TWI753144B - Curable composition and structure - Google Patents

Curable composition and structure Download PDF

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TWI753144B
TWI753144B TW107110650A TW107110650A TWI753144B TW I753144 B TWI753144 B TW I753144B TW 107110650 A TW107110650 A TW 107110650A TW 107110650 A TW107110650 A TW 107110650A TW I753144 B TWI753144 B TW I753144B
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meth
curable composition
compound
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TW107110650A
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TW201900733A (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
    • C08F2/46—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
    • 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
    • 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)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (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

本發明提供一種含有(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。The present invention provides a compound containing (1) a (meth)acryloyl group, (2) a polythiol compound having two or more mercapto groups in one molecule, (3) a photoradical generator, and (4) Hardening composition of latent hardener.

Description

硬化性組成物及構造物Curable 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 curable composition and a structure 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, camera modules mounted on portable devices such as smartphones have been gradually reduced in size. Due to the miniaturization of the camera module, the parts connecting the constituent members of the camera module become finer, and therefore, high adhesive strength of the adhesive layer formed by the adhesive for these connections is required.

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 curability in order to avoid thermal damage to image sensors and the like due to high-temperature processing, and also requires a short period of time from the viewpoint of improving production efficiency. hardening. From such a viewpoint, as a low-temperature short-time curing type adhesive, an ultraviolet curing type adhesive or a thermosetting epoxy resin type adhesive is often used. However, UV-curable adhesives can be cured quickly, but they have disadvantages such as curing deformation due to curing shrinkage, and they cannot be used for adhesion of parts that are not irradiated by light. On the other hand, thermosetting epoxy resin adhesives are low-temperature and short-time hardening type adhesives, but in order to maintain the adhesive posture during adhesion, the components (parts) to be adhered must be fixed with jigs or devices, and due to the heating temperature The viscosity decreases due to the rise, sags before hardening, and there are problems such as flow out of the desired part, etc., 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 above-mentioned problems, in order to arrange the members constituting the camera module with high accuracy, curing (preliminary curing) caused by irradiation with transmitted light (ultraviolet light, visible light) is temporarily fixed, and then the main curing is performed by heating and Several proposals have been made for the type of adhesive that performs main adhesion (main fixation) (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] Japanese Patent Laid-Open No. 2009-51954 [Patent Document 2] Japanese Patent Laid-Open No. 2009-79216

[發明欲解決之問題][Problems to be Solved by Invention]

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。The adhesive layer of the cured product obtained by photo-curing, thermal-curing or photo-and-thermal curing of conventional adhesives does not have sufficient adhesive strength in some cases. In addition, conventional adhesives do not have sufficient storage stability in some cases. In addition, when one of the adherends is a polycarbonate-made member (eg, a lens), when a conventional adhesive is used, the polycarbonate is decomposed and voids are formed in the member, and the adhesive strength may decrease.

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 accomplished in view of the above-mentioned circumstances, and its object is to provide a cured product (adhesive layer) which is excellent in photohardenability and thermosetting property, can form a sufficient adhesive strength, is excellent in storage stability, and is made of polycarbonate. A sclerosing composition that inhibits the decomposition of components when they are adhered. [How to solve 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 repeated diligent studies by the present inventors, it was found that (1) a compound having a (meth)acryloyl group, (2) a polythiol compound having two or more mercapto groups in one molecule, and (3) photoradical generation The above-mentioned object can be achieved by the curable composition of (4) a latent hardener. 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 curable composition comprising the following components (1) to (4): (1) a compound having a (meth)acryloyl group, (2) a polysulfide having two or more mercapto groups in one molecule Alcohol compounds, (3) photo-radical generators, and (4) latent hardeners. [2] The curable composition according to the above [1], wherein the component (1) contains the following components (1-1): (1-1) A compound having a (meth)acryloyl group and an epoxy group. [3] The curable composition according to the above [1] or [2], wherein the component (1) contains the following components (1-2): (1-2) Phosphoric acid modified (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): (1-1) having ( A compound of a meth)acryloyl group and an epoxy group, (1-2) Phosphoric acid modified (meth)acrylate, (1-3) Any of the components (1-1) and (1-2) which do not meet the requirements The latter is a (meth)acryloyl compound. [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(thioglycolate), trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), 1,4-bis (3-Mercaptobutanoyloxy)butane, 1,3,5-tris(3-mercaptobutanoyloxyethyl)-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-mercaptobutyrate) At least one selected from the group consisting of ethyl) glycoluril and 4,4'-isopropylidene diphenyl bis(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 sum of the acryl group, methacryloyl group and epoxy group in the component (1) is the same as that in the component (2). The molar ratio of the mercapto group (the sum of the acryl group, the methacryloyl group and the epoxy group in the component (1)/the mercapto 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], which further contains a thermal radical generator as the 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 cured product of the curable composition of any one of ] to [10]. [12] The structure according to the above [11] 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 photocurability and thermosetting property, can form a cured product (adhesive layer) having sufficient adhesive strength, is excellent in storage stability, and is used in the case of adhering a member made of polycarbonate. Its decomposition can be inhibited.

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 containing (1) a compound having a (meth)acryloyl group, and (2) a polythiol compound having two or more mercapto (-SH) groups in one molecule (the following Sometimes referred to simply as "polythiol compounds"), (3) photoradical generators, and (4) latent hardeners. Below, 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) Compound having a (meth)acryloyl group> In the present invention, the "compound having a (meth)acryloyl group" of the component (1) mainly plays the role of a component responsible for enhancing the adhesive strength. The "(meth)acryloyl group" in the present invention means "acryloyl group and/or methacryloyl group". The component (1) may be used alone or in combination of two or more.

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)acryloyl groups in one molecule of the compound having a (meth)acryloyl group may be 1 or more. When the compound which has a (meth)acryloyl group is a mixture, this number represents the average value per molecule. In addition, when both acryl group and methacryloyl group exist in 1 molecule, the said number means the total number of objects of acryl group and methacryloyl group in 1 molecule. The number of (meth)acryloyl groups in one molecule of the compound having a (meth)acryloyl group is preferably 1 to 4, and more preferably 1 to 2.

