TW201900733A - Sturdy composition and structure - Google Patents

Sturdy composition and structure Download PDF

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TW201900733A
TW201900733A TW107110650A TW107110650A TW201900733A TW 201900733 A TW201900733 A TW 201900733A TW 107110650 A TW107110650 A TW 107110650A TW 107110650 A TW107110650 A TW 107110650A TW 201900733 A TW201900733 A TW 201900733A
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TWI753144B (en
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田村賢
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日商味之素股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
    • G02B7/02—Mountings, adjusting means, or light-tight connections, for optical elements for lenses
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B17/00—Details of cameras or camera bodies; Accessories therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B30/00—Camera modules comprising integrated lens units and imaging units, specially adapted for being embedded in other devices, e.g. mobile phones or vehicles

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention provides a curable composition which contains (1) a compound having a (meth)acryloyl group, (2) a polythiol compound having two or more mercapto groups in each molecule, (3) a photoradical generator and (4) a latent curing agent.

Description

硬化性組成物及構造物Hardening composition and structure

本發明為關於硬化性組成物、以及含有上述硬化性組成物之硬化物以作為第一黏附體及第二黏附體的黏著層之構造物。The present invention relates to a structure of a curable composition and a cured product containing the curable composition as an adhesive layer of a first adherend and a second adherend.

近年，伴隨著智慧型手機等的攜帶型機器的薄型化，智慧型手機等之攜帶型機器所搭載的相機模組也逐漸小型化。由於相機模組的小型化，將相機模組之構成構件間連結之部位也變得更精細，因此要求將此等連結之黏著劑所形成的黏著層之高黏著強度。In recent years, with the reduction in the thickness of portable devices such as smartphones, the camera modules mounted on portable devices such as smartphones have gradually become smaller. Due to the miniaturization of the camera module, the positions where the constituent components of the camera module are connected are also made finer. Therefore, it is required to have a high adhesive strength of the adhesive layer formed by the adhesive that connects these.

又，相機模組等之組裝時所使用的黏著劑，為了避免由於高溫處理對圖像傳感器等的熱損壞而需要低溫硬化性，又，從提升生產效率的角度來看，同時也需要短時間硬化性。從這樣的角度來看，作為低溫短時間硬化型黏著劑，常使用紫外線硬化型黏著劑或熱硬化環氧樹脂系黏著劑。然而，紫外線硬化型黏著劑，雖然可快速硬化，但有由於硬化收縮會發生硬化變形、無法於光照射不到的部分之黏著中使用等的缺點。另一方面，熱硬化環氧樹脂系黏著劑，雖然是低溫短時間硬化型黏著劑，但在黏著時為了保持黏著姿勢，黏著之構件(零件)必須以夾具或裝置固定，又，由於加熱溫度上升而導致黏度降低，在硬化之前發生下垂，出現流到期望部分之外等的問題，為不一定能令人滿意之物。In addition, the adhesive used in the assembly of camera modules and the like requires low-temperature hardening in order to avoid thermal damage to the image sensor and the like due to high-temperature processing. From the perspective of improving production efficiency, it also requires a short time. Sclerosing. From such a viewpoint, as a low-temperature short-time curing adhesive, a UV-curing adhesive or a thermosetting epoxy resin-based adhesive is often used. However, although UV-curable adhesives can harden quickly, they have disadvantages such as hardening and deformation due to curing shrinkage, and inability to be used for adhesion to parts not exposed to light. On the other hand, although thermosetting epoxy resin-based adhesives are low-temperature, short-time-curing adhesives, in order to maintain the adhesive posture during adhesion, the adhered members (parts) must be fixed by fixtures or devices. Increasing causes viscosity to decrease, sags occur before hardening, and problems such as flowing out of the desired part occur, which are not necessarily satisfactory.

因此，為了解決如上述之問題，為了將構成相機模組之構件間高度準確地配置，進行透過光(紫外光、可見光)照射而引起的硬化(初步硬化)暫時固定，再透過加熱正式硬化及進行正式黏著(正式固定)的類型之黏著劑提出了數個提案(例如，專利文獻1及2)。 [先前技術文獻] [專利文獻]Therefore, in order to solve the problems as described above, in order to highly accurately arrange the components constituting the camera module, the hardening (preliminary hardening) caused by the transmission of light (ultraviolet light and visible light) is temporarily fixed, and then the hardening is formally hardened by heating and Several proposals have been made for adhesives of the type that is formally adhered (formally fixed) (for example, Patent Documents 1 and 2). [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開2009-51954號公報 　　[專利文獻2]日本特開2009-79216號公報[Patent Document 1] JP 2009-51954 [Patent Document 2] JP 2009-79216

[發明欲解決之問題][Invention to solve the problem]

透過將習知的黏著劑光硬化、熱硬化或光及熱硬化所得之硬化物的黏著層，在某些情況下不具有足夠的黏著強度。又，習知的黏著劑在某些情況下不具有足夠的保存安定性。此外，在其中一個黏附體為聚碳酸酯製的構件(例如，鏡片)的情況下，使用習知的黏著劑時，聚碳酸酯分解，並且在該構件發生空隙，從而黏著強度有降低可能。Adhesive layers of hardened materials obtained by photo-hardening, heat-hardening, or light- and heat-hardening of conventional adhesives do not have sufficient adhesive strength in some cases. Moreover, conventional adhesives do not have sufficient storage stability in some cases. In addition, in the case where one of the adherends is a member made of polycarbonate (for example, a lens), when a conventional adhesive is used, the polycarbonate is decomposed, and voids occur in the member, which may reduce the adhesive strength.

鑒於上述情況而完成了本發明，其目的為提供光硬化性及熱硬化性優異、可形成具有足夠的黏著強度之硬化物(黏著層)，保存安定性優異，且在將聚碳酸酯製之構件黏著之情況下可抑制其分解的硬化性組成物。 [解決問題之方法]The present invention has been made in view of the above circumstances, and an object thereof is to provide a cured product (adhesive layer) having excellent photo-hardening property and thermo-hardening property, sufficient adhesive strength, and excellent storage stability. A hardening composition that suppresses decomposition of a member when it is adhered. [Solution to the problem]

經本發明者反覆勤奮研究的結果，發現含有(1)具有(甲基)丙烯醯基的化合物、(2)1分子中具有2個以上之巰基的多硫醇化合物、(3)光自由基產生劑、以及(4)潛伏性硬化劑之硬化性組成物可以實現上述目標。根據該發現的本發明如下。As a result of intensive research by the inventors, it was found that (1) a compound having a (meth) acrylfluorenyl group, (2) a polythiol compound having two or more thiol groups in one molecule, and (3) photoradical generation The hardening composition of the agent and (4) the latent hardener can achieve the above-mentioned object. The present invention based on this finding is as follows.

[1]一種硬化性組成物，含有以下之成分(1)~(4)： 　　(1)具有(甲基)丙烯醯基的化合物， 　　(2)1分子中具有2個以上之巰基的多硫醇化合物， 　　(3)光自由基產生劑，以及 　　(4)潛伏性硬化劑。 　　[2]如上述[1]之硬化性組成物，其中成分(1)含有以下之成分(1-1)： 　　(1-1)具有(甲基)丙烯醯基以及環氧基之化合物。 　　[3]如上述[1]或[2]之硬化性組成物，其中成分(1)含有以下之成分(1-2)： 　　(1-2)磷酸變性(甲基)丙烯酸酯。 　　[4]如上述[1]~[3]之任一項的硬化性組成物，其中成分(1)含有以下之成分(1-1)~(1-3)： 　　(1-1)具有(甲基)丙烯醯基以及環氧基之化合物， 　　(1-2)磷酸變性(甲基)丙烯酸酯， 　　(1-3)具有不符合成分(1-1)及成分(1-2)任一者之(甲基)丙烯醯基的化合物。 　　[5]如上述[1]~[4]之任一項的硬化性組成物，其中成分(2)含有1分子中具有2~6個之巰基的多硫醇化合物。 　　[6]如上述[1]~[5]之任一項的硬化性組成物，其中成分(2)含有自季戊四醇四(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、三(3-巰基丙基)異氰脲酸酯、三羥甲基丙烷三(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)、三[(3-巰基丙醯氧基)乙基]異氰脲酸酯、乙二醇雙(巰基乙酸酯)、三羥甲基丙烷三(巰基乙酸酯)、季戊四醇四(巰基乙酸酯)、1,4-雙(3-巰基丁醯氧基)丁烷、1,3,5-三(3-巰基丁醯氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷三(3-巰基丁酸酯)、三羥甲基乙烷三(3-巰基丁酸酯)、1,3,4,6-四(2-巰基乙基)甘脲、以及4,4’-異亞丙基二苯基雙(3-巰基丙基)醚所組成之群組中選擇出之至少一種。 　　[7]如上述[1]~[5]之任一項的硬化性組成物，其中成分(2)含有自季戊四醇四(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、三(3-巰基丙基)異氰脲酸酯、以及二季戊四醇六(3-巰基丙酸酯)所組成之群組中選擇出之至少一種。 　　[8]如上述[1]~[7]之任一項的硬化性組成物，其中成分(1)中之丙烯醯基、甲基丙烯醯基以及環氧基之總計與成分(2)中之巰基的莫耳比(成分(1)中之丙烯醯基、甲基丙烯醯基以及環氧基之總計/成分(2)中之巰基)為0.5~2.0。 　　[9]如上述[1]~[8]之任一項的硬化性組成物，其中成分(4)含有自胺-環氧加合物系化合物以及胺-異氰酸酯加合物系化合物所組成之群組中選擇出之至少一種。 　　[10]如上述[1]~[9]之任一項的硬化性組成物，其中作為成分(5)，係更進一步含有熱自由基產生劑。 　　[11]一種構造物，其係含有第一黏附體、第二黏附體與此等之黏著層之構造物，其中； 　　第一黏附體為聚碳酸酯製之構件， 　　該黏著層為前述[1]~[10]之任一項的硬化性組成物的硬化物。 　　[12]如上述[11]之構造物，其係相機模組。 [發明效果][1] A hardenable composition containing the following components (1) to (4):) (1) a compound having a (meth) acrylic fluorenyl group, 硫 (2) a polysulfide having two or more thiol groups in one molecule Alcohol compounds, (3) photoradical generators, and (4) latent hardeners. [2] The curable composition according to the above [1], wherein the component (1) contains the following component (1-1): (1) A compound having a (meth) acrylfluorenyl group and an epoxy group. [3] The hardenable composition according to the above [1] or [2], wherein the component (1) contains the following component (1-2): (1-2) phosphoric acid-denatured (meth) acrylate. [4] The curable composition according to any one of the above [1] to [3], wherein the component (1) contains the following components (1-1) to (1-3): (1) has ( Compounds of meth) acrylfluorenyl and epoxy groups, (1-2) phosphoric acid modified (meth) acrylate, (1-3) has any of components (1-1) and (1-2) which do not meet the requirements (Meth) acrylfluorenyl compounds. [5] The curable composition according to any one of the above [1] to [4], wherein the component (2) contains a polythiol compound having 2 to 6 mercapto groups in one molecule. [6] The curable composition according to any one of the above [1] to [5], wherein the component (2) contains pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) , Tris (3-mercaptopropyl) isocyanurate, trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tris [(3-mercaptopropionate) (Oxy) ethyl] isocyanurate, ethylene glycol bis (mercaptoacetate), trimethylolpropane tri (mercaptoacetate), pentaerythritol tetra (mercaptoacetate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), 1,3,4,6-tetrakis (2-mercapto At least one selected from the group consisting of ethyl) glycoluril and 4,4'-isopropylidenediphenylbis (3-mercaptopropyl) ether. [7] The curable composition according to any one of the above [1] to [5], wherein the component (2) contains pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) At least one selected from the group consisting of tris (3-mercaptopropyl) isocyanurate, and dipentaerythritol hexa (3-mercaptopropionate). [8] The curable composition according to any one of the above [1] to [7], wherein the total of acrylfluorenyl group, methacrylfluorenyl group, and epoxy group in component (1) and in component (2) The molar ratio of the mercapto group (the total of the propylene fluorenyl group, the methacryl fluorenyl group in the component (1), and the epoxy group / the thiol group in the component (2)) is 0.5 to 2.0. [9] The curable composition according to any one of the above [1] to [8], wherein the component (4) contains a compound composed of an amine-epoxy adduct-based compound and an amine-isocyanate adduct-based compound At least one selected from the group. [10] The curable composition according to any one of the above [1] to [9], further comprising a thermal radical generator as a component (5). [11] A structure comprising a first adherend, a second adherend, and an adhesive layer thereof, wherein: the first adherend is a member made of polycarbonate, and the adhesive layer is the aforementioned [1] ] A hardened product of the hardening composition of any one of [10]. [12] The structure as in [11] above, which is a camera module. [Inventive effect]

本發明的硬化性組成物係光硬化性及熱硬化性優異、可形成具有足夠的黏著強度之硬化物(黏著層)，保存安定性優異，且在將聚碳酸酯製之構件黏著之情況下可抑制其分解。The curable composition of the present invention is excellent in photo-curability and heat-curability, can form a hardened material (adhesive layer) having sufficient adhesive strength, has excellent storage stability, and is adhered to a member made of polycarbonate. Can suppress its decomposition.

本發明之硬化性組成物，其特徵為含有， (1)具有(甲基)丙烯醯基的化合物， (2)1分子中具有2個以上之巰基(-SH)的多硫醇化合物(以下有時簡稱為「多硫醇化合物」)， (3)光自由基產生劑，以及 (4)潛伏性硬化劑。 　　以下，依序說明各成分。The curable composition of the present invention is characterized by comprising: (1) a compound having a (meth) acrylfluorenyl group; and (2) a polythiol compound having two or more mercapto groups (-SH) in one molecule (hereinafter (Sometimes referred to simply as "polythiol compounds"), (3) photo radical generators, and (4) latent hardeners. Hereinafter, each component is explained in order.

＜(1)具有(甲基)丙烯醯基的化合物＞ 　　本發明中，成分(1)之「具有(甲基)丙烯醯基的化合物」，主要為負責增強黏著強度的成分的角色。本發明中的「(甲基)丙烯醯基」意指「丙烯醯基及/或甲基丙烯醯基」。成分(1)可單獨為1種，亦可為2種以上。<(1) A compound having a (meth) acrylfluorenyl group> 中 In the present invention, the "compound having a (meth) acrylfluorenyl group" as the component (1) mainly functions as a component responsible for enhancing the adhesive strength. The "(meth) acrylfluorenyl" in the present invention means "acrylfluorenyl and / or methacrylfluorenyl". The component (1) may be one kind alone, or two or more kinds.

具有(甲基)丙烯醯基的化合物之1分子中的(甲基)丙烯醯基之個數，只要為1以上即可。在具有(甲基)丙烯醯基的化合物為混和物的情況下，該個數代表每分子的平均值。又，1分子中存在丙烯醯基以及甲基丙烯醯基兩者的情況下，該個數意指1分子中之丙烯醯基以及甲基丙烯醯基的合計個數。具有(甲基)丙烯醯基的化合物之1分子中的(甲基)丙烯醯基之個數，以1~4為佳，1~2為較佳。The number of (meth) acrylfluorenyl groups in one molecule of the compound having a (meth) acrylfluorenyl group may be 1 or more. In the case where the compound having a (meth) acrylfluorenyl group is a mixture, the number represents an average value per molecule. When both acrylfluorenyl group and methacrylfluorenyl group are present in one molecule, the number means the total number of acrylfluorenyl group and methacrylfluorenyl group in one molecule. The number of (meth) acrylfluorenyl groups in one molecule of the compound having a (meth) acrylfluorenyl group is preferably 1 to 4, and 1 to 2 is more preferable.

