品名「耐熱パイレックス(登録商標)ガラス」、長さ25mm×幅25mm×厚さ2.0mm)を用いて、接着部位を直径8mmの円形として、仮固定用接着剤組成物を使用して、2枚の耐熱ガラスを貼り合わせ、ベルトコンベア式メタルハライドランプを使用し、365nmの波長の積算光量2000mJ/cm2の条件にて光を上面から照射、硬化させ、引張せん断接着強さ試験片を作製した。作製した試験片は、万能試験機を使用して、温度23℃、湿度50%の環境下、引張速度10mm/minで引張せん断接着強さを測定した。 Tensile shear adhesive strength by UV irradiation (“Adhesive strength (UV irradiation)” in the table): Measured according to JIS K 6850. Adhesion for temporary fixing, using a heat-resistant glass (trade name “Heat-resistant Pyrex (registered trademark) glass”, length 25 mm × width 25 mm × thickness 2.0 mm) as the adherend, and making the bonding part a circle with a diameter of 8 mm Two heat-resistant glasses are bonded together using the agent composition, a belt conveyor type metal halide lamp is used, light is irradiated and cured from the upper surface under the condition of an integrated light amount of 2000 mJ / cm 2 at a wavelength of 365 nm, and tension is applied. A shear bond strength test piece was prepared. The prepared test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.
(接着・剥離試験(A))
接着基材である石英硝子A(長さ60mm×幅60mm×厚さ2mm、表面粗さRa:0.7μm)上に、第一剤と第二剤を等量混合した接着剤組成物を3g塗布し、石英硝子B(長さ40mm×幅40mm×厚さ2mm、表面粗さRa:0.7μm)を貼り合わせ、23℃で24時間養生して硬化させ、完全に接着していることを確認した後、得られた試験体を、温水(95℃)に浸漬し、石英硝子同士が剥離する時間を測定し、又剥離後のフィルムの状態も確認した。剥離時間は、温水に浸漬してから、部材が剥離するまでの時間をいう。
(Adhesion / peeling test (A))
3 g of an adhesive composition obtained by mixing equal amounts of the first agent and the second agent on quartz glass A (length 60 mm × width 60 mm × thickness 2 mm, surface roughness Ra: 0.7 μm) as an adhesive substrate Apply and paste quartz glass B (length 40 mm x width 40 mm x thickness 2 mm, surface roughness Ra: 0.7 μm), cure at 23 ° C. for 24 hours, cure and fully adhere After confirmation, the obtained specimen was immersed in warm water (95 ° C.), the time for separating the quartz glass from each other was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from immersing in warm water until the member peels.
(接着・剥離試験(B))
接着基材である石英硝子A(長さ150mm×幅150mm×厚さ2mm、表面粗さRa:0.7μm)上に、第一剤と第二剤を等量混合した接着剤組成物を7g塗布し、石英硝子B(長さ150mm×幅150mm×厚さ2mm、表面粗さRa:0.7μm)を貼り合わせ、23℃で24時間養生して硬化させ、石英硝子同士を接着した。その後、得られた試験体を、ホットプレートにて160℃に加熱し、石英硝子同士が剥離する時間を測定し、又剥離後のフィルムの状態も確認した。剥離時間は、160℃に加熱したホットプレート上に試験体を載置してから、部材が剥離するまでの時間をいう。
(Adhesion / peeling test (B))
7 g of an adhesive composition in which equal amounts of the first agent and the second agent are mixed on quartz glass A (length 150 mm × width 150 mm × thickness 2 mm, surface roughness Ra: 0.7 μm) as an adhesive substrate. Then, quartz glass B (length 150 mm × width 150 mm × thickness 2 mm, surface roughness Ra: 0.7 μm) was bonded, cured at 23 ° C. for 24 hours and cured, and the quartz glasses were bonded to each other. Then, the obtained test body was heated at 160 degreeC with the hotplate, the time which quartz glass peeled was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from when the test body is placed on a hot plate heated to 160 ° C. until the member peels.