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)acryloyl group is preferably 50 to 5,000, preferably 70 to 4,000, and more preferably 100 to 2,000. When the molecular weight is less than 50, the volatility is high, and it is not favorable from the viewpoints 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, the molecular weight of 1000 or more means the weight average molecular weight, which can be measured by gel permeation chromatography (GPC). Molecular weights less than 1,000 can be measured by gravimetric analyzers 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。As a compound which has a (meth)acryloyl group, the following compounds are mentioned, for example. In addition, any of the following compounds may be used alone or in combination of two or more.

(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(Compounds having one acryl or methacryloyl group in one molecule) β-carboxyethyl (meth)acrylate (meth)acrylate isobornyl octyl/decyl (meth)acrylate Ethoxylated phenyl (meth)acrylates (meth)acrylates with epoxy groups Phosphoric acid-denatured (meth)acrylates EO-denatured phenol (meth)acrylates EO-denatured o-phenylphenol (meth) AcrylatesEO denatured p-Colylphenol (meth)acrylate EO denatured Nonylphenol (meth)acrylate PO denatured Nonylphenol (meth)acrylateN-(meth)acryloyloxyethylhexahydro 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 acid denaturation" means denaturation by bonding with an ester of 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(Compounds having two (meth)acryloyl 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 Modified 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)acryloyl groups in the molecule Polyester having two (meth)acryloyl groups in one 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(Compounds having 3 or more (meth)acryloyl groups in one molecule) Trimethylolpropane tri(meth)acrylate PO modified trimethylolpropane tri(meth)acrylate EO modified trimethylol Propane tri(meth)acrylate EO denatured isocyanuric acid(tri)(meth)acrylate Pentaerythritol(tri/tetra)(meth)acrylate Glycerol Propoxytri(meth)acrylate Pentaerythritol ethoxy Tetrakis(meth)acrylate Di-trimethylolpropane Tetra(meth)acrylate Dipentaerythritol(penta/hexa)(meth)acrylate Dipentaerythritol Hex(meth)acrylate Polyurethane having 3 (meth)acryloyl groups in 1 molecule Polyester having 3 (meth)acryloyl groups in 1 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。In addition, pentaerythritol (tri/tetra) (meth)acrylate is a mixture of pentaerythritol tri (meth)acrylate and pentaerythritol tetra (meth)acrylate. This mixing ratio (pentaerythritol tri(meth)acrylate/pentaerythritol tetra(meth)acrylate), the weight ratio is preferably 5/95~95/5, preferably 30/70~70/30.

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。Moreover, dipentaerythritol (penta/hexa) (meth)acrylate is the mixture of dipentaerythritol penta (meth)acrylate and dipentaerythritol hexa (meth)acrylate. This mixing ratio (dipentaerythritol penta(meth)acrylate/dipentaerythritol hexa(meth)acrylate), the weight ratio is preferably 5/95~95/5, preferably 30/70~70/30.

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。Moreover, as a compound which has a (meth)acryloyl group, EO-modified isocyanuric acid (di/tri)(meth)acrylate can be used. Here, EO-modified isocyanuric acid (di/tri)(meth)acrylate is a mixture of EO-modified isocyanuric acid di(meth)acrylate and EO-modified isocyanuric acid tri(meth)acrylate thing. This mixing ratio (EO modified isocyanuric acid di(meth)acrylate/EO modified isocyanuric acid tri(meth)acrylate), the weight ratio is preferably 1/99~99/1, 10/90~ 90/10 is better, 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 properties and adhesiveness, it is preferable that the component (1) contains a compound having a (meth)acryloyl group and an epoxy group (hereinafter, it may be simply referred to as "component (1-1)".) better. A component (1-1) may be used individually by 1 type, and may be 2 or more types.

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 to this. (i) A method in which a compound having two or more epoxy groups in one molecule and (meth)acrylic acid are reacted in proportion to the residual amount of the epoxy groups in the above epoxy compound. In addition, in the present invention, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid".

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 above-mentioned method (i) is not particularly limited, and examples thereof include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenyl type epoxy resin, and biphenyl aralkyl type epoxy resin. Epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus epoxy resin, bisphenol S type epoxy resin, aromatic glycidyl amine type epoxy resin, resin Cyclic epoxy resin, aliphatic chain epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, etc. Among these, bisphenol A type epoxy resin is preferable, and bisphenol A diglycidyl ether is 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」。Ingredient (1-1) may also use a commercially available product. Examples of such commercially available products include "UVACURE 1561" manufactured by Daicel-Allnex Co., Ltd., "EA-1010N" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and "4HBAGE" manufactured by Nippon Chemical Industries, Ltd..

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 having a (meth)acryloyl 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)acryloyl groups in 1 molecule of the compound having a (meth)acryloyl group and an epoxy group is preferably 1 to 4, preferably 1 to 3, and more preferably 1 to 2 , 1 is excellent. In addition, when the compound which has a (meth)acryloyl group and an epoxy group is a mixture, this number represents the 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 one molecule of the compound having a (meth)acryloyl group and an epoxy group is preferably 1 to 4, preferably 1 to 3, more preferably 1 to 2, and 1 is particularly good. In addition, when the compound which has a (meth)acryloyl group and an epoxy group is a mixture, this number represents the 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)acryloyl group and an epoxy group is preferably 100-2,000, more preferably 200-1,000, more preferably 300-500. In addition, "epoxy equivalent" is the number of grams (g/eq) of resin containing 1 gram equivalent of epoxy groups, and is measured according to the method prescribed 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)acryloyl group and an epoxy group is preferably 100-2,000, more preferably 200-1,000, and more preferably 300-500.

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。In the case of using the component (1-1), from the viewpoint of the viscosity and sclerosis of the entire composition, the usage amount is preferably 10 to 90 parts by weight relative to the total 100 parts by weight of the component (1), and 20 parts by weight. ~80 parts by weight is preferred, and 30-70 parts by weight is more preferred.

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 phosphoric acid-modified (meth)acrylate (hereinafter, it may be abbreviated as "component (1-2)" in some cases.). The component (1-2) may be used alone or in combination of two or more. The component (1-2) is preferably 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)acryloyl 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。A compound having a (meth)acryloyl group and a hydroxyl group in one molecule that can be used in the above-mentioned method (ii) can be produced, for example, 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)acrylic acid ester with a polyhydric alcohol (such as alkylene glycol, glycerin, etc.) in proportion to the residual amount of the hydroxyl group of the above polyhydric alcohol. (iv) A method of adding an alkylene oxide (such as 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) may also use commercially available products. Examples of such commercially available products include "EBECRYL168" manufactured by Allnex Co., Ltd., "KAYAMER PM-2" and "KAYAMER PM-21" 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)", "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)acryloyl groups in one molecule of the phosphoric acid-modified (meth)acrylate is preferably 0.5 to 3, more preferably 1 to 2, and more preferably 1 to 1.5. In addition, when the phosphoric acid-denatured (meth)acrylate is a mixture, this number represents the 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 100-1,000, preferably 150-800, and more preferably 200-600.

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。In the case of using the component (1-2), from the viewpoint of storage stability and curability, the usage amount is preferably 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight relative to the total 100 parts by weight of the component (1). Parts by weight are preferred, and 0.05 to 2 parts by weight are more preferred.

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。Component (1) consists of Component (1-1), Component (1-2), and a compound having a (meth)acryloyl group that does not conform to either Component (1-1) or Component (1-2) (Hereinafter, it may be abbreviated as "component (1-3)" in some cases.) Preferably. In this aspect, any one of the components (1-1) to (1-3) may be used alone, or two or more types may be used.

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 the component (1) contains the components (1-1) to (1-3), it corresponds to 100 parts by weight of the total of the component (1), and the amount of the component (1-1) is determined from the viscosity of the entire composition, From the viewpoint of hardenability, it is considered that 10-90 parts by weight is better, 20-80 parts by weight is better, and 30-70 parts by weight is better, and the amount of the component (1-2) is considered from the perspective of storage stability, hardening From the viewpoint of performance, 0.001-5 parts by weight is preferred, 0.01-3 parts by weight is preferred, and 0.05-2 parts by weight is more preferred, and the amount of component (1-3) is the residual weight part.

＜(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 mercapto groups in one molecule> In the curable composition of the present invention, the "polythiol compound having two or more mercapto groups in one molecule" of component (2), It mainly acts as a curing agent responsible for curing the component (1) by irradiation with light such as ultraviolet rays. The component (2) may be used alone or in combination of two or more. The number of mercapto groups in one molecule of the polythiol compound is preferably 2 to 6, more preferably 3 to 6, more preferably 3 to 5, and particularly preferably 3 or 4.

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, the method described in JP-A 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 partial esters and complete esters of polyhydric alcohols and mercapto organic acids. Here, the partial ester is an ester of a polyhydric alcohol and a carboxylic acid, which means that a part of the hydroxyl groups of the polyol forms an ester bond, and the complete ester means that all 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。As a polyhydric alcohol, ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. are mentioned, for example.

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 mercaptoorganic acid include mercaptoaliphatic monomers such as mercaptoacetic acid, mercaptopropionic acid (eg, 3-mercaptopropionic acid), and mercaptobutyric acid (eg, 3-mercaptobutyric acid and 4-mercaptobutyric acid). Carboxylic acids; esters with sulfhydryl and carboxyl groups obtained by esterification between hydroxy acids and mercapto organic acids; mercapto aliphatics of mercaptosuccinic acid, dimercaptosuccinic acid (eg 2,3-dimercaptosuccinic acid), etc. mercaptoaromatic monocarboxylic acids such as mercaptobenzoic acid (eg, 4-mercaptobenzoic acid). The number of carbon atoms of the above-mentioned mercaptoaliphatic monocarboxylic acid is preferably 2 to 8, preferably 2 to 6, more preferably 2 to 4, and particularly preferably 3. Among the above-mentioned mercapto organic acids, mercapto aliphatic monocarboxylic acids having 2 to 8 carbon atoms are preferred, mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid are preferred, and 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 partial esters of polyhydric alcohols and mercapto organic acids include trimethylolethanebis(thioglycolate), trimethylolethanebis(3-mercaptopropionate), trimethylolethanebis(3-mercaptopropionate), Alkane bis(3-mercaptobutyrate), trimethylolethane bis(4-mercaptobutyrate), trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptobutyrate) propionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(3-mercaptobutyrate) propionate), pentaerythritol tris(3-mercaptobutyrate), pentaerythritol tris(4-mercaptobutyrate), dipentaerythritol tetrakis(mercaptoacetate), dipentaerythritol tetrakis(3-mercaptobutyrate), di- Pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol tetrakis (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 complete esters of polyhydric alcohols and mercapto organic acids include ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), and ethylene glycol bis(3-mercaptobutyrate) ), ethylene glycol bis(4-mercaptobutyrate), trimethylolethane tris(thioglycolate), trimethylolethane tris(3-mercaptopropionate), trimethylolethane tris(3-mercaptopropionate) Alkane tris(3-mercaptobutyrate), trimethylolethane tris(4-mercaptobutyrate), trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(3-mercaptobutyrate) propionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(4-mercaptobutyrate), pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptobutyrate) propionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(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 viewpoint of storage stability, the above-mentioned partial esters and complete esters are preferably those with a very low content of basic impurities, and those that do not require the use of basic substances in production are preferable.

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 component (2), alkane polythiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc.; terminal mercapto-containing polyether; terminal mercapto-containing polysulfides; polythiol compounds obtained by reacting epoxy compounds with hydrogen sulfide; polythiol compounds with mercapto groups at the end obtained by reacting polythiol compounds and epoxy compounds; etc. can also be used in The polythiol compound produced by using basic substances as reaction catalysts in its production process. The polythiol compound produced by the alkaline substance is used for the dealkalization treatment, and the alkali metal ion concentration is adjusted 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。As a dealkalization treatment of the polythiol compound produced by using a basic substance, for example, the polythiol compound is dissolved in an organic solvent such as acetone and methanol, and neutralized by adding an acid such as dilute hydrochloric acid or dilute sulfuric acid. Then, the method of desalination by extraction, washing, etc.; the method of adsorption using an ion exchange resin; the method of purification 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。Moreover, as the component (2), for example, tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, 1,3,5-tris(3-mercaptobutanoyloxyethyl)-1 can be used ,3,5-triazine-2,4,6(1H,3H,5H)-trione, tris(3-mercaptopropyl)isocyanurate, bis(3-mercaptopropyl)isocyanurate ester, 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril, and 4,4'-isopropylidene diphenyl bis(3-mercaptopropyl) ether, etc.

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。Component (2) is preferably a polythiol compound having 2 to 6 mercapto groups in one molecule, preferably 3 to 6, more preferably 3 to 5, and particularly preferably 3 or 4.

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, component (2) is composed of pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl) isocyanuric acid ester, trimethylolpropane tris(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, ethyl acetate Glycol bis(mercaptoacetate), trimethylolpropane tris(mercaptoacetate), pentaerythritol tetrakis(mercaptoacetate), 1,4-bis(3-mercaptobutyryloxy)butane, 1 ,3,5-Tris(3-mercaptobutanoyloxyethyl)-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, component (2) is preferably at least one selected from the above-mentioned 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, component (2) comprises pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl) isocyanuric acid ester and at least one selected from the group consisting of dipentaerythritol hexa(3-mercaptopropionate). In this aspect, it is particularly preferable that at least one of the component (2) is selected from the above-mentioned group.

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 curability, the molar ratio of the sum of the acryl group, methacryloyl group and epoxy group in the component (1) to the mercapto group in the component (2) (the acryl group in the component (1) The total of the group, methacryloyl group and epoxy group/mercapto group in component (2)) is preferably 0.5-2.0, preferably 0.6-1.6, more preferably 0.7-1.5, and particularly preferably 0.8-1.3. 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)), "the acryl group in the component (1), methacrylic acid "Total of acyl group and epoxy group" is "total of acryl group and methacryloyl group in component (1)". Also, for example, when the component (1) has an acryl group and does not contain a methacryloyl group, "the total of the acryl group, the methacryloyl group and the epoxy group in the component (1)" is "component ( 1) The total of acrylyl 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 curability and adhesiveness, the amount of the component (1) is preferably 20 wt % or more, more preferably 30 wt % or more, and more preferably 40 wt % or more with respect to the entire curable composition. Similarly, from the viewpoint of curability and adhesiveness, the amount of the component (1) is preferably 85% by weight or less, preferably 80% by weight or less, and preferably 75% by weight or less with respect to the entire curable 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 curability and adhesiveness, the amount of the component (2) is preferably 10% by weight or more, more preferably 15% by weight or more, and more preferably 20% by weight or more, based on the entire curable composition. Similarly, from the viewpoint of curability and adhesiveness, the amount of the component (2) is preferably 70% by weight or less, preferably 65% by weight or less, and preferably 55% by weight or less with respect to the entire curable 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 curability and adhesiveness, the total amount of the components (1) and (2) is preferably 30% by weight or more, more preferably 50% by weight or more, and 70% by weight relative to the entire curable composition. The above is better. Similarly, from the viewpoint of sclerosing properties and tackiness, the total amount of the components (1) and (2) is preferably 99 wt % or less, more preferably 97 wt % or less, and 95 wt % or less with respect to the entire curable composition. The weight % or less is more preferable.

＜(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 alkylphenone-based photo-radical generators, acylphosphine oxide-based photo-radical generators, and oximes. Ester-based photo-radical generators, α-ketone-based photo-radical generators, and the like. The component (3) may be used alone or in combination of two or more. The photoradical generator is preferably an alkylphenone-based photoradical 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 alkylphenone-based photoradical generator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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-phenylene Tolyl benzoic acid, benzyl ether, 2,2-diethoxy, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzyl)oxidation Phosphine, ethyl-(2,4,6-trimethylbenzyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexylphenyl Ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl -1-Propan-1-one, oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one, etc.

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 acylphosphine oxide-based photoradical generator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl) acyl)-phenyl-phosphine oxide, etc.

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-benzyl oxime), 1-[6 -(2-Methylbenzyl)-9-ethyl-9H-carbazol-3-yl]ethanone O-acetoxime, etc.

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-ketone-based photoradical generator include benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexyl phenyl ketone, and 1-phenyl-2-hydroxy-2-methyl ether. Propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, etc.

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。Commercially available products of the photoradical generator include, for example, "IRGACURE 1173" (2-hydroxy-2-methyl-1-phenylpropan-1-one), "IRGACURE OXE-01" (1 -[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzyl oxime)), "IRGACURE OXE-02" (1-[6-(2-methyl) Benzyl)-9-ethyl-9H-carbazol-3-yl)ethanone O-acetoxime), "Esacure KTO 46" (2,4,6-trimethylbenzyl) manufactured by DKSH diphenylphosphine oxide and oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane] and a mixture of methylbenzophenone derivatives) , "ESACURE KIP 150" (oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-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, preferably 0.01% by weight or more, relative to the entire curable composition, from the viewpoint of obtaining a curable composition that can be efficiently photocured when irradiated with light. Preferably, it is more preferably 0.1% by weight or more. In addition, from the viewpoint of suppressing outgassing by the photoradical generator remaining in the cured product or through its decomposition product, it is preferably 10% by weight or less, more preferably 5% by weight or less, 2% by weight or less with respect to the entire curable composition. The weight % or less is more preferable.

＜(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 component (4) is a well-known additive in the field of epoxy resins and the like, which means that the epoxy resin is not hardened at room temperature (25°C), but is heated by heating. Hardener for hardening such as epoxy resin. A component (4) may be used individually by 1 type, and may be 2 or more types.

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 latent hardeners include imidazole compounds that are solid at room temperature, amine-epoxy adduct-based compounds (reaction products of amine compounds and epoxy compounds), and amine-isocyanate adduct-based compounds ( reaction products of amine compounds and isocyanate compounds) 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 imidazole compounds that are solid at room 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-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-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 epoxy compounds used as raw materials for amine-epoxy adduct compounds include polyphenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or glycerin or polyethylene glycol. 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 and β-hydroxynaphthoic acid with epichlorohydrin; phthalic acid, Polyglycidyl esters obtained from the reaction of polycarboxylic acids such as terephthalic acid with epichlorohydrin; glycidylamine compounds obtained from the reaction of 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; In addition, polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin, epoxidized polyolefin, etc. or monofunctional ring such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, etc. 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。The amine compound used as a raw material for the amine-epoxy adduct type compound may have active hydrogen capable of addition reaction with an epoxy group or an isocyanate group (also called an isocyanate group) in one molecule. One or more atoms and one or more amino groups (at least one of a primary amino group, a secondary amino group, and a tertiary amino group) in one molecule may be sufficient. Examples of such amine compounds include lipids such as diethylenetriamine, triethylenetetramine, propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexyl. family of amine compounds; aromatic amine compounds such as 4,4'-diaminodiphenylmethane, 2-methylaniline, etc.; 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2 , 4-dimethylimidazoline, piperidine, piperazine and other heterocyclic compounds containing nitrogen atoms; 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。In addition, if a compound having a tertiary amine is used, an excellent latent hardener can be produced. Examples of compounds having a tertiary amine include dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylaminoethylamine. Amines with tertiary amines such as piperazine, 2-methylimidazole, 2-ethylimino, 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc.; 2-dimethylaminoethanol, 1-Methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol 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-(bis Methylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, niacin, isoflurane Alcohols and phenols with tertiary amines such as acid, picolinic acid, N,N-dimethylglycine hydrazine, N,N-dimethylpropionic acid hydrazine, nicotinic acid hydrazine, isonicotinic acid hydrazine, etc. , thiols, carboxylic acids and hydrazides; 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。When an epoxy compound and an amine compound are subjected to an addition reaction to prepare an amine-epoxy adduct type compound, 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 resins. , polyols such as trimethylolpropane, polycarboxylic acids such as adipic acid and phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy- 2-Propanol, thioglycolic 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 isocyanate compounds used as raw materials for amine-isocyanate adduct compounds 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 cholone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, etc.; A compound containing an isocyanate group at the end obtained by the reaction of a functional isocyanate compound and an active hydrogen compound; etc. Examples of such a compound having an isocyanate group at a terminal include an addition compound having an isocyanate group at a terminal obtained by reacting toluene diisocyanate with trimethylolpropane, and an addition compound having an isocyanate group at a 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。For the latent hardener of component (4), for example, the above-mentioned production raw materials are appropriately mixed, reacted at a temperature from room temperature to 200°C, cooled and solidified, and then ground, or mixed with methyl ethyl ketone, dioxane, etc. The above-mentioned production raw materials are reacted in a solvent such as tetrahydrofuran and tetrahydrofuran, and after removing the solvent, it can be easily obtained by grinding the solid part.

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 component (4), a commercially available product can also be used. Examples of commercially available amine-epoxy adduct compounds include "Amicure PN-23", "Amicure PN-40", "Amicure PN-50", "Amicure PN-50" and "Amicure PN-50" manufactured by Ajinomoto Fine-Techno Co., Ltd. Amicure PN-H", "Hardener X-3661S", "Hardener X-3670S" manufactured by ACR Corporation, "Novacure HX-3742" and "Novacure HX-3721" manufactured by Asahi Kasei Corporation. In addition, examples of commercially available amine-isocyanate adduct compounds 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。Component (4) a latent thermal anionic polymerization initiator, preferably containing at least one selected from the group consisting of amine-epoxy adduct-based compounds and amine-isocyanate adduct-based compounds, with It is preferable to select at least one composition from the above group, and it is more preferable to use an amine-epoxy adduct type compound or an amine-isocyanate adduct type 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-induced curability, the amount of the component (4) is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and more preferably 0.5% by weight or more, based on the entire curable composition. In addition, from the viewpoint of storage stability, the weight of the component (4) is preferably 15 wt % or less, preferably 10 wt % or less, and more preferably 6 wt % with respect to 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 the component (5). The component (5) may be used alone or in combination of two or more. As a thermal free generator, an azo compound, an organic peroxide, etc. are mentioned, for example.

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), 2,2'-azobis Bis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methyl)dihydrochloride, 1,1' -Azobis(1-acetoxy-1-phenylethane, 1,1'-azobis(cyclohexane-1-carbonitrile), 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]formamide, 2-phenylazo-4-methoxy-2, 4-dimethylpentane, 2,2'-azodimethylester (2-methylpropionate), etc.

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 organic peroxides include benzyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, methyl ethyl ketone peroxide, 1,1-di(tert-hexyl peroxide) oxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)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-bis(tertiary Butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butylperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-3, iso Butyl peroxide, bis(3,5,5-t-methylhexanoyl) peroxide, dilaurin peroxide, disuccinic acid peroxide, bis(3-methylbenzyl) peroxide oxide, dibenzyl peroxide, di-n-propyl peroxycarbonate, diisopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxycarbonate, bis(2-ethylhexyl) ) peroxycarbonate, di-sec-butyl peroxycarbonate, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, tert-peroxyneodecanoate Hexyl ester, tert-butyl peroxyneodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoic acid, 2,5-dimethyl-2,5-di(tert-ethylhexylperoxy)hexane, tert-hexylperoxy-2-ethylhexanoic acid, tert-butylperoxy-2-ethyl Caproic acid, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl Monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzylperoxy)hexane , tert-butyl peroxyacetate, mixture of tert-butyl peroxy-3-methylbenzoate and tert-butyl peroxybenzoate, tert-butyl peroxybenzoate, tert-butyl allyl peroxide Monocarbonate, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, etc.

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 preferably 50°C or higher and 90°C or lower, from the viewpoint of low-temperature curability.

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。Component (5) is preferably at least one selected from the group consisting of azo compounds and organic peroxides, preferably azo compounds or organic peroxides.

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 more preferably 0.1% by weight with respect to the entire curable composition from the viewpoint of promoting thermosetting. . On the other hand, from the viewpoint of suppressing outgassing by the thermal radical generator remaining in the cured product or by its decomposition product, it is preferably 5 wt % or less, and preferably 3 wt % or less with respect to the entire curable composition. , 2 wt% or less is better.

＜(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> The curable composition of the present invention may contain other components different from the above-mentioned components (1) to (5) within the range that does not impair the effects of the present invention. Examples of other components include polymerization inhibitors (eg, dibutylhydroxytoluene, barbituric acid); antioxidants; inorganic fillers (eg, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate) , zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, quartz powder, etc.); Organic fillers composed of copolymers of polystyrene monomers and polymerizable monomers; thixotropic agents; defoaming agents; leveling agents; coupling agents; flame retardants; pigments; dyes; fluorescent agent, etc. As for the other components, any one may be used alone, or two or more may be used.

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 curable composition, a polymerization inhibitor may also be used. The polymerization inhibitor has the effect of suppressing the reaction at the working environment temperature in which the curable composition is used and the non-reaction under light irradiation (that is, the so-called dark reaction). The operating ambient temperature mentioned here is usually in the range of about 15°C to about 30°C. In addition, 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。Although it does not specifically limit as a polymerization inhibitor which suppresses a radical reaction, For example, a quinoid-type polymerization inhibitor, a hydroquinone-type polymerization inhibitor, a nitrosamine-type polymerization inhibitor, etc. are mentioned. Specifically, hydroquinone, tert-butyl hydroquinone, p-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum salt, etc. are mentioned, for example. When using the polymerization inhibitor which suppresses a radical reaction, the amount is preferably 0.0001 to 2.0% by weight, 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, sufficient effects cannot be obtained, and when the amount is more 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 suppress ionic reactions (especially anionic reactions) include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid 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, triacryl borate, trihexyl borate, tricyclohexyl borate, tricyclooctyl borate, trinonyl borate, tridecyl borate, trilauryl borate , tris (hexadecyl) borate, tris (octadecyl) borate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxane ( Undecyl) alkyl) (1,4,7,10,13-pentaoxa (tetradecyl) alkyl) (1,4,7-trioxa (undec) alkyl) borane, tribenzyl borate , Triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, etc.

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。As a titanate compound, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl titanate, etc. are mentioned, for example.

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。As an aluminate compound, triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, trioctyl aluminate, etc. are mentioned, for example.

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。As a zirconate compound, a tetraethyl zirconate, a tetrapropyl zirconate, a tetraisopropyl zirconate, a tetrabutyl zirconate etc. are mentioned, for example.

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, 2 -Ethylphenylisocyanate, 2,6-dimethylphenylisocyanate, toluene diisocyanate (Example: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate), 1,5-naphthalene diisocyanate, diisocyanate Phenylmethane-4,4'-diisocyanate, toluidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, bicycloheptane triisocyanate, etc.

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, caproic acid, and octanoic acid; unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid; Halogenated fatty acids such as acetic acid, dichloroacetic acid, monobasic hydroxy acids such as glycolic acid, lactic acid, and gluconic acid, aliphatic aldehydes and keto acids such as glyoxylic acid, oxalic acid, malonic acid, succinic acid, maleic acid, etc. Aliphatic 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, etc.

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 acid anhydrides include succinic anhydride, dodecylsuccinic anhydride, maleic anhydride, adducts of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Aliphatic polybasic acid anhydrides such as phthalic anhydride; aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyrrolidine dianhydride.

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 mercaptoorganic acids include mercaptoacetic acid, mercaptoaliphatic monocarboxylic acids such as mercaptopropionic acid (eg, 3-mercaptopropionic acid), and mercaptobutyric acid (eg, 3-mercaptobutyric acid and 4-mercaptobutyric acid). ; Esters containing mercapto and carboxyl groups obtained by esterification of hydroxy acid and mercapto organic acid; ; mercapto-aromatic monocarboxylic acid 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 suppresses ionic reaction, from the viewpoints of high versatility, safety, and improvement of storage stability, boric acid ester compounds are preferred, such as triethyl borate, tripropyl borate, and triisoborate. Propyl borate and tributyl borate are 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 ionic reaction is preferably 0.001 to 2.0% by weight, more preferably 0.001 to 1.0% by weight, relative to 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 is unfavorable because the reaction during heating or the like is adversely affected.

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, either the polymerization inhibitor for inhibiting the radical reaction and the polymerization inhibitor for inhibiting the ionic reaction may be used either or both of them 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 curable composition> There is no particular difficulty in producing the curable composition of the present invention. For example, using a kneader, a stirring mixer, a three-roll mill, or the like, by uniformly mixing each component, a single-liquid type curable composition can be prepared. The temperature of the curable 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 the light irradiated when the curable composition of the present invention is photocured, infrared rays, visible light, ultraviolet rays, electron beams, etc. having a wavelength of 800 nm or more can be used, and ultraviolet rays are preferable. The peak wavelength of ultraviolet rays is preferably 300~500nm. The illuminance of ultraviolet rays is preferably 100~5,000mW/cm 2 , and preferably 300~4,000mW/cm 2 . The exposure amount is preferably 500~3,000mJ/cm 2 , and preferably 1,000~3,000mJ/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 light irradiation methods include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, and fluorescent lamps. Lamp, LED type SPOT type UV radiator, xenon lamp, DEEP UV lamp, 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 thermosetting the curable composition of the present invention is not particularly limited, but is usually 50 to 150°C, preferably 60 to 100°C. The heating time when thermosetting the curable composition of the present invention is not particularly limited, but is usually 10 to 120 minutes, 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。<Application of Curable Composition> The curable composition of the present invention has both excellent photocurability and excellent thermosetting properties, and can be a cured product with high adhesive strength. Therefore, as the use of the curable composition of the present invention, an adhesive, a sealant, a coating agent, and the like can be exemplified. Among these uses, adhesives are 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 comprising a first adherend, a second adherend, and an adhesive layer thereof, wherein the first adherend is a polycarbonate member, and the adhesive layer is the above-mentioned adhesive layer. The 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. As a polycarbonate-made member of a 1st adherend, a lens, a lens holder, a case, etc. are mentioned, for example. The structure of the present invention is preferably used as a camera module mounted on a portable device such as a smartphone.

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 the parts that are arranged with high accuracy and that need to be adhered with high adhesion between parts Strong adhesion to assembled high-quality structures. (1) The step of applying the curable composition of the present invention to the sensor casing, and positioning the sensor casing and the casing to which the curable composition is coated. (II) The step of temporarily fixing the first adherend and the second adherend by hardening the hardening composition by light irradiation (preliminary hardening). (III) The step of hardening the curable composition by heating (formal hardening) to form an adhesive layer (that is, the hardening of the curable composition), and formally 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 the step (II), due to the relationship between the arrangement positions of the first adherend and the second adherend, many unirradiated parts that are not irradiated with light remain in the coated curable composition. However, since the curable composition of the present invention has a relatively good thermosetting property, even if the portion not irradiated with light occurs, not only the portion hardened by light irradiation (preliminary hardened portion) but also the portion not irradiated with light is transmitted through The thermosetting is sufficiently hardened to lead to complete hardening, and the coated curable composition as a whole forms a hardened product with 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 by way of examples. However, the present invention is not limited to the following examples. Of course, the present invention may be appropriately changed and implemented within the scope of the above-mentioned and the following points, all of which are included in the 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 a (meth)acryloyl group> (1A) UVACURE 1561: manufactured by DAICEL-ALLNEX Co., Ltd., epoxy resin half acrylate (a compound having an acryl group and an epoxy group) , Epoxy equivalent: 450g/eq, Molecular weight: 450, Number of acrylyl groups in 1 molecule: 1, Number of epoxy groups in 1 molecule: 1 (1B) IRR-214K: DAICEL-ALLNEX Co., Ltd. Company manufacture, tricyclodecane dimethanol diacrylate, molecular weight: 300, number of acrylyl groups in 1 molecule: 2 , Molecular weight: 512, Number of acryloyl groups in 1 molecule: 2 : 6 (1E) EBECRYL810: manufactured by DAICEL-ALLNEX Co., Ltd., polyester acrylate (polyester having acryl group), molecular weight: 1,000, number of acryl groups in one molecule: 4 (1F) EBECRYL168: DAICEL-ALLNEX Co., Ltd. product, phosphoric acid-modified methacrylate, the number of methacryloyl groups in 1 molecule: 1.5 (1G) KAYAMER PM-2: Nippon Kayaku Co., Ltd. product, phosphoric acid-modified methacrylic acid Ester, molecular weight: 259, number of methacryloyl groups in 1 molecule: 1.5 The number of methacryloyl 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 The number of mercapto groups: 4 (2B) PE-1: "Karenz MT PE-1" manufactured by Showa Denko Co., Ltd., pentaerythritol tetrakis (3-mercaptobutyrate), molecular weight: 544, the number of mercapto groups in 1 molecule Number: 4 (2C) TMPIC: Tris(3-mercaptopropyl) isocyanurate, Molecular weight: 351, Number of mercapto groups in 1 molecule: 3 (2D) DPMP: manufactured by Yodo Chemical Industry Co., Ltd., two Pentaerythritol hexa(3-mercaptopropionate), molecular weight: 783, number of mercapto groups in 1 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) Optical radical generator> (3A) IRGACURE 1173: manufactured by BASF, 2-hydroxy-2-methyl-1-phenylpropan-1-one (3B) ESACURE KIP 150: manufactured by Lamberti SPA, Oligomers of 2-Hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-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: manufactured by Ajinomoto Fine-Techno Co., Ltd., amine-epoxy adduct type compound (4B) FXR1081: manufactured by T&K TOKA Co., Ltd., amine- Isocyanate adduct series compounds

＜(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 NOF Corporation, 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: Pure Chemical Industry Co., Ltd. Co., Ltd. manufacture (6C) barbituric acid: manufactured 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 properties] Use thickness: about 50μm interval on glass epoxy resin laminates with width 2.5mm×length 8.0mm×thickness 0.8mm. The curable composition was coated with a bar coater to form a coating film of the curable composition, heated in a hot air circulation oven at 80°C for 60 minutes to harden, and the thermosetting property was evaluated by observing the appearance of the coating film by touch according to the following standards . <Evaluation Criteria> ○: No uncured component △: Slightly sticky ×: Uncured

[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 Adhesion Strength] (1) Measurement of Adhesion Strength 1 after Light Hardening A polycarbonate sheet with a width of 25mm×length of 100mm×thickness of 2.0mm (manufactured by Mitsubishi Engineering-Plastics Co., Ltd., lupilo NF-2000) was placed in 80 It was pre-dried at ℃ for 20 minutes, and after cooling to room temperature, the curable composition was applied in an amount of 1 to 3 mg on a polycarbonate plate, and a condenser chip (JIS name: 2012 specification) was placed on the polycarbonate plate under the following conditions. Photo-hardening was performed, and the adhesive strength 1 of the hardened product was measured and evaluated according to the following criteria. (2) The measurement of the adhesive strength 2 after light and heat curing is the same as the above, the coating of the curable composition on the polycarbonate plate which has been dried in advance, and the loading of the condenser chips are carried out under the following conditions. and thermal hardening, the adhesive strength 2 of the hardened product was measured and evaluated according to the following criteria. (3) The measurement of adhesive strength 3 after thermal hardening is the same as above. The coating of the curable composition on the pre-dried polycarbonate plate, and the thermal hardening of the load on the condenser chip are carried out under the following conditions: The adhesive strength 3 of the cured product was measured and evaluated according to 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 adhesion strength (N/mm 2 ) was measured with a Bond tester (Series 4000 manufactured by Dega Corporation) disconnecting the chip from the side direction. The average value was obtained by performing 3 measurements.

＜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。<Curing conditions> (1) Photo curing Through the UV-LED irradiation device UJ35 manufactured by Panasonic Corporation, ultraviolet rays (peak wavelength: 365nm) with an illuminance of 2,500mW/ cm2 are irradiated from two directions at an angle of 45° (to the surface of the condenser chip). The incident angle of light was 45°), and the curable composition was irradiated for 1.2 seconds (the exposure amount was 3,000 mJ/cm 2 ). (2) Light and thermal hardening Through the UV-LED irradiation device UJ35 manufactured by Panasonic, the ultraviolet rays (peak wavelength: 365nm) with an illuminance of 2,500mW/ cm2 are irradiated from two directions at an angle of 45° (to the light on the surface of the condenser chip). The incident angle was 45°), and the curable composition was irradiated for 1.2 seconds (the exposure amount was 3,000 mJ/cm 2 ). Next, the curable composition irradiated with light was heated in a hot air circulation oven at 80° C. for 60 minutes. (3) Thermosetting 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 Adhesion Strength 1 After Light Hardening ○: 5N/ mm2 or more △: Less than 2~5N/ mm2 ×: Less than 2N/ mm2 (2) Adhesion after light thermal curing Evaluation Criteria of Strength 2 ○: 10N/ mm2 or more △: Less than 5~10N/ mm2 ×: Less than 5N/ mm2 (3) Evaluation Criteria of Adhesive Strength 3 after Thermal Hardening ○: 10N/ mm2 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] The state of the polycarbonate at which the adhesion point after the above-mentioned adhesive strength 3 after thermal curing was measured was observed with a digital microscope (manufactured by Keyence Corporation, VHX-2000, magnification: 250 times). The void ratio (area %) relative to the entire bonding point was measured and evaluated according to the following criteria. <Evaluation Criteria> ○: Void amount is less than 5 area% △: Void amount is less than 5~10 area% ×: 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] The curable composition was stored in a plastic airtight container at 25°C, and the number of days until gelation was confirmed, and evaluated according to the following criteria. <Evaluation Criteria> ○: More than 7 days △: 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 Each component was mixed in the amounts shown in Tables 1 to 3 below to prepare curable compositions of Examples 1 to 15 and Comparative Examples 1 to 4. The number of each component in the table represents the blending amount (parts by weight). In addition, in the following Tables 1 to 3, "the molar ratio of the sum of the acryl group, methacryloyl group and epoxy group in the component (1) and the mercapto group in the component (2)" is described in "((methyl) group) acryl group + epoxy group)/mercapto group" field.

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, followed by adding the component (4) and mixing again, then adding the component (2) and fully dispersing, and then standing for defoaming to prepare a curable composition. In Examples 11 and 12, in the above operation, the component (6) was further added simultaneously with the components (1) and (3), and the component (5) was further added simultaneously with the component (2). In Comparative Examples 1 and 2, the components (1) and (3) were mixed, and the component (4) was added next and dispersed sufficiently, and then the curable composition was adjusted for defoaming by standing. In Comparative Examples 3 and 4, the components (1) and (6) were mixed, and the component (4) was added and mixed again, followed by adding the component (2) and sufficiently dispersed, and then left to defoaming to adjust the curable composition. These preparations were all carried out 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。The results of the evaluation tests of the curable compositions of Examples 1 to 15 and Comparative Examples 1 to 4 are shown in Tables 1 to 3.

Figure 02_image001
Figure 02_image001

Figure 02_image003
Figure 02_image003

Figure 02_image005
Figure 02_image005

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]From the results of Examples 1 to 15, it can be seen that the curable compositions satisfying the requirements of the present invention have both excellent photocurability and excellent thermosetting properties, and can obtain cured products with high adhesive strength and good properties. Preservation stability, and can inhibit the decomposition of polycarbonate. Therefore, when the curable composition of the present invention is used, curing by heating and curing by light irradiation may be selectively performed, or both may be combined according to the usage environment or application. 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. On the other hand, from the results of Comparative Examples 1 to 4, it can be seen that the curable compositions that do not satisfy the requirements of the present invention cannot be cured in terms of thermosetting properties, adhesive strength, storage stability, and polycarbonate. The level of the curable composition of the present invention is achieved. [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, etc., especially as an adhesive used in the manufacture of camera modules.

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 filed in Japan, and the entire contents thereof are incorporated in the description of this application.

Claims (11)

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，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。 A curable composition comprising the following components (1) to (4): (1) a compound having a (meth)acryloyl group, (2) a polythiol compound having two or more mercapto groups in one molecule, (3) A photoradical generator, and (4) a latent curing agent, wherein the component (1) contains the following component (1-2): (1-2) phosphoric acid modified (meth)acrylate. 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。 The curable composition according to claim 1, wherein the component (1) contains the following component (1-1): (1-1) a compound having a (meth)acryloyl 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(1-1)~(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 curable composition according to claim 1 or 2, wherein the component (1) contains the following components (1-1) to (1-3): (1-1) having a (meth)acryloyl group and an epoxy group The compound, (1-2) phosphoric acid-modified (meth)acrylate, (1-3) having a (meth)acryloyl group not conforming to any one of components (1-1) and (1-2) compound. 如請求項1或2之硬化性組成物，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 claim 1 or 2, wherein the component (2) contains a polythiol compound having 2 to 6 mercapto groups in one molecule. 如請求項1或2之硬化性組成物，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 curable composition according to claim 1 or 2, wherein component (2) contains pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)iso cyanurate, trimethylolpropane tris(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), tris[(3-mercaptopropionyloxy)ethyl]isocyanuric acid Esters, ethylene glycol bis(thioglycolate), trimethylolpropane tris(thioglycolate), pentaerythritol tetra(thioglycolate), 1,4-bis(3-mercaptobutyryloxy)butane Alkane, 1,3,5-tris(3-mercaptobutanoyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylol Propane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril, and 4,4 At least one selected from the group consisting of '-isopropylidene diphenyl bis(3-mercaptopropyl) ether. 如請求項1或2之硬化性組成物，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 curable composition according to claim 1 or 2, wherein component (2) contains pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)iso At least one selected from the group consisting of cyanurate and dipentaerythritol hexa(3-mercaptopropionate). 如請求項1或2之硬化性組成物，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 curable composition according to claim 1 or 2, wherein the molar ratio of the sum of the acryl group, methacryloyl group and epoxy group in the component (1) to the mercapto group in the component (2) (component (1) ) in the total of acryl group, methacryloyl group and epoxy group/mercapto group in component (2)) is 0.5 to 2.0. 如請求項1或2之硬化性組成物，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 claim 1 or 2, wherein the component (4) contains an amine-epoxy adduct-based compound and an amine-isocyanate adduct-based compound At least one selected from the group formed. 如請求項1或2之硬化性組成物，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 claim 1 or 2, wherein the component (5) further contains a thermal radical generator. 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1~9中之任一項的硬化性組成物的硬化物。 A structure, which is a structure containing a first adherend, a second adherend, and an adhesive layer thereof, wherein: the first adherend is a polycarbonate-made member, and the adhesive layer is as claimed in Items 1 to 9 A cured product of any of the curable compositions. 如請求項10之構造物，其係相機模組。 The structure of claim 10 is a camera module.
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