具有(甲基)丙烯醯基的化合物之分子量，以50~5,000為佳，70~4,000為較佳，100~2,000為更佳。當分子量小於50時，揮發性高，從臭氣和處理性的觀點來看並不佳，當分子量大於5,000時，組成物之黏度提高，組成物之塗布性有降低的趨向。此外，1000以上之分子量意指重量平均分子量，可透過凝膠滲透層析(GPC)進行測量。小於1,000之分子量可透過重量分析儀(例如ESI-MS)進行測量。The molecular weight of the compound having a (meth) acryl group is preferably 50 to 5,000, more preferably 70 to 4,000, and even more preferably 100 to 2,000. When the molecular weight is less than 50, the volatility is high, and it is not good from the viewpoint of odor and handleability. When the molecular weight is more than 5,000, the viscosity of the composition increases, and the coatability of the composition tends to decrease. In addition, a molecular weight of 1,000 or more means a weight average molecular weight and can be measured by gel permeation chromatography (GPC). Molecular weights less than 1,000 can be measured by a gravimetric analyzer (such as ESI-MS).

作為具有(甲基)丙烯醯基的化合物，例如可列舉以下之化合物。此外，以下之化合物，不論何者，皆可單獨使用1種，亦可同時使用2種以上。Examples of the compound having a (meth) acrylfluorenyl group include the following compounds. In addition, any of the following compounds may be used singly or in combination of two or more kinds.

(1分子中具有1個之丙烯醯基或甲基丙烯醯基的化合物) 　　β-羧乙基(甲基)丙烯酸酯 　　(甲基)丙烯酸異冰片酯 　　辛基/癸基(甲基)丙烯酸酯 　　乙氧基化苯基(甲基)丙烯酸酯 　　具有環氧基之(甲基)丙烯酸酯 　　磷酸變性(甲基)丙烯酸酯 　　EO變性酚(甲基)丙烯酸酯 　　EO變性鄰苯基苯酚(甲基)丙烯酸酯 　　EO變性對甲醯苯酚(甲基)丙烯酸酯 　　EO變性壬基酚(甲基)丙烯酸酯 　　PO變性壬基酚(甲基)丙烯酸酯 　　N-(甲基)丙烯醯氧基乙基六氫鄰苯二甲醯亞胺 　　ω-羧基-聚己內酯單(甲基)丙烯酸酯 　　鄰苯二甲酸(甲基)丙烯酸單羥乙酯 　　2-羥基-3-苯氧基丙基(甲基)丙烯酸酯(A compound having one acryl group or methacryl group in one molecule) β-carboxyethyl (meth) acrylate (isobornyl methacrylate) octyl / decyl (meth) acrylate Ethoxylated phenyl (meth) acrylates (meth) acrylates with epoxy groups phosphate modified (meth) acrylate EO modified phenol (meth) acrylate EO modified o-phenylphenol (meth) Acrylate EO denatured p-methylphenol (meth) acrylate EO denatured nonylphenol (meth) acrylate PO denatured nonylphenol (meth) acrylate N- (meth) acrylic acid oxyethyl hexahydro Phthalimide ω-carboxy-polycaprolactone mono (meth) acrylate monohydroxyethyl phthalate (meth) acrylate 2-hydroxy-3-phenoxypropyl (methyl) Acrylate

此外，在本發明中「(甲基)丙烯酸酯」意指「丙烯酸酯和/或甲基丙烯酸酯」。又，「EO變性」意指透過添加環氧乙烷(EO)而變性。又，「PO變性」意指通過添加環氧丙烷(PO)而變性。又，「磷酸變性」意指透過與磷酸之酯鍵結而變性。Further, in the present invention, "(meth) acrylate" means "acrylate and / or methacrylate". In addition, "EO denaturation" means denaturation by adding ethylene oxide (EO). In addition, "PO denaturation" means denaturation by adding propylene oxide (PO). In addition, "phosphoric denaturation" means denaturation by an ester bond with phosphoric acid.

(1分子中具有2個之(甲基)丙烯醯基的化合物) 　　二丙二醇二(甲基)丙烯酸酯 　　1,6-己二醇二(甲基)丙烯酸酯 　　三丙二醇二(甲基)丙烯酸酯 　　PO變性新戊二醇二(甲基)丙烯酸酯 　　三環癸烷二甲醇二(甲基)丙烯酸酯 　　EO變性雙酚F二(甲基)丙烯酸酯 　　EO變性雙酚A二(甲基)丙烯酸酯 　　EO變性異氰脲酸二(甲基)丙烯酸酯 　　聚丙二醇二(甲基)丙烯酸酯 　　聚乙二醇二(甲基)丙烯酸酯 　　新戊二醇羥基新戊酸酯二(甲基)丙烯酸酯 　　1分子中具有2個之(甲基)丙烯醯基的聚氨酯 　　1分子中具有2個之(甲基)丙烯醯基的聚酯(A compound having two (meth) acrylfluorenyl groups in one molecule) Dipropylene glycol di (meth) acrylate 1,6-hexanediol di (meth) acrylate tripropylene glycol di (meth) acrylate PO denatured neopentyl glycol di (meth) acrylate tricyclodecane dimethanol di (meth) acrylate EO denatured bisphenol F di (meth) acrylate EO denatured bisphenol A di (meth) acrylate EO denatured isocyanurate di (meth) acrylate polypropylene glycol di (meth) acrylate polyethylene glycol di (meth) acrylate neopentyl glycol hydroxypivalate di (meth) acrylate 1 Polyurethane having two (meth) acrylfluorene groups in the molecule 1 Polyester having two (meth) acrylfluorene groups in the molecule

(1分子中具有3個以上之(甲基)丙烯醯基的化合物) 　　三羥甲基丙烷三(甲基)丙烯酸酯 　　PO變性三羥甲基丙烷三(甲基)丙烯酸酯 　　EO變性三羥甲基丙烷三(甲基)丙烯酸酯 　　EO變性異氰脲酸(三)(甲基)丙烯酸酯 　　季戊四醇(三/四)(甲基)丙烯酸酯 　　甘油丙氧基三(甲基)丙烯酸酯 　　季戊四醇乙氧基四(甲基)丙烯酸酯 　　雙三羥甲基丙烷四(甲基)丙烯酸酯 　　二季戊四醇(五/六)(甲基)丙烯酸酯 　　二季戊四醇六(甲基)丙烯酸酯 　　EO變性雙甘油四(甲基)丙烯酸酯 　　1分子中具有3個之(甲基)丙烯醯基的聚氨酯 　　1分子中具有3個之(甲基)丙烯醯基的聚酯(A compound having 3 or more (meth) acrylfluorenyl groups in one molecule) Trimethylolpropane tri (meth) acrylate PO modified trimethylolpropane tri (meth) acrylate EO modified trimethylol Propane tri (meth) acrylate EO denatured isocyanurate (tri) (meth) acrylate pentaerythritol (tri / tetra) (meth) acrylate glycerol propoxy tri (meth) acrylate pentaerythritol ethoxylate Tetrakis (meth) acrylate bistrimethylolpropane tetra (meth) acrylate dipentaerythritol (penta / hexa) (meth) acrylate dipentaerythritol hexa (meth) acrylate EO denatured diglycerol tetra (methyl) (Meth) acrylic ester Polyurethane having three (meth) acrylfluorene groups in one molecule Polyester having three (meth) acrylfluorene groups in one molecule

又，季戊四醇(三/四)(甲基)丙烯酸酯為季戊四醇三(甲基)丙烯酸酯及季戊四醇四(甲基)丙烯酸酯之混和物。此混和比(季戊四醇三(甲基)丙烯酸酯/季戊四醇四(甲基)丙烯酸酯)，重量比以5/95~95/5為佳，30/70~70/30為較佳。The pentaerythritol (tri / tetra) (meth) acrylate is a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. The mixing ratio (pentaerythritol tri (meth) acrylate / pentaerythritol tetra (meth) acrylate) is preferably 5/95 to 95/5 by weight, and more preferably 30/70 to 70/30.

又，二季戊四醇(五/六)(甲基)丙烯酸酯為二季戊四醇五(甲基)丙烯酸酯及二季戊四醇六(甲基)丙烯酸酯之混和物。此混和比(二季戊四醇五(甲基)丙烯酸酯/二季戊四醇六(甲基)丙烯酸酯)，重量比以5/95~95/5為佳，30/70~70/30為較佳。The dipentaerythritol (penta / hexa) (meth) acrylate is a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. This mixing ratio (dipentaerythritol penta (meth) acrylate / dipentaerythritol hexa (meth) acrylate) is preferably 5/95 to 95/5 by weight, and more preferably 30/70 to 70/30.

又，作為具有(甲基)丙烯醯基的化合物，可使用EO變性異氰脲酸(二/三)(甲基)丙烯酸酯。此處，EO變性異氰脲酸(二/三)(甲基)丙烯酸酯為EO變性異氰脲酸二(甲基)丙烯酸酯及EO變性異氰脲酸三(甲基)丙烯酸酯之混和物。此混和比(EO變性異氰脲酸二(甲基)丙烯酸酯/EO變性異氰脲酸三(甲基)丙烯酸酯)，重量比以1/99~99/1為佳，10/90~90/10為較佳，40/60~60/40為更佳。As the compound having a (meth) acrylfluorenyl group, EO-denatured isocyanuric acid (di / tri) (meth) acrylate can be used. Here, the EO-modified isocyanurate (di / tri) (meth) acrylate is a mixture of EO-modified isocyanurate di (meth) acrylate and EO-modified isocyanurate tri (meth) acrylate. Thing. The mixing ratio (EO modified isocyanurate di (meth) acrylate / EO modified isocyanurate tri (meth) acrylate), the weight ratio is preferably 1/99 ~ 99/1, 10/90 ~ 90/10 is better, and 40/60 ~ 60/40 is better.

從熱硬化性、黏著性的角度來看，成分(1)以包含具有(甲基)丙烯醯基和環氧基之化合物為佳(以下有時簡稱為「成分(1-1)」。)為佳。成分(1-1)可單獨為1種，亦可為2種以上。From the viewpoint of thermosetting property and adhesiveness, it is preferable that the component (1) contains a compound having a (meth) acrylfluorenyl group and an epoxy group (hereinafter sometimes referred to as "component (1-1)"). Better. The component (1-1) may be one kind alone, or two or more kinds.

成分(1-1)，例如可透過以下之方法(i)來製造，但本發明不限於此。 　　(i)1分子中具有2個以上之環氧基的化合物與(甲基)丙烯酸，以上述環氧化合物之環氧基的殘留量比例反應之方法。 　　此外，本發明中「(甲基)丙烯酸」意指「丙烯酸和/或甲基丙烯酸」。The component (1-1) can be produced, for example, by the following method (i), but the present invention is not limited thereto. (I) A method in which a compound having two or more epoxy groups in one molecule and (meth) acrylic acid are reacted in the proportion of the remaining amount of the epoxy group of the epoxy compound. In addition, in the present invention, "(meth) acrylic" means "acrylic and / or methacrylic".

可使用於上述方法(i)之環氧化合物並無特別限定，例如可列舉雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、聯苯型環氧樹脂、聯苯芳烷基型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、雙酚F型環氧樹脂、含磷環氧樹脂、雙酚S型環氧樹脂、芳香族縮水甘油胺型環氧樹脂、脂環族環氧樹脂、脂肪族鏈環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂等。在此等之中，以雙酚A型環氧樹脂為佳，雙酚A二縮水甘油醚為較佳。The epoxy compound that can be used in the method (i) is not particularly limited, and examples thereof include a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a biphenyl type epoxy resin, and a biphenylaralkyl type. Epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin, grease Cyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, etc. Among these, bisphenol A type epoxy resin is preferable, and bisphenol A diglycidyl ether is more preferable.

成分(1-1)亦可使用市售產品。作為該市售產品例如可列舉DAICEL-ALLNEX股份有限公司製造之「UVACURE　1561」、新中村化學工業股份有限公司製造之「EA-1010N」、日本化成股份有限公司製造之「4HBAGE」。As the component (1-1), a commercially available product can also be used. Examples of the commercially available products include "UVACURE 1561" manufactured by DAICEL-ALLNEX Corporation, "EA-1010N" manufactured by Shin Nakamura Chemical Industry Co., Ltd., and "4HBAGE" manufactured by Nippon Kasei Corporation.

成分(1-1)，以具有雙酚A型環氧樹脂骨架、並且具有(甲基)丙烯醯基和環氧基之化合物為佳。The component (1-1) is preferably a compound having a bisphenol A type epoxy resin skeleton and a (meth) acrylfluorenyl group and an epoxy group.

具有(甲基)丙烯醯基和環氧基之化合物的1分子中之(甲基)丙烯醯基的個數，以1~4為佳，1~3為較佳，1~2為更佳，1為特佳。此外，在具有(甲基)丙烯醯基和環氧基之化合物為混合物的情況下，該個數代表每分子的平均值。The number of (meth) acrylfluorenyl groups in one molecule of a compound having a (meth) acrylfluorenyl group and an epoxy group is preferably from 1 to 4, more preferably from 1 to 3, and more preferably from 1 to 2 , 1 is particularly good. In addition, when a compound having a (meth) acrylfluorenyl group and an epoxy group is a mixture, the number represents an average value per molecule.

具有(甲基)丙烯醯基和環氧基之化合物的1分子中之環氧基的個數，以1~4為佳，1~3為較佳，1~2為更佳，1為特佳。此外，在具有(甲基)丙烯醯基和環氧基之化合物為混合物的情況下，該個數代表每分子的平均值。The number of epoxy groups in a molecule of a compound having a (meth) acrylfluorenyl group and an epoxy group is preferably 1 to 4, 1 to 3 is more preferred, 1 to 2 is more preferred, and 1 is a special feature. good. In addition, when a compound having a (meth) acrylfluorenyl group and an epoxy group is a mixture, the number represents an average value per molecule.

具有(甲基)丙烯醯基和環氧基之化合物之環氧當量，以100~2,000為佳，200~1,000為較佳，300~500為更佳。此外，「環氧當量」為含有1克當量之環氧基之樹脂的克數(g/eq)，並根據JIS K 7236中規定的方法測量。The epoxy equivalent of the compound having a (meth) acrylfluorenyl group and an epoxy group is preferably 100 to 2,000, 200 to 1,000 is more preferable, and 300 to 500 is more preferable. In addition, the "epoxy equivalent" is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method specified in JIS K 7236.

具有(甲基)丙烯醯基和環氧基之化合物之分子量，以100~2,000為佳，200~1,000為較佳，300~500為更佳。The molecular weight of the compound having a (meth) acrylfluorenyl group and an epoxy group is preferably 100 to 2,000, 200 to 1,000 is more preferable, and 300 to 500 is more preferable.

使用成分(1-1)的情況下，從組成物整體的黏度、硬化性的角度來看，該使用量相對於成分(1)之總計100重量份，以為10~90重量份為佳，20~80重量份為較佳，30~70重量份為更佳。When using the component (1-1), from the viewpoint of the viscosity and hardenability of the entire composition, the usage amount is preferably 10 to 90 parts by weight based on 100 parts by weight of the total of the component (1). 20 ~ 80 parts by weight is preferable, and 30 to 70 parts by weight is more preferable.

從保存安定性的角度來看，成分(1)以含有磷酸變性(甲基)丙烯酸酯(以下有時簡稱為「成分(1-2)」。)。成分(1-2)可單獨為1種，亦可為2種以上。成分(1-2)以磷酸變性甲基丙烯酸酯為佳。From the viewpoint of storage stability, the component (1) contains a phosphoric acid-denatured (meth) acrylate (hereinafter sometimes referred to simply as "component (1-2)"). The component (1-2) may be one kind alone, or two or more kinds. The component (1-2) is preferably a phosphoric acid-modified methacrylate.

成分(1-2)例如可透過以下之方法(ii)來製造，但本發明不限於此。 　　(ii)使具有(甲基)丙烯醯基和羥基之化合物與磷酸反應之方法。The component (1-2) can be produced, for example, by the following method (ii), but the present invention is not limited thereto. (Ii) A method of reacting a compound having a (meth) acrylfluorenyl group and a hydroxyl group with phosphoric acid.