(接着・剥離試験(C))
接着基材である石英硝子A(長さ60mm×幅60mm×厚さ2mm、表面粗さRa:0.7μm)上に、仮固定用接着剤組成物を3g塗布し、石英硝子B(長さ40mm×幅40mm×厚さ2mm、表面粗さRa:0.7μm)を貼り合わせ、ベルトコンベア式メタルハライドランプを使用し、365nmの波長の積算光量2000mJ/cm2の条件にて石英硝子B上面から光を照射、硬化させ、石英硝子同士を接着した。その後、得られた試験体を、温水(95℃)に浸漬し、石英硝子同士が剥離する時間を測定し、又剥離後のフィルムの状態も確認した。剥離時間は、温水に浸漬してから、部材が剥離するまでの時間をいう。
(Adhesion / peeling test (C))
3 g of the adhesive composition for temporary fixing was applied to quartz glass A (length 60 mm × width 60 mm × thickness 2 mm, surface roughness Ra: 0.7 μm) as an adhesive base material, and quartz glass B (length 40mm × width 40mm × thickness 2mm, surface roughness Ra: 0.7 μm), using a belt conveyor type metal halide lamp, from the upper surface of quartz glass B under the condition of an integrated light amount of 2000 mJ / cm 2 at a wavelength of 365 nm Light was irradiated and cured, and the quartz glasses were bonded together. Then, the obtained test body was immersed in warm water (95 degreeC), the time which quartz glass peeled was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from immersing in warm water until the member peels.
(接着・剥離試験(D))
接着基材である石英硝子A(長さ150mm×幅150mm×厚さ2mm、表面粗さRa:0.7μm)上に、仮固定用接着剤組成物を7g塗布し、石英硝子B(長さ150mm×幅150mm×厚さ2mm、表面粗さRa:0.7μm)を貼り合わせ、ベルトコンベア式メタルハライドランプを使用し、365nmの波長の積算光量2000mJ/cm2の条件にて石英硝子B上面から光を照射、硬化させ、石英硝子同士を接着した。その後、得られた試験体を、ホットプレートにて160℃に加熱し、石英硝子同士が剥離する時間を測定し、又剥離後のフィルムの状態も確認した。
(Adhesion / peeling test (D))
7 g of the adhesive composition for temporary fixing was applied to quartz glass A (length 150 mm × width 150 mm × thickness 2 mm, surface roughness Ra: 0.7 μm) as an adhesive substrate, and quartz glass B (length 150mm × width 150mm × thickness 2mm, surface roughness Ra: 0.7 μm), using a belt conveyor type metal halide lamp, from the upper surface of quartz glass B under the condition of an integrated light quantity of 2000 mJ / cm 2 at a wavelength of 365 nm Light was irradiated and cured, and the quartz glasses were bonded together. Then, the obtained test body was heated at 160 degreeC with the hotplate, the time which quartz glass peeled was measured, and the state of the film after peeling was also confirmed.
(実施例10〜18、比較例6〜10)
以下の方法により評価した。
(Examples 10 to 18, Comparative Examples 6 to 10)
Evaluation was made by the following method.
(積層接着・加工・剥離試験(A))
1.石英ガラス積層体の作製
接着基材である石英ガラス(長さ150mm×幅150mm×厚さ2mm、表面粗さRa:1.5μm)上に、接着剤組成物を介して石英ガラス(長さ150mm×幅150mm×厚さ2mm、表面粗さRa:1.5μm)を12枚貼り合わせ、石英ガラスの積層体を作製した。
二剤型の接着剤組成物では、第一剤と第二剤を等量混合した接着剤組成物を介して作製した積層体を、23℃で24時間養生し、硬化させた。光ラジカル重合開始剤を含有する接着剤組成物(一剤型の接着剤組成物)では、ベルトコンベア式メタルハライドランプを使用し、波長365nmの積算光量2000mJ/cm2の条件にて石英ガラス上面から光を照射し、硬化させた。尚、光照射は、石英ガラスを1枚積層する度に実施し、11回繰り返すことにより石英ガラスの積層体を作製した。
(Lamination adhesion / processing / peeling test (A))
1. Production of quartz glass laminate On quartz glass (length 150 mm × width 150 mm × thickness 2 mm, surface roughness Ra: 1.5 μm) as an adhesive substrate, quartz glass (length 150 mm) is passed through an adhesive composition. 12 sheets of width 150 mm × thickness 2 mm, surface roughness Ra: 1.5 μm) were bonded together to produce a quartz glass laminate.
In the two-component adhesive composition, the laminate produced through the adhesive composition in which equal amounts of the first agent and the second agent were mixed was cured at 23 ° C. for 24 hours and cured. In an adhesive composition containing a radical photopolymerization initiator (single-component adhesive composition), a belt conveyor type metal halide lamp is used, and the quartz glass top surface is used under the condition of an integrated light quantity of 2000 mJ / cm 2 with a wavelength of 365 nm. It was irradiated with light and cured. Light irradiation was performed every time one quartz glass was laminated, and was repeated 11 times to produce a quartz glass laminate.
2.石英ガラス積層体の切断加工
次に、板ガラスの積層体をバンドソーによって所定の切断線に沿って厚み方向に切断し、分割された石英ガラスの積層体を作製した。このとき、石英ガラスは、横40mm×縦40mm×厚み2mmに分割された。
2. Cutting processing of quartz glass laminate Next, the laminate of plate glass was cut in the thickness direction along a predetermined cutting line with a band saw to produce a divided quartz glass laminate. At this time, the quartz glass was divided into 40 mm wide × 40 mm long × 2 mm thick.
3.得られた石英ガラス積層体を温水(95℃)に浸漬し、石英ガラス同士が剥離する時間を測定し、又剥離後のフィルムの状態も確認した。剥離時間は、温水に浸漬してから、12枚全ての石英ガラスが剥離するまでに要した時間とした。剥離した切断試験片を無作為に10個取り出し、その切断試験片の裏面(仮固定用接着剤組成物で仮固定した面)の各片を、光学顕微鏡を用いて観察し、石英ガラスが欠けている箇所の最大幅を測定し、その平均値と標準偏差を求めた。結果を表3、表5、表7、表9、表10に示す。 3. The obtained quartz glass laminate was immersed in warm water (95 ° C.), the time for the quartz glass to peel off was measured, and the state of the film after peeling was also confirmed. The peeling time was the time required for all 12 quartz glasses to peel after being immersed in warm water. Ten pieces of the peeled test specimens were taken out at random, and each piece on the back surface (the surface temporarily fixed with the temporary fixing adhesive composition) was observed using an optical microscope, and the quartz glass was missing. The maximum width of the spot was measured, and the average value and standard deviation were obtained. The results are shown in Table 3, Table 5, Table 7, Table 9, and Table 10.
(実施例19〜27、比較例11〜15)
以下の方法により評価した。
(Examples 19 to 27, Comparative Examples 11 to 15)
Evaluation was made by the following method.
(積層接着・加工・剥離試験(B))
1.石英ガラス積層体の作製
接着基材である石英ガラス(長さ150mm×幅150mm×厚さ2mm、表面粗さRa:1.5μm)上に、第一剤と第二剤を等量混合した接着剤組成物を介して石英ガラス(長さ150mm×幅150mm×厚さ2mm、表面粗さRa:1.5μm)を12枚貼り合わせ、石英ガラスの積層体を作製した。
二剤型の接着剤組成物では、第一剤と第二剤を等量混合した接着剤組成物を介して作製した積層体を、23℃で24時間養生し、硬化させた。光ラジカル重合開始剤を含有する接着剤組成物(一剤型の接着剤組成物)では、ベルトコンベア式メタルハライドランプを使用し、波長365nmの積算光量2000mJ/cm2の条件にて石英ガラス上面から光を照射、硬化させた。尚、光照射は、石英ガラスを1枚積層する度に実施し、11回繰り返すことにより石英ガラスの積層体を作製した。
(Lamination adhesion / processing / peeling test (B))
1. Fabrication of quartz glass laminate Adhesive mixture of equal amounts of the first agent and the second agent on quartz glass (length 150 mm x width 150 mm x thickness 2 mm, surface roughness Ra: 1.5 μm) as an adhesion base material 12 sheets of quartz glass (length 150 mm × width 150 mm × thickness 2 mm, surface roughness Ra: 1.5 μm) were bonded together through the agent composition to prepare a quartz glass laminate.
In the two-component adhesive composition, the laminate produced through the adhesive composition in which equal amounts of the first agent and the second agent were mixed was cured at 23 ° C. for 24 hours and cured. In an adhesive composition containing a radical photopolymerization initiator (single-component adhesive composition), a belt conveyor type metal halide lamp is used, and the quartz glass top surface is used under the condition of an integrated light quantity of 2000 mJ / cm 2 with a wavelength of 365 nm. Light was irradiated and cured. Light irradiation was performed every time one quartz glass was laminated, and was repeated 11 times to produce a quartz glass laminate.
2.石英ガラス積層体の切断加工
次に、板ガラスの積層体をバンドソーによって所定の切断線に沿って厚み方向に切断し、分割された石英ガラスの積層体を作製した。このとき、石英ガラスは、横75mm×縦75mm×厚み2mmに分割された。
2. Cutting processing of quartz glass laminate Next, the laminate of plate glass was cut in the thickness direction along a predetermined cutting line with a band saw to produce a divided quartz glass laminate. At this time, the quartz glass was divided into a width of 75 mm, a length of 75 mm, and a thickness of 2 mm.