可使用於上述方法(ii)之1分子中具有(甲基)丙烯醯基和羥基之化合物，例如可透過以下的方法(iii)或(iv)來製造，但本發明不限於此。 　　(iii)將(甲基)丙烯酸或(甲基)丙烯酸酯與、多元醇(例如亞烷基二醇、甘油等)，以上述多元醇之羥基的殘留量比例反應之方法。 　　(iv)將環氧烷(例如環氧乙烷、環氧丙烷等)添加至(甲基)丙烯酸中之方法。The compound having a (meth) acrylfluorenyl group and a hydroxyl group in one molecule of the method (ii) can be produced by the following method (iii) or (iv), but the present invention is not limited thereto. (Iii) A method of reacting (meth) acrylic acid or (meth) acrylate with a polyhydric alcohol (for example, alkylene glycol, glycerin, etc.) at a ratio of the remaining amount of hydroxyl groups of the polyhydric alcohol. (Iv) A method of adding alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) to (meth) acrylic acid.

成分(1-2)亦可使用市售產品。作為該市售產品例如可列舉ALLNEX股份有限公司製造之「EBECRYL168」、日本化藥股份有限公司製造之「KAYAMER　PM-2」、「KAYAMER　PM-21」、共榮社化學股份有限公司製造之「輕酯P-1M」、「輕酯P-2M」、「輕質丙烯酸酯P-1A(N)」、城北化學工業股份有限公司製造之「JPA-514」。Ingredient (1-2) can also use a commercially available product. Examples of the commercially available products include "EBECRYL168" manufactured by ALLNEX Co., Ltd., "KAYAMER PM-2" manufactured by Nippon Kayaku Co., Ltd., and "KAYAMER PM-21" manufactured by Kyoeisha Chemical Co., Ltd. "Light Ester P-1M", "Light Ester P-2M", "Light Acrylate P-1A (N)", and "JPA-514" manufactured by Chengbei Chemical Industry Co., Ltd.

磷酸變性(甲基)丙烯酸酯之1分子中的(甲基)丙烯醯基的個數，以0.5~3為佳，1~2為較佳，1~1.5為更佳。此外，磷酸變性(甲基)丙烯酸酯為混和物的情況下，該個數代表每分子的平均值。The number of (meth) acrylfluorenyl groups in one molecule of the phosphoric acid-denatured (meth) acrylate is preferably 0.5 to 3, more preferably 1 to 2, and even more preferably 1 to 1.5. When the phosphoric acid-denatured (meth) acrylate is a mixture, this number represents an average value per molecule.

磷酸變性(甲基)丙烯酸酯之分子量，以100~1,000為佳，150~800為較佳，200~600為更佳。The molecular weight of the phosphoric acid modified (meth) acrylate is preferably from 100 to 1,000, more preferably from 150 to 800, and even more preferably from 200 to 600.

使用成分(1-2)的情況下，從保存安定性、硬化性的角度來看，該使用量相對於成分(1)之總計100重量份，以為0.001~5重量份為佳，0.01~3重量份為較佳，0.05~2重量份為更佳。When using ingredient (1-2), from the standpoint of storage stability and hardenability, the usage amount is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the total of ingredient (1), 0.01 to 3 Part by weight is preferable, and 0.05 to 2 parts by weight is more preferable.

成分(1)以包含成分(1-1)、成分(1-2)、以及具有不符合成分(1-1)及成分(1-2)任一者之(甲基)丙烯醯基的化合物(以下有時簡稱為「成分(1-3)」。)為佳。在此態樣中，成分(1-1)~(1-3)不論何者可單獨為1種，亦可為2種以上。The component (1) is a compound containing a component (1-1), a component (1-2), and a (meth) acrylfluorenyl group which does not conform to any of the component (1-1) and the component (1-2) (Hereinafter sometimes referred to as "ingredient (1-3).") In this aspect, the components (1-1) to (1-3) may be one kind alone, or two or more kinds.

成分(1)為包含成分(1-1)~(1-3)的情況下，相當於成分(1)之總計100重量份，成分(1-1)的量係從組成物整體的黏度、硬化性的角度來看，以為10~90重量份為佳，20~80重量份為較佳，30~70重量份為更佳，且成分(1-2)的量，從保存安定性、硬化性的角度來看，以0.001~5重量份為佳，0.01~3重量份為較佳，0.05~2重量份為更佳，且成分(1-3)的量為殘餘重量份。When component (1) includes components (1-1) to (1-3), it corresponds to 100 parts by weight of component (1) in total, and the amount of component (1-1) is based on the viscosity of the entire composition, From the viewpoint of hardenability, it is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, and the amount of the component (1-2), from storage stability and hardening From the standpoint of performance, 0.001 to 5 parts by weight is preferred, 0.01 to 3 parts by weight is more preferred, 0.05 to 2 parts by weight is more preferred, and the amount of component (1-3) is the residual parts by weight.

＜(2)1分子中具有2個以上之巰基的多硫醇化合物＞ 　　本發明之硬化性組成物中，成分(2)之「1分子中具有2個以上之巰基的多硫醇化合物」，主要作為負責透過紫外線等之光照射而使成分(1)硬化之硬化劑的角色。成分(2)可單獨為1種，亦可為2種以上。多硫醇化合物之1分子中之巰基的個數，以2~6為佳，3~6為較佳，3~5為更佳，3或4為特佳。<(2) Polythiol compound having two or more thiol groups in one molecule> 物 中 In the curable composition of the present invention, the "polythiol compound having two or more thiol groups in one molecule" of component (2), It is mainly used as a hardener that hardens the component (1) by irradiating light such as ultraviolet rays. The component (2) may be one kind alone, or two or more kinds. The number of thiol groups in one molecule of the polythiol compound is preferably 2 to 6, 3 to 6 is more preferred, 3 to 5 is more preferred, and 3 or 4 is particularly preferred.

多硫醇化合物可使用市售產品，亦可使用已知的方法(例如，日本特開2012-153794或國際公開2001/00698號所記載之方法)所製造之化合物。As the polythiol compound, a commercially available product may be used, or a compound produced by a known method (for example, a method described in Japanese Patent Application Laid-Open No. 2012-153794 or International Publication No. 2001/00698) may be used.

多硫醇化合物，例如可列舉出多元醇和巰基有機酸的部分酯、完全酯。此處，部分酯為多元醇和羧酸的酯，意指多元醇之羥基的一部分形成酯鍵結之物，完全酯意指多元醇之羥基的全部形成酯鍵結之物。Examples of the polythiol compound include a partial ester and a complete ester of a polyhydric alcohol and a mercapto organic acid. Here, the partial ester is an ester of a polyol and a carboxylic acid, and means that a part of the hydroxyl groups of the polyol forms an ester bond, and a complete ester means that all of the hydroxyl groups of the polyol form an ester bond.

作為多元醇例如可列舉乙二醇，三羥甲基乙烷，三羥甲基丙烷，季戊四醇和二季戊四醇等。Examples of the polyhydric alcohol include ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

作為巰基有機酸，例如，可列舉出巰基乙酸、巰基丙酸(例如：3-巰基丙酸)、巰基丁酸(例如：3-巰基丁酸、4-巰基丁酸)等之巰基脂肪族單羧酸；透過羥基酸和巰基有機酸之間的酯化反應而得之具有巰基和羧基的酯；巰基琥珀酸、二巰基琥珀酸(例如：2,3-二巰基琥珀酸)等之巰基脂肪族二羧酸；巰基苯甲酸(例如，4-巰基苯甲酸)等之巰基芳香族單羧酸。上述巰基脂肪族單羧酸的碳原子數以2~8為佳，2~6為較佳，2~4為更佳，3為特佳。在上述巰基有機酸中，以碳原子數為2~8之巰基脂肪族單羧酸為佳，巰基乙酸、3-巰基丙酸、3-巰基丁酸和4-巰基丁酸為較佳，3-巰基丙酸為更佳。Examples of the mercapto organic acid include mercaptoacetic acid, mercaptopropionic acid (for example: 3-mercaptopropionic acid), mercaptobutyric acid (for example: 3-mercaptobutyric acid, 4-mercaptobutyric acid) and the like. Carboxylic acid; Esters with thiol and carboxyl groups obtained by esterification reaction between hydroxy acid and mercapto organic acid; Mercapto fatty acids such as mercaptosuccinic acid and dimercaptosuccinic acid (for example: 2,3-dimercaptosuccinic acid) Group dicarboxylic acids; mercapto aromatic monocarboxylic acids such as mercaptobenzoic acid (eg, 4-mercaptobenzoic acid). The carbon number of the mercapto aliphatic monocarboxylic acid is preferably 2 to 8, 2 to 6 is more preferred, 2 to 4 is more preferred, and 3 is particularly preferred. Among the above mercapto organic acids, a mercapto aliphatic monocarboxylic acid having 2 to 8 carbon atoms is preferred, and mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, and 4-mercaptobutyric acid are more preferred. 3 -Mercaptopropionic acid is more preferred.

作為多元醇和巰基有機酸的部分酯之具體例，可列舉三羥甲基乙烷雙(巰基乙酸酯)、三羥甲基乙烷雙(3-巰基丙酸酯)、三羥甲基乙烷雙(3-巰基丁酸酯)、三羥甲基乙烷雙(4-巰基丁酸酯)、三羥甲基丙烷雙(巰基乙酸酯)、三羥甲基丙烷雙(3-巰基丙酸酯)、三羥甲基丙烷雙(3-巰基丁酸酯)、三羥甲基丙烷雙(4-巰基丁酸酯)、季戊四醇三(巰基乙酸酯)、季戊四醇三(3-巰基丙酸酯)、季戊四醇三(3-巰基丁酸酯)、季戊四醇三(4-巰基丁酸酯)、二季戊四醇四(巰基乙酸酯)、二季戊四醇四(3-巰基丙酸酯)、二季戊四醇四(3-巰基丁酸酯)、二季戊四醇四(4-巰基丁酸酯)等。Specific examples of the partial esters of a polyhydric alcohol and a mercapto organic acid include trimethylolethane bis (mercaptoacetate), trimethylolethane bis (3-mercaptopropionate), and trimethylolethyl Alkanebis (3-mercaptobutyrate), trimethylolethane bis (4-mercaptobutyrate), trimethylolpropane bis (mercaptoacetate), trimethylolpropane bis (3-mercapto Propionate), trimethylolpropane bis (3-mercaptobutyrate), trimethylolpropane bis (4-mercaptobutyrate), pentaerythritol tri (mercaptoacetate), pentaerythritol tri (3-mercapto Propionate), pentaerythritol tri (3-mercaptobutyrate), pentaerythritol tri (4-mercaptobutyrate), dipentaerythritol tetra (mercaptoacetate), dipentaerythritol tetra (3-mercaptopropionate), two Pentaerythritol tetra (3-mercaptobutyrate), dipentaerythritol tetra (4-mercaptobutyrate), and the like.

作為多元醇和巰基有機酸的完全酯之具體例，可列舉乙二醇雙(巰基乙酸酯)、乙二醇雙(3-巰基丙酸酯)、乙二醇雙(3-巰基丁酸酯)、乙二醇雙(4-巰基丁酸酯)、三羥甲基乙烷三(巰基乙酸酯)、三羥甲基乙烷三(3-巰基丙酸酯)、三羥甲基乙烷三(3-巰基丁酸酯)、三羥甲基乙烷三(4-巰基丁酸酯)、三羥甲基丙烷三(巰基乙酸酯)、三羥甲基丙烷三(3-巰基丙酸酯)、三羥甲基丙烷三(3-巰基丁酸酯)、三羥甲基丙烷三(4-巰基丁酸酯)、季戊四醇四(巰基乙酸酯)、季戊四醇四(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、季戊四醇四(4-巰基丁酸酯)、二季戊四醇六巰基(巰基乙酸酯)、二季戊四醇六(3-巰基丙酸酯)、二季戊四醇六(3-巰基丁酸酯)、二季戊四醇六(4-巰基丁酸酯)等。Specific examples of the complete ester of a polyhydric alcohol and a mercapto organic acid include ethylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), and ethylene glycol bis (3-mercaptobutyrate). ), Ethylene glycol bis (4-mercaptobutyrate), trimethylolethane tri (mercaptoacetate), trimethylolethane tri (3-mercaptopropionate), trimethylolethane Alkyltris (3-mercaptobutyrate), trimethylolethane tris (4-mercaptobutyrate), trimethylolpropane tri (mercaptoacetate), trimethylolpropane tri (3-mercapto) Propionate), trimethylolpropane tri (3-mercaptobutyrate), trimethylolpropane tri (4-mercaptobutyrate), pentaerythritol tetra (mercaptoacetate), pentaerythritol tetra (3-mercapto) Propionate), pentaerythritol tetra (3-mercaptobutyrate), pentaerythritol tetra (4-mercaptobutyrate), dipentaerythritol hexamercapto (thioglycolate), dipentaerythritol hexa (3-mercaptopropionate), Dipentaerythritol hexa (3-mercaptobutyrate), dipentaerythritol hexa (4-mercaptobutyrate) and the like.

從保存安定性的角度來看，上述部分酯以及完全酯以鹼性雜質含量極低之物為佳，製造上不需要使用鹼性物質之物為較佳。From the standpoint of storage stability, the above-mentioned partial esters and complete esters are preferably those having a very low content of basic impurities, and those that do not require the use of a basic substance are more preferred in manufacturing.

又，作為成分(2)如1,4-丁二硫醇、1,6-己二硫醇、1,10-癸二硫醇等之烷烴多硫醇化合物；末端含巰基的聚醚；末端含巰基的聚硫醚；透過環氧化合物與硫化氫反應而得之多硫醇化合物；透過多硫醇化合物和環氧化合物反應而得之末端具有巰基的多硫醇化合物；等亦可使用在其製造過程上使用鹼性物質作為反應催化劑所製造之多硫醇化合物。使用鹼性物質所製造之多硫醇化合物以進行脫鹼處理，將鹼金屬離子濃度調節至50重量ppm以下來使用為佳。Also, as the component (2), an alkane polythiol compound such as 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc .; a mercapto group-containing polyether at the terminal end; Polythioethers containing thiol groups; polythiol compounds obtained by reacting epoxy compounds with hydrogen sulfide; polythiol compounds having thiol groups at the ends obtained by reacting polythiol compounds and epoxy compounds; etc. can also be used in In the manufacturing process, a polythiol compound produced by using a basic substance as a reaction catalyst is used. It is preferable to use a polythiol compound produced by a basic substance to perform alkali removal treatment, and adjust the alkali metal ion concentration to 50 ppm by weight or less.

作為使用鹼性物質所製造之多硫醇化合物之脫鹼處理，例如可列舉出將多硫醇化合物溶解在丙酮、甲醇等之有機溶劑中，透過加入稀鹽酸、稀硫酸等之酸進行中和後，藉由萃取‧洗滌等進行脫鹽之方法；使用離子交換樹脂吸附的方法；透過蒸餾純化的方法；等，但不限於此。Examples of the debasing treatment of a polythiol compound produced using a basic substance include dissolving the polythiol compound in an organic solvent such as acetone, methanol, and the like, and neutralizing by adding an acid such as dilute hydrochloric acid or dilute sulfuric acid. Later, a method of desalting by extraction, washing, etc .; a method using ion exchange resin adsorption; a method of purifying by distillation; etc., but not limited thereto.

又，作為成分(2)例如可使用三[(3-巰基丙醯氧基)乙基]異氰脲酸酯、1,3,5-三(3-巰基丁醯氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、三(3-巰基丙基)異氰脲酸酯、雙(3-巰基丙基)異氰脲酸酯、1,3,4,6-四(2-巰基乙基)甘脲、以及4,4’-異亞丙基二苯基雙(3-巰基丙基)醚等。As the component (2), for example, tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, and 1,3,5-tris (3-mercaptobutyryloxyethyl) -1 can be used. , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, tris (3-mercaptopropyl) isocyanurate, bis (3-mercaptopropyl) isocyanurate Esters, 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, and 4,4'-isopropylidenediphenylbis (3-mercaptopropyl) ether.

成分(2)以包含1分子中具有2~6個之巰基的多硫醇化合物為佳，3~6個為較佳，3~5為更佳，3或4個為特佳。The component (2) is preferably a polythiol compound containing 2 to 6 mercapto groups in one molecule, 3 to 6 is more preferred, 3 to 5 is more preferred, and 3 or 4 is particularly preferred.

本發明之較佳態樣中，成分(2)為包含自季戊四醇四(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、三(3-巰基丙基)異氰脲酸酯、三羥甲基丙烷三(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)、三[(3-巰基丙醯氧基)乙基]異氰脲酸酯、乙二醇雙(巰基乙酸酯)、三羥甲基丙烷三(巰基乙酸酯)、季戊四醇四(巰基乙酸酯)、1,4-雙(3-巰基丁醯氧基)丁烷、1,3,5-三(3-巰基丁醯氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷三(3-巰基丁酸酯)、三羥甲基乙烷三(3-巰基丁酸酯)、1,3,4,6-四(2-巰基乙基)甘脲、以及4,4’-異亞丙基二苯基雙(3-巰基丙基)醚組成之群組中選擇至少1種。在此態樣中，成分(2)以自上述群組中選擇至少1種為較佳。In a preferred aspect of the present invention, the component (2) comprises pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate. Ester, trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, ethyl Diol bis (mercaptoacetate), trimethylolpropane tri (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), 1,4-bis (3-mercaptobutoxy) butane, 1 , 3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tri ( 3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, and 4,4'-iso At least one selected from the group consisting of propylene diphenyl bis (3-mercaptopropyl) ether. In this aspect, it is preferable that the component (2) be selected from at least one kind from the above group.

本發明之更佳態樣中，成分(2)為包含自季戊四醇四(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、三(3-巰基丙基)異氰脲酸酯、以及二季戊四醇六(3-巰基丙酸酯)組成之群組中選擇至少1種。在此態樣中，成分(2)以自上述群組中選擇至少1種為特佳。In a more preferred aspect of the present invention, the component (2) comprises pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate. At least one is selected from the group consisting of an ester and dipentaerythritol hexa (3-mercaptopropionate). In this aspect, the component (2) is particularly preferably selected from at least one of the above-mentioned groups.

從硬化性的角度來看，成分(1)中之丙烯醯基、甲基丙烯醯基和環氧基的總計與成分(2)中之巰基的莫耳比(成分(1)中之丙烯醯基、甲基丙烯醯基和環氧基的總計/成分(2)中之巰基)以0.5~2.0為佳，0.6~1.6為較佳，0.7~1.5為更佳，0.8~1.3為特佳。此外，在成分(1)不含有環氧基的情況下(即是，成分(1)不含有成分(1-1)的情況下)，「成分(1)中之丙烯醯基、甲基丙烯醯基和環氧基的總計」為「成分(1)中之丙烯醯基和甲基丙烯醯基的總計」。又，例如成分(1)具有丙烯醯基、不含有甲基丙烯醯基之情況下，「成分(1)中之丙烯醯基、甲基丙烯醯基和環氧基的總計」為「成分(1)中之丙烯醯基和環氧基的總計」。From the viewpoint of hardenability, the molar ratio of the total of acryl, methacryl, and epoxy groups in the component (1) to the thiol group in the component (2) (the acryl in the component (1)) The total of the base group, the methacryl group, and the epoxy group (mercapto group in the component (2)) is preferably 0.5 to 2.0, more preferably 0.6 to 1.6, more preferably 0.7 to 1.5, and particularly preferably 0.8 to 1.3. In addition, when the component (1) does not contain an epoxy group (that is, when the component (1) does not contain the component (1-1)), "propenyl fluorenyl and methacrylic acid in the component (1) "Total of fluorenyl and epoxy groups" is "total of propylene fluorenyl and methacryl fluorenyl groups in component (1)". In addition, for example, when the component (1) has an acrylfluorenyl group and does not contain a methacrylfluorenyl group, "the total of the acrylfluorenyl group, the methacrylfluorenyl group, and the epoxy group in the component (1)" is "component ( 1) Total of allyl acryl and epoxy groups. "

從硬化性、黏著性的角度來看，成分(1)之量，相對於硬化性組成物整體，以為20重量%以上為佳，30重量%以上為較佳，40重量%以上為更佳。同樣地，從硬化性、黏著性的角度來看，成分(1)之量，相對於硬化性組成物整體，以為85重量%以下為佳，80重量%以下為較佳，75重量%以下為更佳。From the viewpoint of hardenability and adhesiveness, the amount of the component (1) is preferably 20% by weight or more, more preferably 30% by weight or more, and more preferably 40% by weight or more with respect to the entire hardenable composition. Similarly, from the viewpoint of hardenability and adhesiveness, the amount of component (1) is preferably 85% by weight or less, more preferably 80% by weight or less, and 75% by weight or less with respect to the entire hardenable composition. Better.

從硬化性、黏著性的角度來看，成分(2)之量，相對於硬化性組成物整體，以為10重量%以上為佳，15重量%以上為較佳，20重量%以上為更佳。同樣地，從硬化性、黏著性的角度來看，成分(2)之量，相對於硬化性組成物整體，以為70重量%以下為佳，65重量%以下為較佳，55重量%以下為更佳。From the viewpoint of hardenability and adhesiveness, the amount of the component (2) is preferably 10% by weight or more, more preferably 15% by weight or more, and even more preferably 20% by weight or more with respect to the entire hardenable composition. Similarly, from the viewpoint of hardenability and adhesiveness, the amount of the component (2) is preferably 70% by weight or less, more preferably 65% by weight or less, and 55% by weight or less with respect to the entire hardenable composition. Better.

從硬化性、黏著性的角度來看，成分(1)以及(2)之合計量，相對於硬化性組成物整體，以為30重量%以上為佳，50重量%以上為較佳，70重量%以上為更佳。同樣地從硬化性、黏著性的角度來看，成分(1)以及(2)之合計量，相對於硬化性組成物整體，以為99重量%以下為佳，97重量%以下為較佳，95重量%以下為更佳。From the viewpoint of hardenability and adhesion, the total amount of components (1) and (2) is preferably 30% by weight or more, more preferably 50% by weight or more, and 70% by weight with respect to the entire hardenable composition. The above is even better. Similarly, from the viewpoint of hardenability and adhesiveness, the total amount of components (1) and (2) is preferably 99% by weight or less, more preferably 97% by weight or less, with respect to the entire hardenable composition. It is more preferable that the content is not more than% by weight.

＜(3)光自由基產生劑＞ 　　本發明中的光自由基產生劑並無特別限定，例如可列舉烷基苯酮類光自由基產生劑、醯基氧化膦系光自由基產生劑、肟酯類光自由基產生劑、α-酮系光自由基產生劑等。成分(3)可單獨為1種，亦可為2種以上。光自由基產生劑，以烷基苯酮系光自由基產生劑為佳。<(3) Photo radical generator> The photo radical generator in the present invention is not particularly limited, and examples thereof include alkyl phenone-based photo radical generator, fluorenyl phosphine oxide-based photo radical generator, and oxime Esters photoradical generators, α-keto photoradical generators, and the like. The component (3) may be one kind alone, or two or more kinds. The photo radical generator is preferably an alkyl phenone-based photo radical generator.

作為烷基苯酮系光自由基產生劑，例如可列舉2-羥基-2-甲基-1-苯基丙烷-1-酮、2-苄基-2-二甲基氨基-1-(4-嗎啉代苯基)-1-丁酮、2-(二甲基氨基)-2-[(4-甲基苯基)甲基]-[4-(4-嗎啉基)苯基]-1-丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙-1-酮、二苯甲酮、甲基二苯甲酮、鄰苯甲醯苯甲酸、苯甲醯乙醚、2,2-二乙氧基、2,4-二乙基噻噸酮、二苯基-(2,4,6-三甲基苯甲醯基)氧化膦、乙基-(2,4,6-三甲基苯甲醯基)苯基次膦酸酯、4,4’-雙(二乙氨基)二苯甲酮、1-羥基環己基苯基酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-1-(4-異丙烯基苯基)-2-甲基丙烷-1-酮之寡聚物等。Examples of the alkyl phenone-based photoradical generator include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]-[4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzophenone, methylbenzophenone, o-benzene Formamidinebenzoic acid, benzamidine ether, 2,2-diethoxy, 2,4-diethylthioxanthone, diphenyl- (2,4,6-trimethylbenzyl) oxidation Phosphine, ethyl- (2,4,6-trimethylbenzyl) phenyl phosphinate, 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenyl Ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl Oligomers of 1-propane-1-one, 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropane-1-one, and the like.

作為醯基氧化膦系光自由基產生劑，例如可列舉出2,4,6-三甲基苯甲醯基-二苯基-氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基-氧化膦等。Examples of the fluorenylphosphine oxide-based photoradical generator include 2,4,6-trimethylbenzylfluorenyl-diphenyl-phosphine oxide, and bis (2,4,6-trimethylbenzyl) Fluorenyl) -phenyl-phosphine oxide and the like.

作為肟酯系光自由基產生劑，例如可列舉1-[4-(苯硫基)苯基]-1,2-辛二酮2-(O-苯甲醯基肟)、1-[6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基]乙酮O-乙醯肟等。Examples of the oxime ester-based photoradical generator include 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzylideneoxime), 1- [6 -(2-methylbenzyl) -9-ethyl-9H-carbazol-3-yl] ethanone O-acetamoxime and the like.

作為α-酮系光自由基產生劑，例如可列舉出安息香、苯偶姻甲醚、苯偶姻丁醚、1-羥基環己基苯基酮、1-苯基-2-羥基-2-甲基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、4-(2-羥基乙氧基)苯基-(2-羥基-2-丙基)酮、1-羥基環己基苯基酮等。Examples of the α-keto photoradical generator include benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexylphenyl ketone, and 1-phenyl-2-hydroxy-2-methyl Propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy 2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone and the like.

作為光自由基產生劑之市售產品，例如可列舉BASF公司製造「IRGACURE　1173」(2-羥基-2-甲基-1-苯基丙烷-1-酮)、「IRGACURE OXE-01」(1-[4-(苯硫基)苯基]-1,2-辛二酮2-(O-苯甲醯基肟))、「IRGACURE OXE-02」(1-[6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基)乙酮O-乙醯肟)、DKSH公司製造「Esacure KTO 46」(2,4,6-三甲基苯甲醯基二苯基氧化膦和寡聚[2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙烷]與甲基二苯甲酮衍生物之混和物)、Lamberti SPA公司製造「ESACURE KIP 150」(2-羥基-1-(4-異丙烯基苯基)-2-甲基丙烷-1-酮之寡聚物)等。As commercially available products of the photo radical generator, for example, "IRGACURE 1173" (2-hydroxy-2-methyl-1-phenylpropane-1-one), "IRGACURE OXE-01" (1 -[4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzylideneoxime)), "IRGACURE OXE-02" (1- [6- (2-methyl Benzamidine) -9-ethyl-9H-carbazol-3-yl) ethanone O-acetamoxime), "Esacure KTO 46" (2,4,6-trimethylbenzidine) manufactured by DKSH Of diphenylphosphine oxide and oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane] and methylbenzophenone derivatives) "ESACURE KIP 150" (oligomer of 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropane-1-one) manufactured by Lamberti SPA, etc.

成分(3)的量，從獲得光照射時能夠有效率地光硬化之硬化性組成物的角度來看，相對於硬化性組成物整體，以為0.001重量%以上為佳，0.01重量%以上為較佳，0.1重量%以上為更佳。另外，硬化物中殘存的光自由基產生劑或透過其分解物抑制排氣的角度來看，相對於硬化性組成物全體，以為10重量%以下為佳，5重量%以下為較佳，2重量%以下為更佳。The amount of the component (3) is preferably 0.001% by weight or more, and 0.01% by weight or more, relative to the entire curable composition, from the viewpoint of obtaining a curable composition capable of efficiently photocuring when light is irradiated. Preferably, it is more preferably 0.1% by weight or more. In addition, from the viewpoint of suppressing the exhaust gas by the photo radical generator remaining in the hardened material or the decomposed product, it is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the entire hardenable composition. 2 It is more preferable that the content is not more than% by weight.

＜(4)潛伏性硬化劑＞ 　　成分(4)之潛伏性硬化劑為在環氧樹脂等領域中眾所周知的添加劑，意指在常溫(25℃)下使環氧樹脂不要硬化，透過加熱而使環氧樹脂等硬化之硬化劑。成分(4)可單獨為1種，亦可為2種以上。<(4) Latent hardener> The latent hardener of the component (4) is a well-known additive in the field of epoxy resin and the like, which means that the epoxy resin is not hardened at normal temperature (25 ° C) and is heated to make it Hardening agent such as epoxy resin. The component (4) may be one kind alone, or two or more kinds.

作為潛伏性硬化劑，例如可列舉出在室溫下為固體之咪唑化合物、胺-環氧加合物系化合物(胺化合物與環氧化合物的反應產物)、胺-異氰酸酯加合物系化合物(胺化合物與異氰酸酯化合物的反應產物)等。Examples of the latent curing agent include imidazole compounds, amine-epoxy adduct-based compounds (reaction products of amine compounds and epoxy compounds), and amine-isocyanate adduct-based compounds (solid Reaction product of an amine compound and an isocyanate compound) and the like.

作為常溫下為固體之咪唑化合物，例如可列舉出2-十七烷基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-十一烷基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2-苯基-4-苄基-5-羥甲基咪唑、2,4-二氨-6-[2-(2-甲基-1-咪唑基)乙基]-1,3,5-三嗪、2,4-二氨基-6-[2-(2-甲基-1-咪唑基)乙基]-1,3,5-三嗪·異氰脲酸加合物、2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑-偏苯三酸酯、1-氰基乙基-2-苯基咪唑-偏苯三酸酯、N-(2-甲基咪唑基-1-乙基)-脲等。Examples of the imidazole compound that is solid at normal temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, and 2-phenyl-4 -Methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6- [2- (2-methyl-1-imidazolyl ) Ethyl] -1,3,5-triazine, 2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine · Isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl 2-methylimidazole-trimellitic acid ester, 1-cyanoethyl-2-phenylimidazole-trimellitic acid ester, N- (2-methylimidazol-1-ethyl) -urea, etc. .

作為用作胺-環氧加合物系化合物之原料所使用的環氧化合物，例如可列舉雙酚A、雙酚F、兒茶酚、間苯二酚等之多元酚、或甘油或聚乙二醇等之多元醇和表氯醇反應而得之聚縮水甘油醚；對羥基苯甲酸、β-羥基萘甲酸等之羥基酸和表氯醇反應而得之縮水甘油醚酯；鄰苯二甲酸、對苯二甲酸等之多元羧酸和表氯醇反應而得之聚縮水甘油酯；4,4’-二氨基二苯甲烷或間氨基苯酚等和表氯醇反應而得之縮水甘油胺化合物；此外環氧化苯酚酚醛清漆樹脂、環氧化甲酚酚醛樹脂、環氧化聚烯烴等之多官能環氧化合物或丁基縮水甘油醚、苯基縮水甘油醚、甲基丙烯酸縮水甘油酯等之單官能環氧化合物；等。Examples of the epoxy compound used as a raw material of the amine-epoxy adduct-based compound include polyphenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or glycerol or polyethylene. Polyglycidyl ethers obtained by reacting polyhydric alcohols such as diols with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxy acids such as p-hydroxybenzoic acid, β-hydroxynaphthoic acid and epichlorohydrin; phthalic acid, Polyglycidyl esters obtained by reacting polycarboxylic acids such as terephthalic acid and epichlorohydrin; glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; In addition, epoxidized phenol novolac resins, epoxidized cresol novolac resins, epoxidized polyolefins, and other polyfunctional epoxy compounds or monofunctional rings such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate. Oxygen compounds; etc.

作為用作胺-環氧加合物系化合物之原料所使用的胺化合物，只要為1分子中具有可與環氧基或異氰酸酯基(又名：異氰酸基)進行加成反應之活性氫原子1個以上，且1分子中具有胺基(1級胺基、2級胺基以及3級胺基之至少1個)1個以上者即可。作為此種胺化合物，例如可列舉二亞乙基三胺、三亞乙基四胺、丙胺、2-羥乙基氨基丙胺、環己胺、4,4’-二氨基-二環己基等之脂族胺化合物；4,4’-二氨基二苯甲烷、2-甲基苯胺等之芳香胺化合物；2-乙基-4-甲基咪唑、2-乙基-4-甲基咪唑啉、2,4-二甲基咪唑啉、哌啶、哌嗪等之含有氮原子的雜環化合物；等。As long as the amine compound used as a raw material of the amine-epoxy adduct compound has an active hydrogen capable of performing an addition reaction with an epoxy group or an isocyanate group (also known as an isocyanate group) in one molecule, It is only necessary that one or more atoms have at least one amine group (at least one of a primary amine group, a secondary amine group, and a tertiary amine group) in one molecule. Examples of such amine compounds include lipids such as diethylenetriamine, triethylenetetramine, propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexyl, and the like. Group amine compounds; aromatic amine compounds such as 4,4'-diaminodiphenylmethane, 2-methylaniline; 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2 , 4-dimethylimidazoline, piperidine, piperazine and the like containing nitrogen atom-containing heterocyclic compounds; etc.

又，如果使用具有3級胺之化合物，可製造優異之潛伏性硬化劑。作為具有3級胺之化合物，例如可列舉二甲氨基丙胺、二乙基氨基丙胺、二丙基氨基丙胺、二丁基氨基丙胺、二甲氨基乙胺、二乙氨基乙胺、N-甲基哌嗪、2-甲基咪唑、2-乙基亞氨基、2-乙基-4-甲基咪唑、2-苯基咪唑等之具有3級胺之胺類；2-二甲基氨基乙醇、1-甲基-2-二甲基氨基乙醇、1-苯氧基甲基-2-二甲基氨基乙醇、2-二乙基氨基乙醇、1-丁氧基甲基-2-二甲氨基乙醇、1-(2-羥基-3-苯氧基丙基)-2-甲基咪唑、1-(2-羥基-3-苯氧基丙基)-2-乙基-4-甲基咪唑、1-(2-羥基-3-丁氧基丙基)-2-甲基咪唑、1-(2-羥基-3-丁氧基丙基)-2-乙基-4-甲基咪唑、1-(2-羥基-3-苯氧基丙基)-2-苯基咪唑啉、1-(2-羥基-3-丁氧基丙基)-2-甲基咪唑啉、2-(二甲基氨基甲基)苯酚、2,4,6-三(二甲基氨基甲基)苯酚、N-β-羥乙基嗎啉、2-二甲基氨基乙硫醇、2-巰基吡啶、2-苯並咪唑、2-巰基苯並咪唑、2-巰基苯並噻唑、4-巰基吡啶、N,N-二甲基氨基苯甲酸、N,N-二甲基甘氨酸、菸酸、異菸酸、吡啶甲酸、N,N-二甲基甘氨酸醯肼、N,N-二甲基丙酸醯肼、菸酸醯肼、異菸酸醯肼等之具有3級胺之醇類、酚類、硫醇類、羧酸類和醯肼類；等。Further, if a compound having a tertiary amine is used, an excellent latent hardener can be produced. Examples of the compound having a tertiary amine include dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methyl Piperazines, 2-methylimidazole, 2-ethylimino, 2-ethyl-4-methylimidazole, 2-phenylimidazole and other amines with tertiary amines; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylamino Ethanol, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole , 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (di Methylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethyl mercaptan, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N, N-dimethylglycine hydrazine, N, N- Alcohols with tertiary amines such as hydrazine dimethyl propionate, hydrazine nicotinate, hydrazine isonicotinate, phenols, thiols, carboxylic acids and hydrazines; etc.

使環氧化合物和胺化合物進行加成反應，在製備胺-環氧加合物系化合物時，還可以添加在1分子中具有2個以上活性氫之活性氫化合物。作為此種活性氫化合物，例如可列舉雙酚A、雙酚F、雙酚S、對苯二酚、兒茶酚、間苯二酚、連苯三酚、苯酚酚醛清漆樹脂等之多元酚類、三羥甲基丙烷等之多元醇類、己二酸、鄰苯二甲酸等之多元羧酸類、1,2-二巰基乙烷、2-巰基乙醇、1-巰基-3-苯氧基-2-丙醇、巰基乙酸、鄰氨基苯甲酸、乳酸等。An epoxy compound and an amine compound are subjected to an addition reaction, and when an amine-epoxy adduct-based compound is prepared, an active hydrogen compound having two or more active hydrogens in one molecule may be added. Examples of such active hydrogen compounds include polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resin. , Polyhydric alcohols such as trimethylolpropane, polycarboxylic acids such as adipic acid, phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy- 2-propanol, mercaptoacetic acid, anthranilic acid, lactic acid, etc.

作為用作胺-異氰酸酯加合物系化合物的原料之異氰酸酯化合物，例如可列舉異氰酸丁酯、異氰酸異丙酯、苯基異氰酸酯、苄基異氰酸酯等之單官能異氰酸酯化合物；六亞甲基二異氰酸酯、甲苯二異氰酸酯(例：2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯)、1,5-萘二異氰酸酯、二苯基甲烷-4,4’-二異氰酸酯、異佛爾酮二異氰酸酯、亞二甲苯基二異氰酸酯、對亞苯基二異氰酸酯、1,3,6-六亞甲基三異氰酸酯、雙環庚烷三異氰酸酯等之多官能異氰酸酯化合物；此外，透過此等多官能異氰酸酯化合物與活性氫化合物之反應而得之末端含有異氰酸酯基之化合物；等。作為此種末端含有異氰酸酯基之化合物，例如可列舉透過甲苯二異氰酸酯與三羥甲基丙烷反應而得之末端具有異氰酸酯基之加成化合物、透過甲苯二異氰酸酯與季戊四醇反應而得之末端具有異氰酸酯基之加成化合物等。Examples of the isocyanate compound used as a raw material of the amine-isocyanate adduct-based compound include monofunctional isocyanate compounds such as butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; hexamethylene Diisocyanate, toluene diisocyanate (example: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophor Polyfunctional isocyanate compounds such as ketene diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, etc .; Compounds containing isocyanate groups at the ends obtained by the reaction of a functional isocyanate compound and an active hydrogen compound; etc. Examples of such a compound containing an isocyanate group at the terminal include an addition compound having an isocyanate group at the terminal obtained by reacting toluene diisocyanate with trimethylolpropane, and an isocyanate group at the terminal obtained by reacting toluene diisocyanate with pentaerythritol. Addition compounds, etc.

成分(4)之潛伏性硬化劑，例如將上述之製造原料適當混和，在自室溫至200℃之溫度下使之反應後，冷卻固化後磨碎、或在甲基乙基酮、二噁烷、四氫呋喃等之溶劑中使上述之製造原料反應，除去溶劑後，可透過磨碎固體部分後簡單獲得。As the latent hardener of component (4), for example, the above-mentioned manufacturing materials are appropriately mixed, and the reaction is performed at a temperature from room temperature to 200 ° C, and then cooled and solidified and ground, or methyl ethyl ketone and dioxane The above-mentioned production raw materials are reacted in a solvent such as THF or tetrahydrofuran. After removing the solvent, it can be easily obtained by grinding the solid portion.

成分(4)之潛伏性硬化劑，亦可使用市售產品。作為胺-環氧加合物系化合物之市售產品，例如可列舉出味之素Fine-Techno公司製造之「Amicure PN-23」、「Amicure PN-40」、「Amicure PN-50」、「Amicure PN-H」、ACR公司製造之「硬化劑X-3661S」、「硬化劑X-3670S」、旭化成公司製造之「Novacure HX-3742」、「Novacure HX-3721」。另外，作為胺-異氰酸酯加合物系化合物之市售產品，例如可列舉T&K TOKA公司製造之「Fujicure FXE-1000」、「Fujicure FXR-1030」、「Fujicure FXR-1020」、「Fujicure FXR-1030」、「Fujicure FXR-1081」、「Fujicure FXR-1121」。As the latent hardener of the component (4), a commercially available product can also be used. As commercially available products of the amine-epoxy adduct-based compound, for example, "Amicure PN-23", "Amicure PN-40", "Amicure PN-50", " "Amicure PN-H", "Hardener X-3661S", "Hardener X-3670S" manufactured by ACR, "Novacure HX-3742" and "Novacure HX-3721" manufactured by Asahi Kasei Corporation. Examples of commercially available products of the amine-isocyanate adduct-based compound include "Fujicure FXE-1000", "Fujicure FXR-1030", "Fujicure FXR-1020", and "Fujicure FXR-1030" manufactured by T & K TOKA Corporation. "," Fujicure FXR-1081 "," Fujicure FXR-1121 ".

成分(4)潛伏性熱陰離子聚合起始劑，以含有自胺-環氧加合物系化合物和胺-異氰酸酯加合物系化合物所組成之群組中選擇出之至少一種為佳，以自上述群組選擇至少一種組成為較佳，以胺-環氧加合物系化合物或胺-異氰酸酯加合物系化合物為更佳。The component (4) is a latent thermal anionic polymerization initiator, and preferably contains at least one selected from the group consisting of an amine-epoxy adduct-based compound and an amine-isocyanate adduct-based compound. In the above group, it is preferable to select at least one composition, and it is more preferable to use an amine-epoxy adduct-based compound or an amine-isocyanate adduct-based compound.

由熱引起之硬化性的角度來看，成分(4)之量，相對於硬化性組成物整體，以為0.01重量%以上為佳，0.1重量%以上為較佳，0.5重量%以上為更佳。又，自保存安定性的角度來看，成分(4)之重量，相對於硬化性組成物整體，以為15重量%以下為佳，10重量%以下為較佳，6重量%為更佳。From the viewpoint of heat-hardenability, the amount of the component (4) is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and even more preferably 0.5% by weight or more based on the entire curable composition. From the viewpoint of storage stability, the weight of the component (4) is preferably 15% by weight or less, more preferably 10% by weight or less, and more preferably 6% by weight based on the entire curable composition.

＜(5)熱自由基產生劑＞ 　　本發明之硬化性組成物，作為成分(5)亦還可含有熱自由基產生劑。成分(5)可單獨為1種，亦可為2種以上。作為熱自由產生劑，例如可列舉出偶氮化合物、有機過氧化物等。<(5) Thermal radical generator> The curable composition of the present invention may further contain a thermal radical generator as a component (5). The component (5) may be one kind alone, or two or more kinds. Examples of the thermal free generator include an azo compound and an organic peroxide.

作為偶氮化合物，例如可列舉出2,2’-偶氮二(異丁腈)、2,2’-偶氮二(2,4-二甲基戊腈)、2,2’-偶氮二(2-甲基丁腈)、4,4’-偶氮二(4-氰基戊酸)、2,2’-偶氮二(2-甲基)二鹽酸鹽、1,1’-偶氮二(1-乙醯氧基-1-苯乙烷、1,1’-偶氮二(環己烷-1-腈)、2,2’-偶氮二甲基(異丁酸酯)、2,2’-偶氮二(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮二(2-甲基丙腈)、2,2’-偶氮二(2-甲基丁腈)、1[(1-氰基-1-甲基乙基)偶氮]甲醯胺、2-苯基偶氮-4-甲氧基-2,4-二甲基戊、2,2’-偶氮二甲酯(2-甲基丙酸酯)等。Examples of the azo compound include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azo Bis (2-methylbutyronitrile), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-methyl) dihydrochloride, 1,1 ' -Azobis (1-ethoxyl-1-phenylethane, 1,1'-azobis (cyclohexane-1-nitrile), 2,2'-azodimethyl (isobutyric acid Ester), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2 ' -Azobis (2-methylbutyronitrile), 1 [(1-cyano-1-methylethyl) azo] formamidine, 2-phenylazo-4-methoxy-2, 4-dimethylpentane, 2,2'-azodimethyl (2-methylpropionate) and the like.

作為有機過氧化物，例如可列舉出過氧化苯甲醯、叔丁基過氧化氫、異丙苯過氧化氫、過氧化二叔丁基、過氧化甲乙酮、1,1-二(叔己基過氧)環己烷、2,2-二(叔丁基過氧)丁烷、n-丁基4,4-二(t-過氧化丁基)戊酸酯、2,2-二(4,4-二(叔丁基過氧)環己基)丙烷、對-甲烷氫過氧化物、二異丙氧基苯過氧化物、1,1,3,3-四甲基丁基氫過氧化物、氫過氧化枯烯、叔丁基過氧化氫、二(2-叔丁基過氧異丙基)苯、過氧化二枯基、2,5-二甲基-2,5-二(叔丁基過氧)己烷、叔丁基過氧化枯基、二叔丁基過氧化物、2,5-二甲基-2,5-二(叔丁基過氧)己烷-3、異丁過氧化物、二(3,5,5-t-甲基己醯基)過氧化物、過氧化二月桂醯、二琥珀酸過氧化物、二(3-甲基苯甲醯基)過氧化物、過氧化二苯甲醯、過氧碳酸二正丙酯、二異丙基過氧二碳酸酯、二(4-叔丁基環己基)過氧碳酸酯、二(2-乙基己基)過氧碳酸酯、二仲丁基過氧碳酸酯、枯基過氧新癸酸酯、1,1,3,3-四甲基丁基過氧新癸酸酯、過氧新癸酸叔己酯、過氧新癸酸叔丁酯、過氧新戊酸叔己酯、過氧新戊酸叔丁酯、1,1,3,3-四甲基丁基過氧-2-乙基己酸、2,5-二甲基-2,5-二(叔乙基己醯基過氧)己烷、叔己基過氧-2-乙基己酸、叔丁基過氧-2-乙基己酸、叔己基過氧異丙基單碳酸酯、叔丁基過氧化-3,5,5-三甲基己酸酯、過氧化月桂酸叔丁酯、叔丁基過氧異丙基單碳酸酯、叔丁基過氧-2-乙基己基單碳酸酯、過氧化苯甲酸叔己酯、2,5-二甲基-2,5-二(苯甲醯基過氧)己烷、過氧乙酸叔丁酯、叔丁基過氧-3-甲基苯甲酸酯和過氧化苯甲酸叔丁酯之混和物、過氧化苯甲酸叔丁酯、叔丁基過氧化烯丙基單碳酸酯、3,3’,4,4’-四(叔丁基過氧羰基)二苯甲酮等。Examples of the organic peroxide include benzamidine peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, methyl ethyl ketone peroxide, and 1,1-di (tert-hexyl peroxide). Oxygen) cyclohexane, 2,2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-peroxybutyl) valerate, 2,2-bis (4, 4-Di (tert-butylperoxy) cyclohexyl) propane, p-methane hydroperoxide, diisopropoxybenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide , Cumene hydroperoxide, tert-butyl hydroperoxide, bis (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert Butylperoxy) hexane, t-butylperoxycumyl, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, iso Butyl peroxide, bis (3,5,5-t-methylhexyl) peroxide, dilauryl peroxide, disuccinic acid peroxide, bis (3-methylbenzyl) peroxide Oxides, dibenzofluorene peroxide, di-n-propyl peroxycarbonate, diisopropylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxycarbonate, bis (2-ethylhexyl) ) Peroxy carbonate, Sec-butyl peroxycarbonate, cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, tert-hexyl peroxy neodecanoate, peroxyneodecane Tert-butyl acid ester, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoic acid, 2,5- Dimethyl-2,5-bis (tert-ethylhexylperoxy) hexane, tert-hexylperoxy-2-ethylhexanoic acid, tert-butylperoxy-2-ethylhexanoic acid, tert-hexyl peroxy Oxyisopropyl monocarbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperlaurate, tert-butylperoxyisopropylmonocarbonate, tert-butyl Peroxy-2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzylideneperoxy) hexane, tert-butyl peroxyacetate , A mixture of tert-butyl peroxy-3-methylbenzoate and tert-butyl peroxybenzoate, tert-butyl peroxybenzoate, tert-butyl perallyl monocarbonate, 3,3 ', 4,4'-tetrakis (t-butylperoxycarbonyl) benzophenone and the like.

熱自由基產生劑之10小時半衰期溫度，從低溫硬化性的角度來看，以40℃以上、小於100℃為佳，50℃以上、90℃以下為較佳。The 10-hour half-life temperature of the thermal radical generator is preferably 40 ° C or higher and less than 100 ° C, and more preferably 50 ° C or higher and 90 ° C or lower from the viewpoint of low-temperature hardenability.

成分(5)以自偶氮化合物和有機過氧化物所組成之群組中選擇出之至少一種為佳，以偶氮化合物或有機過氧化物為較佳。The component (5) is preferably at least one selected from the group consisting of an azo compound and an organic peroxide, and more preferably an azo compound or an organic peroxide.

在使用成分(5)的情況下，其量，從促進熱硬化的角度來看，相對於硬化性組成物整體，以為0.001重量%為佳，0.01重量%為較佳，0.1重量%為更佳。另一方面，硬化物中殘存的熱自由基產生劑或透過其分解物抑制排氣的角度來看，相對於硬化性組成物整體，以為5重量%以下為佳，3重量%以下為較佳，2重量%以下為更佳。In the case of using the component (5), the amount thereof is preferably 0.001% by weight, more preferably 0.01% by weight, and even more preferably 0.1% by weight based on the entire curable composition from the viewpoint of promoting thermal curing. . On the other hand, from the viewpoint of suppressing the exhaust gas by the thermal radical generator remaining in the hardened material or through its decomposed matter, it is preferably 5 wt% or less, and more preferably 3 wt% or less with respect to the entire hardenable composition. , 2% by weight or less is more preferable.

＜(6)其他之成分＞ 　　在不損害本發明之效果的範圍內，本發明之硬化性組成物，亦可含有與上述成分(1)~(5)不同的其他之成分。作為其他之成分，例如可列舉出聚合抑制劑(例如，二丁基羥基甲苯、巴比妥酸)；抗氧化劑；無機填料(例如，碳酸鈣、碳酸鎂、硫酸鋇、硫酸鎂、矽酸鋁、矽酸鋯、氧化鐵、氧化鈦、氧化鋁(礬土)、氧化鋅、二氧化矽、鈦酸鉀、高嶺土、滑石、石英粉等)；自使構成聚甲基丙烯酸甲酯和/或聚苯乙烯這些之單體與可聚合之單體聚合之共聚物等所組成之有機填料；觸變劑；消泡劑；流平劑；偶聯劑；阻燃劑；顏料；染料；螢光劑等。其他之成分，不論何者，可單獨為1種，亦可為2種以上。<(6) Other components> As long as the effect of the present invention is not impaired, the hardenable composition of the present invention may contain other components different from the aforementioned components (1) to (5). Examples of other components include polymerization inhibitors (for example, dibutylhydroxytoluene, barbituric acid); antioxidants; and inorganic fillers (for example, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, and aluminum silicate). , Zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, quartz powder, etc.); self-made polymethyl methacrylate and / or Organic fillers composed of polystyrene monomers and copolymers of polymerizable monomers; thixotropic agents; defoamers; leveling agents; coupling agents; flame retardants; pigments; dyes; fluorescent Agent. Regardless of the other components, they may be used alone or in combination of two or more.

為了提升硬化性組成物之保存安定性，亦可使用聚合抑制劑。聚合抑制劑，發揮抑制在使用硬化性組成物之作業環境溫度下之反應及光照射下不反應(即所謂暗反應)的效果。在此所說之作業環境溫度，通常為約15℃~約30℃之範圍。又，反應為自由基反應或離子反應(特別是陰離子反應)。In order to improve the storage stability of the hardening composition, a polymerization inhibitor may be used. The polymerization inhibitor exhibits the effect of suppressing the reaction under the working environment temperature using the hardening composition and the non-reaction under the light irradiation (so-called dark reaction). The working environment temperature mentioned here is usually in the range of about 15 ° C to about 30 ° C. The reaction is a radical reaction or an ionic reaction (especially an anionic reaction).

作為抑制自由基反應的聚合抑制劑，並無特別限定，例如，可列舉出醌型聚合抑制劑、對苯二酚型聚合抑制劑、亞硝胺型聚合抑制劑等。具體而言，例如，可列舉出對苯二酚，叔丁基對苯二酚，對甲氧基苯酚，N-亞硝基-N-苯基羥胺鋁鹽等。在使用抑制自由基反應的聚合抑制物的情況下，其量，係相對於硬化性組成物整體，以為0.0001~2.0重量%為佳，0.001~1.0重量%為較佳。此量小於0.0001重量%時無法獲得足夠的效果，此量若大於2.0重量%時有影響光照射或加熱時之聚合反應的疑慮。The polymerization inhibitor that inhibits a radical reaction is not particularly limited, and examples thereof include a quinone polymerization inhibitor, a hydroquinone polymerization inhibitor, a nitrosamine polymerization inhibitor, and the like. Specific examples include hydroquinone, tert-butylhydroquinone, p-methoxyphenol, and N-nitroso-N-phenylhydroxylamine aluminum salts. When a polymerization inhibitor that inhibits a radical reaction is used, the amount is preferably 0.0001 to 2.0% by weight, and more preferably 0.001 to 1.0% by weight, based on the entire curable composition. When the amount is less than 0.0001% by weight, a sufficient effect cannot be obtained. When the amount is greater than 2.0% by weight, there is a concern that the polymerization reaction during light irradiation or heating is affected.

作為抑制離子反應(特別是陰離子反應)的聚合抑制劑，例如可列舉出硼酸酯化合物、鈦酸酯化合物、鋁酸鹽化合物、鋯酸鹽化合物、異氰酸酯化合物、羧酸、酸酐和巰基有機酸等。Examples of polymerization inhibitors that inhibit ionic reactions (especially anionic reactions) include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, anhydrides, and mercapto organic acids. Wait.

作為硼酸酯化合物，例如可列舉出三甲基硼酸酯、三乙基硼酸酯、三丙基硼酸酯、三異丙基硼酸酯、三丁基硼酸酯、三戊基硼酸酯、三丙烯硼酸酯、三己基硼酸酯、三環己基硼酸酯、三環辛基硼酸酯、三壬基硼酸酯、三癸基硼酸酯、三月桂基硼酸酯、三(十六)烷基硼酸酯、三(十八)烷基硼酸酯、三(2-乙基己氧基)甲硼烷、雙(1,4,7,10-四噁(十一)烷基)(1,4,7,10,13-五噁(十四)烷基)(1,4,7-三噁(十一)烷基)甲硼烷、硼酸三苄酯，硼酸三苯酯、三-鄰-甲苯基硼酸酯、三-間-甲苯基硼酸酯、三乙醇胺硼酯等。Examples of the borate compound include trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, and tripentyl borate. Acid esters, tripropylene borates, trihexyl borates, tricyclohexyl borates, tricyclooctyl borates, trinonyl borates, tridecyl borates, trilauryl borates , Tris (hexadecyl) boronate, tris (octadecyl) boronate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxo ( Undecyl) alkyl) (1,4,7,10,13-pentaoxa (tetradecyl) alkyl) (1,4,7-trioxa (unde) alkyl) borane, tribenzyl borate , Triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, and the like.

作為鈦酸酯化合物，例如可列舉出鈦酸四乙酯、鈦酸四丙酯、鈦酸四異丙酯、鈦酸四丁酯、鈦酸四辛酯等。Examples of the titanate compound include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.

作為鋁酸酯化合物，例如可列舉出鋁酸三乙酯、鋁酸三丙酯、鋁酸三異丙酯、鋁酸三丁酯、鋁酸三辛酯等。Examples of the aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, and trioctyl aluminate.

作為鋯酸酯化合物，例如可列舉出四乙基鋯酸酯、四丙基鋯酸酯、四異丙基鋯酸酯、四丁基鋯酸酯等。Examples of the zirconate compound include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

作為異氰酸酯化合物，例如可列舉出異氰酸丁酯、異氰酸異丙酯、2-氯乙基異氰酸酯，苯基異氰酸酯、對氯苯基異氰酸酯、苄基異氰酸酯、六亞甲基二異氰酸酯、2-乙基苯基異氰酸酯、2,6-二甲基苯基異氰酸酯、甲苯二異氰酸酯(例：2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯)、1,5-萘二異氰酸酯、二苯基甲烷-4,4’-二異氰酸酯、聯甲苯胺二異氰酸酯、異佛爾酮二異氰酸酯、亞二甲苯基二異氰酸酯、對苯二異氰酸酯、雙環庚烷三異氰酸酯等。Examples of the isocyanate compound include butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, and 2 -Ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, toluene diisocyanate (example: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate), 1,5-naphthalene diisocyanate, di Phenylmethane-4,4'-diisocyanate, ditoluidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, dicycloheptane triisocyanate, and the like.

作為羧酸，例如，可列舉出甲酸、乙酸、丙酸、丁酸、己酸、辛酸等之飽和脂肪族一元酸、丙烯酸、甲基丙烯酸、巴豆酸等之不飽和脂肪族一元酸、一氯乙酸、二氯乙酸等之鹵代脂肪酸、乙醇酸、乳酸、葡萄酸等之一元羥基酸、乙醛酸等之脂肪族醛酸及酮酸、草酸、丙二酸、琥珀酸、馬來酸等之脂肪族多元酸、苯甲酸、鹵代苯甲酸、甲苯甲酸、苯乙酸、肉桂酸、扁桃酸等之芳香族一元酸、鄰苯二甲酸、三苯甲酸等之芳香族多元酸等。Examples of the carboxylic acid include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, hexanoic acid, and octanoic acid; unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid; and monochloride. Halogenated fatty acids such as acetic acid, dichloroacetic acid, monovalent hydroxy acids such as glycolic acid, lactic acid, and grape acid, and glyoxylic acids such as aldehydes and keto acids, oxalic acid, malonic acid, succinic acid, and maleic acid. Aromatic polybasic acids, benzoic acid, halogenated benzoic acid, toluic acid, phenylacetic acid, cinnamic acid, mandelic acid and other aromatic monobasic acids, phthalic acid, tribenzoic acid and other aromatic polybasic acids.

作為酸酐，例如，可列舉出琥珀酸酐、十二烷基琥珀酸酐、馬來酸酐、甲基環戊二烯和馬來酸酐的加合物、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐等之脂肪族多元酸酐；鄰苯二甲酸酐、偏苯三酸酐、吡咯烷二酸酐等之芳香族多元酸酐。Examples of the acid anhydride include succinic anhydride, dodecyl succinic anhydride, maleic anhydride, an adduct of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and methyltetrahydroophthalic acid. Fatty polybasic acid anhydrides such as phthalic anhydride; aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyrrolidine diacid anhydride.

作為巰基有機酸，例如可列舉巰基乙酸，巰基丙酸(例：3-巰基丙酸)、巰基丁酸(例：3-巰基丁酸、4-巰基丁酸)等之巰基脂肪族單羧酸；透過羥基酸和巰基有機酸之酯化反應而得之含有巰基和羧基之酯；巰基琥珀酸、二巰基琥珀酸(例：2,3-二巰基琥珀酸)等之巰基脂肪族二羧酸；巰基苯甲酸(例：4-巰基苯甲酸)等之巰基芳香族單羧酸；等。Examples of the mercapto organic acid include mercaptoacetic acid, mercaptopropionic acid (example: 3-mercaptopropionic acid), mercaptobutyric acid (example: 3-mercaptobutyric acid, 4-mercaptobutyric acid) and the like ; Esters containing thiol and carboxyl groups obtained by esterification reaction of hydroxy acid and thiol organic acid; thiol succinic acid, dimercaptosuccinic acid (eg, 2,3-dimercaptosuccinic acid), etc. ; Mercapto aromatic monocarboxylic acids such as mercaptobenzoic acid (eg, 4-mercaptobenzoic acid); etc.

作為抑制離子反應之聚合抑制劑，從高通用性・安全性、提升保存安定性的角度來看，以硼酸酯化合物為佳，三乙基硼酸酯、三丙基硼酸酯、三異丙基硼酸酯、三丁基硼酸酯為較佳，三乙基硼酸酯為更佳。As a polymerization inhibitor that inhibits ionic reactions, from the viewpoints of high versatility, safety, and improved storage stability, borate compounds are preferred, triethylborate, tripropylborate, and triisocyanate. Propyl borate and tributyl borate are more preferred, and triethyl borate is more preferred.

抑制離子反應之聚合抑制劑的量，相對於硬化性組成物整體，以為0.001~2.0重量%為佳，0.001~1.0重量%為較佳。此量小於0.0001重量%時無法獲得足夠的效果，在此量大於2.0重量%的情況下會因對加熱時等之反應產生不利影響而不佳。The amount of the polymerization inhibitor that suppresses the ion reaction is preferably 0.001 to 2.0% by weight, and more preferably 0.001 to 1.0% by weight, based on the entire curable composition. When the amount is less than 0.0001% by weight, a sufficient effect cannot be obtained, and when the amount is more than 2.0% by weight, it may be unfavorable because it adversely affects the reaction during heating and the like.

在本發明中，抑制自由基反應之聚合抑制劑以及抑制離子反應之聚合抑制劑，可以使用任何一種，亦可以兩種一起使用。In the present invention, any one of a polymerization inhibitor that inhibits a radical reaction and a polymerization inhibitor that inhibits an ionic reaction may be used, or two may be used together.

＜硬化性組成物之製造及硬化＞ 　　製造本發明之硬化性組成物並無特別之困難。例如使用捏合機、攪拌混合機、三輥研磨機等，透過使各成分均勻混和，作為可製備單液型之硬化性組成物。混和時之硬化性組成物之溫度，通常為10~40℃，以20~30℃為佳。<Production and hardening of hardenable composition> There is no particular difficulty in producing the hardenable composition of the present invention. For example, a single-liquid type curable composition can be prepared by using kneaders, stirring mixers, three-roll mills, and the like to uniformly mix the components. The temperature of the hardenable composition during mixing is usually 10 to 40 ° C, preferably 20 to 30 ° C.

作為當光硬化本發明之硬化性組成物時照射之光，可使用波長800nm以上之紅外線、可見光、紫外線、電子束等，以紫外線為佳。紫外線之峰值波長以300~500nm為佳。紫外線的光照度，以100~5,000mW/cm2 為佳，300~4,000mW/cm2 為較佳。曝光量以500~3,000mJ/ cm2 為佳，1,000~3,000mJ/cm2 為較佳。As light to be irradiated when the curable composition of the present invention is light-cured, infrared rays, visible light, ultraviolet rays, electron beams, and the like having a wavelength of 800 nm or more can be used, and ultraviolet rays are preferred. The peak wavelength of ultraviolet is preferably 300 ~ 500nm. The ultraviolet light intensity is preferably 100 to 5,000 mW / cm 2 , and more preferably 300 to 4,000 mW / cm 2 . The exposure amount is preferably 500 to 3,000 mJ / cm 2, and more preferably 1,000 to 3,000 mJ / cm 2 .

作為光照射方法，例如可列舉出低壓汞燈、中壓汞燈、高壓汞燈、超高壓汞燈、準分子激光器、化學燈、黑光燈、微波激發水銀燈、金屬鹵化物燈、鈉燈、螢光燈、LED型SPOT型UV輻射器、氙氣燈、DEEP　UV燈等。Examples of the light irradiation method include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave excited mercury lamp, a metal halide lamp, a sodium lamp, and a fluorescent lamp. Lamps, LED-type SPOT-type UV radiators, xenon lamps, DEEP UV lamps, etc.

當熱硬化本發明之硬化性組成物時之加熱溫度並無特別限定，通常為50~150℃，以60~100℃為佳。當熱硬化本發明之硬化性組成物時之加熱時間並無特別限定，通常為10~120分鐘，以30~60分鐘為佳。The heating temperature when thermally hardening the curable composition of the present invention is not particularly limited, but is usually 50 to 150 ° C, and preferably 60 to 100 ° C. The heating time when the curable composition of the present invention is thermally hardened is not particularly limited, but it is usually 10 to 120 minutes, and preferably 30 to 60 minutes.

＜硬化性組成物之用途＞ 　　本發明之硬化性組成物，兼具優異的光硬化性及優異的熱硬化性，可行成具有高黏著強度之硬化物。因此，作為本發明之硬化性組成物之用途，可舉例黏著劑、密封劑、塗層劑等。在這些用途之中，以黏著劑為佳。<Applications of the hardenable composition> The hardenable composition of the present invention has both excellent light hardenability and excellent heat hardenability, and can be made into a hardened material having high adhesive strength. Therefore, examples of applications of the curable composition of the present invention include adhesives, sealants, and coating agents. Among these uses, an adhesive is preferred.

＜構造物＞ 　　本發明為提供一種構造物，其係含有第一黏附體、第二黏附體與此等之黏著層之構造體，第一黏附體為聚碳酸酯製之構件，黏著層為上述本發明之硬化性組成物之硬化物。此外，本發明之構造物中，第一黏附體與第二黏附體，係透過黏著層黏著。作為第一黏附體的聚碳酸酯製之構件，例如可舉出鏡片、鏡片支架、外殼等。本發明之構造物，以作為智慧型手機等之攜帶型機器所搭載的相機模組為佳。<Structure> The present invention provides a structure, which is a structure including a first adherend, a second adherend, and an adhesive layer. The first adherend is a member made of polycarbonate, and the adhesive layer is the above. A cured product of the curable composition of the present invention. In addition, in the structure of the present invention, the first adherend and the second adherend are adhered through an adhesive layer. Examples of members made of polycarbonate as the first adherend include lenses, lens holders, and cases. The structure of the present invention is preferably a camera module mounted on a portable device such as a smart phone.

在本發明之構造物(例如相機模組)之組裝中，透過以下之步驟(I)~(III)，可有效率地製造各零件都高度準確地配置、且需黏著之零件間以高黏著強度黏著所組裝之高品質的構造物。 　　(I)將本發明之硬化性組成物塗布於傳感器外殼，將塗布此硬化性組成物的傳感器外殼與外殼定位之步驟。 　　(II)透過光照射使硬化組成物硬化(初步硬化)將第一黏附體以及第二黏附體暫時固定之步驟。 　　(III)透過加熱使硬化性組成物硬化(正式硬化)，形成黏著層(即硬化性組成物之硬化物)，將第一黏附體以及第二黏附體正式固定之步驟。In the assembly of the structure (such as a camera module) of the present invention, through the following steps (I) to (III), it is possible to efficiently manufacture each part with high accuracy and highly adhered parts to be adhered. Strong adhesion to assembled high-quality structures. (I) A step of applying the curable composition of the present invention to a sensor case, and positioning the sensor case and the case to which the curable composition is applied. (II) The step of temporarily curing the first adherend and the second adherend by curing (preliminarily curing) the hardened composition through light irradiation. (III) A step of hardening (formally hardening) the hardenable composition by heating to form an adhesive layer (ie, a hardened body of the hardenable composition), and officially fixing the first adherend and the second adherend.

在步驟(II)，因第一黏附體以及第二黏附體之配置位置的關係，被塗布的硬化性組成物仍殘留許多未被光照射之未照射部分。但是，本發明之硬化性組成物因具有相當良好的熱硬化性，即使發生光之未照射的部分，不僅透過光照射進行硬化的部分(初步硬化的部分)，光之未照射的部分也透過熱硬化充分進行硬化而導致完全硬化，被塗布的硬化性組成物整體形成具有高黏著強度之硬化物。 [實施例]In step (II), due to the relationship between the arrangement positions of the first adherend and the second adherend, the coated hardening composition still has many unirradiated portions that are not irradiated with light. However, the hardenable composition of the present invention has a relatively good thermosetting property. Even if the unirradiated portion of light occurs, not only the portion that is hardened by light irradiation (the portion that is initially hardened) but also the unirradiated portion is transmitted. Thermal hardening is sufficiently hardened to cause complete hardening, and the applied hardenable composition as a whole forms a hardened material having high adhesive strength. [Example]

以下，列舉實施例更具體地描述本發明進行，但本發明不受限於以下之實施例，當然也可以在符合上述・下述之要點的範圍內適當地改變及實施，所有這些都包含在本發明之技術範圍內。Hereinafter, the present invention will be described in more detail with examples. However, the present invention is not limited to the following examples. Of course, the present invention can be appropriately changed and implemented within a range that meets the above-mentioned points. All of these are included in Within the technical scope of the present invention.

1.原料 ＜(1)具有(甲基)丙烯醯基的化合物＞ 　　(1A)UVACURE　1561：DAICEL-ALLNEX股份有限公司製造、環氧樹脂半丙烯酸酯(具有丙烯醯基和環氧基之化合物)、環氧當量：450g/eq、分子量：450、1分子中之丙烯醯基的個數：1、1分子中之環氧基的個數：1 　　(1B)IRR-214K：DAICEL-ALLNEX股份有限公司製造、三環癸烷二甲醇二丙烯酸酯、分子量：300、1分子中之丙烯醯基的個數：2 　　(1C)EBECRYL150：DAICEL-ALLNEX股份有限公司製造、EO變性雙酚A二丙烯酸酯、分子量：512、1分子中之丙烯醯基的個數：2 　　(1D)DPHA：DAICEL-ALLNEX股份有限公司製造、二季戊四醇六丙烯酸酯、分子量：524、1分子中之丙烯醯基的個數：6 　　(1E)EBECRYL810：DAICEL-ALLNEX股份有限公司製造、聚酯丙烯酸酯(具有丙烯醯基之聚酯)、分子量：1,000、1分子中之丙烯醯基的個數：4 　　(1F)EBECRYL168：DAICEL-ALLNEX股份有限公司製造、磷酸變性甲基丙烯酸酯、1分子中之甲基丙烯醯基的個數：1.5 　　(1G)KAYAMER　PM-2：日本化藥股份有限公司製造、磷酸變性甲基丙烯酸酯、分子量：259、1分子中之甲基丙烯醯基的個數：1.5 　　(1H)KAYAMER　PM-21：日本化藥股份有限公司製造、磷酸變性甲基丙烯酸酯、分子量：437、1分子中之甲基丙烯醯基的個數：1.51. Raw material <(1) Compound having (meth) acrylfluorenyl group> (1A) UVACURE 1561: made by DAICEL-ALLNEX Co., Ltd., semi-acrylate epoxy resin (compound having acrylfluorenyl group and epoxy group) 1, epoxy equivalent: 450g / eq, molecular weight: 450, the number of propylene fluorenyl groups in one molecule: 1, the number of epoxy groups in one molecule: 1 (1B) IRR-214K: DAICEL-ALLNEX shares limited Manufactured by the company, tricyclodecane dimethanol diacrylate, molecular weight: 300, number of propylene fluorenyl groups in one molecule: 2 (1C) EBECRYL150: manufactured by DAICEL-ALLNEX Co., Ltd., EO denatured bisphenol A diacrylate ， Molecular weight: 512, the number of propylene fluorenyl groups in one molecule: 2 (1D) DPHA: manufactured by DAICEL-ALLNEX Co., Ltd., dipentaerythritol hexaacrylate, molecular weight: 524, the number of propylene fluorenyl groups in one molecule : 6 (1E) EBECRYL810: manufactured by DAICEL-ALLNEX Co., Ltd., polyester acrylate (polyester with acrylic fluorenyl group), molecular weight: 1,000, number of propylene fluorenyl groups in one molecule: 4 (1F) EBECRYL168: DAICEL-AL Manufactured by LNEX Co., Ltd., phosphate-modified methacrylate, the number of methacrylfluorene groups in one molecule: 1.5 (1G) KAYAMERYAPM-2: manufactured by Nippon Kayaku Co., Ltd., phosphate-modified methacrylate, Molecular weight: 259, the number of methacrylfluorenyl groups in one molecule: 1.5 (1H) KAYAMER PM-21: manufactured by Nippon Kayaku Co., Ltd., phosphoric acid modified methacrylate, molecular weight: 437, one in one molecule Number of propylene acryl groups: 1.5

＜(2)1分子中具有2個以上之巰基的多硫醇化合物＞ 　　(2A)PEMP：SC有機化學股份有限公司製造、季戊四醇四(3-巰基丙酸酯)、分子量：489、1分子中之巰基的個數：4 　　(2B)PE-1：昭和電工股份有限公司製造「Karenz MT PE-1」、季戊四醇四(3-巰基丁酸酯)、分子量：544、1分子中之巰基的個數：4 　　(2C)TMPIC：三(3-巰基丙基)異氰脲酸酯、分子量：351、1分子中之巰基的個數：3 　　(2D)DPMP：淀化學工業股份有限公司製造、二季戊四醇六(3-巰基丙酸酯)、分子量：783、1分子中之巰基的個數：6<(2) Polythiol compound having two or more mercapto groups in one molecule> (2A) PEMP: manufactured by SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate), molecular weight: 489, in one molecule Number of sulfhydryl groups: 4 (2B) PE-1: "Karenz MT PE-1" manufactured by Showa Denko Corporation, pentaerythritol tetrakis (3-mercaptobutyrate), molecular weight: 544, number of thiol groups in one molecule Number: 4 (2C) TMPIC: tris (3-mercaptopropyl) isocyanurate, molecular weight: 351, number of thiol groups in one molecule: 3 (2D) DPMP: manufactured by Yodo Chemical Industry Co., Ltd., 2 Pentaerythritol hexa (3-mercaptopropionate), molecular weight: 783, number of thiol groups in one molecule: 6

＜(3)光自由基產生劑＞ 　　(3A)IRGACURE 1173：BASF公司製造、2-羥基-2-甲基-1-苯基丙烷-1-酮 　　(3B)ESACURE KIP 150：Lamberti SPA公司製造、2-羥基-1-(4-異丙烯基苯基)-2-甲基丙烷-1-酮之寡聚物<(3) Photo radical generator> (3A) IRGACURE 1173: manufactured by BASF, 2-hydroxy-2-methyl-1-phenylpropane-1-one (3B) ESACURE KIP 150: manufactured by Lamberti SPA, Oligomers of 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropane-1-one

＜(4)潛伏性硬化劑＞ 　　(4A)PN-23：味之素Fine-Techno股份有限公司製造、胺-環氧加合物系化合物 　　(4B)FXR1081：T&K TOKA股份有限公司製造、胺-異氰酸酯加合物系化合物＜ (4) Latent hardener ＞ (4A) PN-23: Ajinomoto Fine-Techno Co., Ltd., amine-epoxy adduct compound (4B) FXR1081: T & K TOKA Co., Ltd., amine- Isocyanate adducts

＜(5)熱自由基產生劑＞ 　　(5A)V-601：和光純藥工業股份有限公司製造、2,2’-偶氮二甲酯(2-甲基丙酸酯)、10小時半衰期溫度：66℃ 　　(5B)PEROCTAO：日油股份有限公司製造、1,1,3,3-四甲基丁基過氧-2-乙基己酸、10小時半衰期溫度：65.3℃＜ (5) Thermal radical generator ＞ (5A) V-601: manufactured by Wako Pure Chemical Industries, Ltd., 2,2'-Azodimethyl (2-methylpropionate), 10-hour half-life temperature : 66 ° C (5B) PEROCTAO: manufactured by Nippon Oil Co., Ltd., 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoic acid, 10-hour half-life temperature: 65.3 ° C

＜(6)其他之成分＞ 　　(6A)Q-1301：和光純藥工業股份有限公司、N-亞硝基-N-苯基羥胺鋁鹽 　　(6B)三乙基硼酸酯：純正化學工業股份有限公司製造 　　(6C)巴比妥酸：東京化成股份有限公司製造＜ (6) Other ingredients ＞ (6A) Q-1301: Wako Pure Chemical Industries, Ltd., N-nitroso-N-phenylhydroxylamine aluminum salt (6B) triethylborate: Chunzheng Chemical Industry Co., Ltd. (6C) Barbituric acid: Made by Tokyo Chemical Industry Co., Ltd.

2.評估測試 [熱硬化性之評估] 　　於寬度2.5mm×長度8.0mm×厚度0.8mm之玻璃環氧樹脂層壓板(利昌工業公司製造、FR-4.0)使用厚度：約50μm之間隔，透過刮棒塗布機塗布硬化性組合物，形成硬化性組成物之塗膜，於在熱風循環烘箱中80℃下加熱60分鐘使其硬化，根據以下的標準之透過觸摸觀察塗膜外觀，評估熱硬化性。 ＜評估標準＞ 　　○：無未硬化成分 　　△：稍微有一些黏性 　　×：未硬化2. Evaluation test [Evaluation of thermosetting property] For a glass epoxy laminate (width: 4.8 mm × length: 8.0 mm × thickness: 0.8 mm) (manufactured by Lichang Industrial Co., Ltd., FR-4.0) Use thickness: interval of about 50 μm. The bar coater is used to coat the hardening composition to form a coating film of the hardening composition. The coating is heated at 80 ° C for 60 minutes in a hot air circulation oven to harden it. The appearance of the coating film is observed by touch according to the following standards to evaluate the thermosetting property. . <Evaluation criteria> ○: No unhardened component △: Slightly sticky ×: Unhardened

[黏著強度之測量] (1)光硬化後之黏著強度1之測量 　　將寬度25mm×長度100mm×厚度2.0mm之聚碳酸酯板(三菱Engineering-Plastics股份有限公司製造、lupilo NF-2000)於80℃下預先乾燥20分鐘，冷卻至室溫後，於聚碳酸酯板上以1~3mg的量塗布硬化性組成物，在其上放置冷凝器芯片(JIS名稱：2012規格)，以下述之條件進行光硬化，測量硬化物之黏著強度1，以下述標準評估。 (2)光及熱硬化後之黏著強度2之測量 　　與上述相同，向進行預先乾燥之聚碳酸酯板之硬化性組成物之塗布，對於進行冷凝器芯片之裝載之物以下述之條件進行光及熱硬化，測量硬化物之黏著強度2，以下述標準評估。 (3)熱硬化後之黏著強度3之測量 　　與上述相同，向進行預先乾燥之聚碳酸酯板之硬化性組成物之塗布，對於進行冷凝器芯片之裝載之物以下述之條件進行熱硬化，測量硬化物之黏著強度3，以下述標準評估。[Measurement of Adhesive Strength] (1) Measurement of Adhesive Strength after Light Hardening1 Width 25mm × length 100mm × thickness 2.0mm polycarbonate plate (manufactured by Mitsubishi Engineering-Plastics Co., Ltd., lupilo NF-2000) at 80 It was dried in advance at 20 ° C for 20 minutes, and after cooling to room temperature, a curable composition was applied on a polycarbonate plate in an amount of 1 to 3 mg, and a condenser chip (JIS name: 2012 standard) was placed thereon under the following conditions. Light hardening was performed, and the adhesive strength 1 of the hardened material was measured and evaluated in accordance with the following criteria. (2) The measurement of the adhesive strength 2 after light and heat curing is the same as described above. The hardening composition of a polycarbonate plate that has been dried in advance is applied, and the contents of the condenser chip are lighted under the following conditions. And heat curing, the adhesive strength 2 of the cured product was measured, and evaluated according to the following criteria. (3) The measurement of the adhesive strength 3 after heat curing is the same as the above, and the hardening composition of the polycarbonate plate which has been dried in advance is applied, and the contents of the condenser chip are heat cured under the following conditions. The adhesive strength 3 of the cured product was measured and evaluated in accordance with the following criteria.

黏著強度(N/mm2 )以邦德測試儀(dega公司製造系列4000)從側面方向斷開芯片來測量。進行3次測量求出其平均值。The adhesive strength (N / mm 2 ) was measured with a Bond tester (series 4000 manufactured by Dega Corporation) with the chip disconnected from the side. Three measurements were performed to determine the average.

＜硬化條件＞ (1)光硬化 　　透過Panasonic公司製造UV-LED照射裝置UJ35，將照度2,500mW/cm2 之紫外線(峰值波長：365nm)從兩個方向以角度45°(向冷凝器芯片表面之光之入射角為45°)，將硬化性組成物照射1.2秒(曝光量3,000mJ/cm2 )。 (2)光及熱硬化 　　透過Panasonic公司製造UV-LED照射裝置UJ35，將照度2,500mW/cm2 之紫外線(峰值波長：365nm)從兩個方向以角度45°(向冷凝器芯片表面之光之入射角為45°)，將硬化性組成物照射1.2秒(曝光量3,000mJ/cm2 )。其次，將光照射的硬化性組成物於熱風循環烘箱中80℃下加熱60分鐘。 (3)熱硬化 　　將硬化性組成物於熱風循環烘箱中80℃下加熱60分鐘。<Hardening conditions> (1) Light curing is transmitted through a UV-LED irradiation device UJ35 manufactured by Panasonic, and ultraviolet rays (peak wavelength: 365nm) with an illuminance of 2,500 mW / cm 2 are angled at 45 ° from both directions (to the surface of the condenser chip). The incident angle of light was 45 °), and the curable composition was irradiated for 1.2 seconds (exposure amount: 3,000 mJ / cm 2 ). (2) Light and heat curing Through the UV-LED irradiation device UJ35 manufactured by Panasonic, the ultraviolet rays (peak wavelength: 365 nm) with an illuminance of 2,500 mW / cm 2 are angled at 45 ° from both directions (to the surface of the condenser chip). The incident angle was 45 °), and the curable composition was irradiated for 1.2 seconds (exposure amount: 3,000 mJ / cm 2 ). Next, the light-curable curable composition was heated at 80 ° C. for 60 minutes in a hot-air circulation oven. (3) Thermal curing The curable composition was heated in a hot air circulation oven at 80 ° C. for 60 minutes.

＜評估標準＞ (1)光硬化後之黏著強度1之評估標準 　　○：5N/mm2 以上 　　△：小於2~5N/mm2 ×：小於2N/mm2 (2)光之熱硬化後之黏著強度2之評估標準 　　○：10N/mm2 以上 　　△：小於5~10N/mm2 ×：小於5N/mm2 (3)熱硬化後之黏著強度3之評估標準 　　○：10N/mm2 以上 　　△：小於5~10N/mm2 ×：小於5N/mm2 <Evaluation Criteria> (1) Evaluation Criteria for Adhesive Strength 1 after Light Hardening ○: 5N / mm 2 or more △: Less than 2 ~ 5N / mm 2 ×: Less than 2N / mm 2 (2) Adhesion after heat curing by light Evaluation criteria for strength 2: 10 N / mm 2 or more △: less than 5 to 10 N / mm 2 ×: less than 5 N / mm 2 (3) Evaluation criteria for adhesive strength 3 after heat curing ○: 10 N / mm 2 or more △: Less than 5 ~ 10N / mm 2 ×: less than 5N / mm 2

[聚碳酸酯之狀態] 　　將測量上述之熱硬化後之黏著強度3後之黏著點之聚碳酸酯之狀態以數位顯微鏡(Keyence公司製造、VHX-2000、倍率：250倍)觀察。測量相對於黏接點整體之空隙比(面積%)，依據下述標準評估。 ＜評估標準＞ 　　○：空隙量小於5面積% 　　△：空隙量小於5~10面積% 　　×：空隙量10面積%以上[State of Polycarbonate] 状态 The state of the polycarbonate measuring the adhesion point after the heat-cured adhesive strength of 3 was observed with a digital microscope (manufactured by Keyence Corporation, VHX-2000, magnification: 250 times). The void ratio (area%) with respect to the entire adhesion point was measured and evaluated according to the following criteria. <Evaluation Criteria> ○: The void amount is less than 5 area%% △: The void amount is less than 5 to 10 area% ×: The void amount is 10 area% or more

[保存安定性] 　　將硬化性組成物於25℃下保管於塑膠製密封容器，確認直到凝膠化之天數，依據下述標準評估。 ＜評估標準＞ 　　○：7天以上 　　△：3~6天 　　×：小於3天[Storage stability] 硬化 The curable composition was stored in a plastic sealed container at 25 ° C, and the number of days until gelation was confirmed, and evaluated in accordance with the following criteria. <Evaluation criteria> ○: 7 days or more △: 3 ~ 6 days ×: less than 3 days

3.實施例及比較例 　　以下述表1~3所表示之量將各成分進行混和，製備實施例1~15以及比較例1~4之硬化性組成物。表中之各成分的數字表示摻合量(重量份)。又，下述表1~3中將「成分(1)中之丙烯醯基、甲基丙烯醯基和環氧基的總計與成分(2)之巰基的莫耳比」記載於「((甲基)丙烯醯基＋環氧基)/巰基」之欄位。3. Examples and Comparative Examples The components were mixed in the amounts shown in the following Tables 1 to 3 to prepare hardening compositions of Examples 1 to 15 and Comparative Examples 1 to 4. The number of each component in the table indicates the blending amount (parts by weight). In addition, in the following Tables 1 to 3, "the molar ratio of the total of the acrylfluorenyl group, methacrylfluorenyl group, and epoxy group in the component (1) to the mercapto group of the component (2)" is described in "((甲Group).

在實施例1~15，混和成分(1)及(3)，其次添加成分(4)再次進行混和，繼而添加成分(2)並充分分散後，進行靜置消泡製備硬化性組成物。在實施例11及12，上述操作中，與成分(1)及(3)同時地再添加成分(6)，與成分(2)同時地再添加成分(5)。在比較例1以及2，混和成分(1)及(3)，其次添加成分(4)並充分分散後，進行靜置消泡調整硬化性組成物。在比較例3以及4，混和成分(1)及(6)，其次添加成分(4)再次進行混和，繼而添加成分(2)並充分分散後，進行靜置消泡調整硬化性組成物。這些製備作業皆於25℃下進行。In Examples 1 to 15, the components (1) and (3) were mixed, and then the component (4) was added and mixed again. After the component (2) was added and dispersed sufficiently, the composition was subjected to static defoaming to prepare a hardenable composition. In Examples 11 and 12, in the above operation, the component (6) was added simultaneously with the components (1) and (3), and the component (5) was added simultaneously with the component (2). In Comparative Examples 1 and 2, the components (1) and (3) were mixed, and then the component (4) was added and sufficiently dispersed, and then the composition was cured by standing still and defoaming. In Comparative Examples 3 and 4, the components (1) and (6) were mixed, and then the component (4) was added and mixed again. After the component (2) was added and sufficiently dispersed, the defoaming composition was adjusted by standing still and defoaming. These preparations were performed at 25 ° C.

將實施例1~15以及比較例1~4之硬化性組成物之評估測試之結果表示於表1~3。Tables 1 to 3 show the results of the evaluation tests of the hardenable compositions of Examples 1 to 15 and Comparative Examples 1 to 4.

自實施例1~15之結果可得知，滿足本發明之要件的硬化性組成物，兼具優異的光硬化性及優異的熱硬化性，可獲得具有高黏著強度之硬化物，具有良好之保存安定性，且可抑制聚碳酸酯之分解。為此，當使用本發明之硬化性組成物時，根據使用環境或用途，可選擇性地進行透過加熱之硬化及透過光照射之硬化，或可組合兩者來進行。又，將本發明之硬化性組成物進行硬化所得之硬化物，每單位面積之黏著強度高，可用作相機模組中的構成構件間之黏著層。相對於此，自比較例1~4之結果可得知，未滿足本發明之要件的硬化性組成物，在不論是熱硬化性、黏著強度、保存安定性以及聚碳酸酯之狀態中，無法達到如本發明之硬化性組成物的水平。 [產業上之可利用性]It can be seen from the results of Examples 1 to 15 that the hardening composition satisfying the requirements of the present invention has both excellent light hardening property and excellent heat hardening property, and a hardened material having high adhesive strength can be obtained, which has good properties. Stability is kept, and decomposition of polycarbonate can be suppressed. Therefore, when the curable composition of the present invention is used, depending on the use environment or application, curing by heating and curing by light irradiation may be selectively performed, or both may be performed in combination. In addition, the cured product obtained by curing the curable composition of the present invention has high adhesive strength per unit area and can be used as an adhesive layer between constituent members in a camera module. In contrast, from the results of Comparative Examples 1 to 4, it can be seen that the hardenable composition which does not satisfy the requirements of the present invention cannot be obtained in the state of thermosetting, adhesive strength, storage stability, and polycarbonate. It reaches the level of the curable composition according to the present invention. [Industrial availability]

本發明之硬化性組成物，可用作黏著劑等，特別是作為為了製造相機模組所使用之黏著劑。The curable composition of the present invention can be used as an adhesive or the like, particularly as an adhesive used for manufacturing a camera module.

本申請案係基於在日本提出申請之特願2017-066048號，並將其內容全部援用於此申請案說明書。This application is based on Japanese Patent Application No. 2017-066048 for which an application was filed in Japan, and the entire contents thereof are incorporated into this application specification.

Claims (12)

一種硬化性組成物，含有以下之成分(1)~(4)； 　　(1)具有(甲基)丙烯醯基的化合物， 　　(2)1分子中具有2個以上之巰基的多硫醇化合物， 　　(3)光自由基產生劑，以及 　　(4)潛伏性硬化劑。A hardening composition containing the following components (1) to (4): (1) a compound having a (meth) acrylic fluorenyl group, (2) a polythiol compound having two or more mercapto groups in one molecule, (3) a photoradical generator, and (4) a latent hardener. 如請求項1之硬化性組成物，其中成分(1)含有以下之成分(1-1)； 　　(1-1)具有(甲基)丙烯醯基以及環氧基之化合物。For example, the curable composition according to claim 1, wherein the component (1) contains the following component (1-1); (1) A compound having a (meth) acrylfluorenyl group and an epoxy group. 如請求項1或2之硬化性組成物，其中成分(1)含有以下之成分(1-2)； 　　(1-2)磷酸變性(甲基)丙烯酸酯。For example, the curable composition according to claim 1 or 2, wherein the component (1) contains the following component (1-2); (1-2) Phosphate denatured (meth) acrylate. 如請求項1~3之任一項的硬化性組成物，其中成分(1)含有以下之成分(1-1)~(1-3)； 　　(1-1)具有(甲基)丙烯醯基以及環氧基之化合物， 　　(1-2)磷酸變性(甲基)丙烯酸酯， 　　(1-3)具有不符合成分(1-1)及成分(1-2)任一者之(甲基)丙烯醯基的化合物。The hardening composition according to any one of claims 1 to 3, wherein the component (1) contains the following components (1-1) to (1-3); (1-1) has a (meth) acrylic fluorenyl group And epoxy-based compounds, (1-2) phosphate-denatured (meth) acrylate, 不 (1-3) has a (methyl) which is not compatible with any of component (1-1) and component (1-2) Acrylofluorenyl compounds. 如請求項1~4之任一項的硬化性組成物，其中成分(2)含有1分子中具有2~6個之巰基的多硫醇化合物。The curable composition according to any one of claims 1 to 4, wherein component (2) contains a polythiol compound having 2 to 6 mercapto groups in one molecule. 如請求項1~5之任一項的硬化性組成物，其中成分(2)含有自季戊四醇四(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、三(3-巰基丙基)異氰脲酸酯、三羥甲基丙烷三(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)、三[(3-巰基丙醯氧基)乙基]異氰脲酸酯、乙二醇雙(巰基乙酸酯)、三羥甲基丙烷三(巰基乙酸酯)、季戊四醇四(巰基乙酸酯)、1,4-雙(3-巰基丁醯氧基)丁烷、1,3,5-三(3-巰基丁醯氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷三(3-巰基丁酸酯)、三羥甲基乙烷三(3-巰基丁酸酯)、1,3,4,6-四(2-巰基乙基)甘脲、以及4,4’-異亞丙基二苯基雙(3-巰基丙基)醚所組成之群組中選擇出之至少一種。The hardening composition according to any one of claims 1 to 5, wherein the component (2) contains pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercapto (Propyl) isocyanurate, trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) ethyl] Isocyanurate, ethylene glycol bis (mercaptoacetate), trimethylolpropane tri (mercaptoacetate), pentaerythritol tetra (mercaptoacetate), 1,4-bis (3-mercaptobutane) (Oxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, Trimethylolpropane tri (3-mercaptobutyrate), trimethylolethane tri (3-mercaptobutyrate), 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, And at least one selected from the group consisting of 4,4'-isopropylidenediphenylbis (3-mercaptopropyl) ether. 如請求項1~5之任一項的硬化性組成物，其中成分(2)含有自季戊四醇四(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、三(3-巰基丙基)異氰脲酸酯、以及二季戊四醇六(3-巰基丙酸酯)所組成之群組中選擇出之至少一種。The hardening composition according to any one of claims 1 to 5, wherein the component (2) contains pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercapto At least one selected from the group consisting of propyl) isocyanurate and dipentaerythritol hexa (3-mercaptopropionate). 如請求項1~7之任一項的硬化性組成物，其中成分(1)中之丙烯醯基、甲基丙烯醯基以及環氧基之總計與成分(2)中之巰基的莫耳比(成分(1)中之丙烯醯基、甲基丙烯醯基以及環氧基之總計/成分(2)中之巰基)為0.5~2.0。The hardenable composition according to any one of claims 1 to 7, wherein the molar ratio of the total of the acrylfluorenyl group, the methacrylfluorenyl group, and the epoxy group in the component (1) to the thiol group in the component (2) is a molar ratio (Total of acrylfluorenyl group, methacrylfluorenyl group, and epoxy group in component (1) / mercapto group in component (2)) is 0.5 to 2.0. 如請求項1~8之任一項的硬化性組成物，其中成分(4)含有自胺-環氧加合物系化合物以及胺-異氰酸酯加合物系化合物所組成之群組中選擇出之至少一種。The curable composition according to any one of claims 1 to 8, wherein the component (4) contains a compound selected from the group consisting of an amine-epoxy adduct-based compound and an amine-isocyanate adduct-based compound. At least one. 如請求項1~9之任一項的硬化性組成物，其中作為成分(5)，係更進一步含有熱自由基產生劑。The curable composition according to any one of claims 1 to 9, further comprising a thermal radical generator as a component (5). 一種構造物，其係含有第一黏附體、第二黏附體與此等之黏著層之構造物，其中； 　　第一黏附體為聚碳酸酯製之構件， 　　該黏著層為如請求項1~10之任一項的硬化性組成物的硬化物。A structure comprising a first adhesive body, a second adhesive body, and an adhesive layer thereof, wherein: the first adhesive body is a member made of polycarbonate, and the adhesive layer is as in claims 1 to 10 A cured product of any one of the curable compositions. 如請求項11之構造物，其係相機模組。The structure as claimed in claim 11 is a camera module.
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