3.得られた石英ガラス積層体を160℃に加熱されたオーブンの中で30分暴露し、石英ガラス同士を剥離させて剥離性を観察した。又剥離後のフィルムの状態も確認した。剥離した切断試験片を無作為に10個取り出し、その切断試験片の裏面(仮固定用接着剤組成物で仮固定した面)の各片を、光学顕微鏡を用いて観察し、石英ガラスが欠けている箇所の最大幅を測定し、その平均値と標準偏差を求めた。結果を表3、表5、表7、表9、表11に示す。 3. The obtained quartz glass laminate was exposed in an oven heated to 160 ° C. for 30 minutes, and the quartz glass was peeled off to observe the peelability. The state of the film after peeling was also confirmed. Ten pieces of the peeled test specimens were taken out at random, and each piece on the back surface (the surface temporarily fixed with the temporary fixing adhesive composition) was observed using an optical microscope, and the quartz glass was missing. The maximum width of the spot was measured, and the average value and standard deviation were obtained. The results are shown in Table 3, Table 5, Table 7, Table 9, and Table 11.
表1〜11から本発明は優れた効果を有することが判った。比較例1は成分(1)が本発明と異なるため、比較例2は成分(2)が本発明と異なるため、比較例3は成分(4)が本発明と異なるため、比較例4は成分(5)が本発明と異なるため、比較例5は成分(5)を含まないため、効果を示さなかった。 From Tables 1-11, it turned out that this invention has the outstanding effect. Since Comparative Example 1 is different from the present invention in Component (1), Comparative Example 2 is different from the present invention in Component (2), and Comparative Example 3 is different from the present invention in Component (4). Since (5) is different from the present invention, Comparative Example 5 did not contain the component (5), and therefore did not show an effect.
光ラジカル重合開始剤を含有する組成物は、その組成故に光硬化性を有し、可視光線又は紫外線によって硬化し、その硬化体は切削水等に影響されずに、高い接着強度を発現しできる。 The composition containing a radical photopolymerization initiator has photocurability because of its composition, is cured by visible light or ultraviolet light, and the cured product can exhibit high adhesive strength without being affected by cutting water or the like. .
熱ラジカル重合開始剤を含有する組成物は、その組成故に常温硬化性を有し、常温で硬化し、その硬化体は切削水等に影響されずに、高い接着強度を発現できる。 The composition containing the thermal radical polymerization initiator has room temperature curability because of its composition, is cured at room temperature, and the cured product can exhibit high adhesive strength without being affected by cutting water or the like.
従来の技術では表面が粗い部材や大面積の部材を仮固定し、加工した後、糊残り無く容易に剥離することは困難であった。本発明は、特定のオリゴマーと特定の単官能(メタ)アクリレート、ラジカル重合開始剤、特定の粒状物質、特定の有機系熱膨張性粒子を含有することにより、表面が粗い部材や大面積の部材であっても、工程を増やすことなく十分な接着性が得られ、加工時にずれが生じず、寸法精度が向上し、優れた部材が容易に得られる。 In the prior art, it is difficult to easily peel off a member having a rough surface or a large area member after temporarily fixing and processing, without leaving any adhesive residue. The present invention contains a specific oligomer, a specific monofunctional (meth) acrylate, a radical polymerization initiator, a specific granular material, and a specific organic heat-expandable particle, thereby having a rough surface or a large area member. Even so, sufficient adhesion can be obtained without increasing the number of steps, no deviation occurs during processing, dimensional accuracy is improved, and an excellent member can be easily obtained.
本発明は、接着体が温水と接触することにより、接着強度が低下し、部材間又は部材と治具との間の接合力が低下するので、容易に部材の回収ができる。 In the present invention, since the adhesive body is brought into contact with warm water, the adhesive strength is reduced, and the bonding force between the members or between the member and the jig is reduced. Therefore, the member can be easily recovered.
本発明は、接着体を加熱することにより、接着強度が低下し、部材間又は部材と治具との間の接合力が低下するので、容易に部材の回収ができる。 In the present invention, by heating the adhesive body, the adhesive strength is reduced, and the bonding force between the members or between the member and the jig is reduced. Therefore, the member can be easily recovered.
本発明の部材の仮固定方法は、従来技術に於いて必要であった有機溶媒を用いる必要がなく、剥離後も部材に糊残りがなく、部材から硬化体を容易に回収できるので、作業性に優れる。 The method of temporarily fixing the member of the present invention does not require the use of an organic solvent that has been necessary in the prior art, and there is no adhesive residue on the member even after peeling, and the cured product can be easily recovered from the member. Excellent.
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R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |