TWI831839B - Curable polysilsesquioxane compound, curable composition, cured product and method of using the curable composition - Google Patents

Curable polysilsesquioxane compound, curable composition, cured product and method of using the curable composition Download PDF

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TWI831839B
TWI831839B TW108135111A TW108135111A TWI831839B TW I831839 B TWI831839 B TW I831839B TW 108135111 A TW108135111 A TW 108135111A TW 108135111 A TW108135111 A TW 108135111A TW I831839 B TWI831839 B TW I831839B
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梅田明来子
宮脇学
中山秀一
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日商琳得科股份有限公司
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Abstract

本發明係一種硬化性聚倍半矽氧烷化合物、含有該硬化性聚倍半矽氧烷化合物之硬化性組合物、將該硬化性組合物硬化而成之硬化物、以及將前述硬化性組合物使用作為光學元件固定材用接著劑或光學元件固定材用密封劑之方法，該硬化性聚倍半矽氧烷化合物係具有下述式(a-1)所示的重複單元之硬化性聚倍半矽氧烷化合物，其特徵在於：滿足有關29 Si-NMR之特定的必要條件且質量平均分子量(Mw)為特定範圍。本發明的硬化性組合物係具有優異的硬化性且折射率為較低之物。 [R1 表示組成式：Cm H(2m-n+1) Fn 所表示之氟烷基，m表示1~10的整數，n表示2以上且(2m+1)以下的整數，D表示將R1 與Si鍵結之連結基(但是伸烷基除外)或單鍵]。The present invention relates to a curable polysesquioxane compound, a curable composition containing the curable polysesquioxane compound, a cured product obtained by curing the curable composition, and a combination of the foregoing curable compounds. A method of using the curable polysilsesquioxane compound as an adhesive for optical element fixing materials or a sealant for optical element fixing materials, wherein the curable polysilsesquioxane compound has a repeating unit represented by the following formula (a-1). A sesesquioxane compound is characterized in that it satisfies specific necessary conditions regarding 29 Si-NMR and has a mass average molecular weight (Mw) within a specific range. The curable composition of the present invention has excellent curability and a low refractive index. [R 1 represents the composition formula: C m H (2m-n+1) F n represents a fluoroalkyl group, m represents an integer from 1 to 10, n represents an integer from 2 to (2m+1), and D represents A linking group (except an alkylene group) or a single bond that bonds R 1 to Si].

Description

硬化性聚倍半矽氧烷化合物、硬化性組合物、硬化物以及硬化性組合物的使用方法Curable polysilsesquioxane compound, curable composition, cured product and method of using the curable composition

本發明係有關於一種硬化性聚倍半矽氧烷化合物、含有前述硬化性聚倍半矽氧烷化合物之具有優異的硬化性且折射率較低的硬化性組合物、將前述硬化性組合物硬化而成之接著強度較高的硬化物、及將前述硬化性組合物使用作為光學元件固定材用接著劑或光學元件固定材用密封劑之方法。The present invention relates to a curable polysesquioxane compound, a curable composition containing the curable polysesesquioxane compound and having excellent curability and a low refractive index. The curable composition is A method of using the cured product with high adhesive strength as an adhesive for optical element fixing materials or a sealant for optical element fixing materials using the curable composition.

先前，硬化性組合物係按照用途而進行各式各樣的改良且在產業上被廣泛地利用作為光學零件或成形體的原料、接著劑、塗佈劑等。又，硬化性組合物亦作為光學元件固定材用接著劑、光學元件固定材用密封劑等的光學元件固定材用組合物而受到關注。Previously, curable compositions have been variously improved according to their uses and have been widely used industrially as raw materials for optical parts or molded articles, adhesives, coating agents, and the like. In addition, the curable composition is also attracting attention as a composition for optical element fixing materials such as an adhesive for optical element fixing materials and a sealant for optical element fixing materials.

光學元件係有半導體雷射(LD)等的各種雷射和發光二極體(LED)等的發光元件、受光元件、複合光學元件、光積體電路等。近年來，係開發且廣泛地使用發光尖峰波長為較短波長之藍色光或白色光的光學元件。此種發光尖峰波長較短的發光元件的高亮度化係飛躍性地進展且伴隨著該情形，光學元件的發熱量係有進一步變大之傾向。Optical elements include various lasers such as semiconductor lasers (LD), light-emitting elements such as light-emitting diodes (LED), light-receiving elements, composite optical elements, optical integrated circuits, etc. In recent years, optical elements that emit blue light or white light with a peak wavelength of a shorter wavelength have been developed and widely used. The brightness of light-emitting elements having such a short emission peak wavelength is rapidly progressing, and along with this, the amount of heat generated by the optical element tends to further increase.

然而，伴隨著近年來之光學元件的高亮度化，光學元件固定材用組合物的硬化物係長時間被曝露在較高能量的光線和從光學元件所產生的高溫熱量，而產生接著力低落之問題。However, with the recent increase in brightness of optical elements, the cured product of the optical element fixing material composition is exposed to higher energy light and high-temperature heat generated from the optical element for a long time, resulting in a decrease in adhesive strength. problem.

為了解決該問題，專利文獻1~3係提案一種將聚倍半矽氧烷化合物作為主成分之光學元件固定材用組合物。但是即便專利文獻1~3記載之組合物的硬化物，亦有難以在保持充分的接著力之同時，得到耐熱性之情形。In order to solve this problem, Patent Documents 1 to 3 propose a composition for an optical element fixing material containing a polysesesquioxane compound as a main component. However, even in the case of cured products of the compositions described in Patent Documents 1 to 3, it may be difficult to obtain heat resistance while maintaining sufficient adhesive strength.

又，使用硬化性組合物將光學元件等固定時，多半的情形是形成具有配合目的之折射率之硬化物為重要的。特別是因為先前的硬化性組合物或其硬化物多半是折射率較高之物，所以要求折射率較低的硬化性組合物。In addition, when using a curable composition to fix an optical element or the like, it is often important to form a cured product having a refractive index matching the purpose. In particular, since most conventional curable compositions or cured products thereof have a relatively high refractive index, curable compositions having a lower refractive index are required.

專利文獻4係記載一種含有具有氟烷基的硬化性聚倍半矽氧烷化合物之硬化性組合物，作為提供折射率較低的硬化物之硬化性組合物。 但是如專利文獻4的實施例所示，使用含有具有氟烷基的重複單元比率為較高的硬化性聚倍半矽氧烷化合物之硬化性組合物時，係難以得到接著強度較高的硬化物。如此，專利文獻4記載之硬化性組合物的硬化物，在較高的接著強度與較低的折射率之間具有取捨(trade‐off)的關係。因此，使用專利文獻4記載的硬化性組合物時，係難以得到具有較高的接著強度與較低的折射率之雙方的特性之硬化物。Patent Document 4 describes a curable composition containing a curable polysilsesquioxane compound having a fluoroalkyl group as a curable composition that provides a cured product with a low refractive index. However, as shown in the examples of Patent Document 4, when a curable composition containing a curable polysilsesquioxane compound with a high repeating unit ratio of a fluoroalkyl group is used, it is difficult to obtain a cured product with high adhesion strength. things. In this way, the cured product of the curable composition described in Patent Document 4 has a trade-off relationship between high bonding strength and low refractive index. Therefore, when the curable composition described in Patent Document 4 is used, it is difficult to obtain a cured product having both high bonding strength and low refractive index.

又，已知藉由在硬化性組合物添加填料等來改善作業性等。 但是，因為通常含有填料等之硬化性組合物或其硬化物，其折射率係有變高之傾向，所以渴望一種即便添加填料等，折射率亦較低的硬化性組合物。 [先前技術文獻] [專利文獻]Moreover, it is known that workability|operativity etc. are improved by adding filler etc. to a curable composition. However, the refractive index of a curable composition or a cured product thereof that contains a filler or the like generally tends to increase. Therefore, a curable composition having a low refractive index even when a filler or the like is added is desired. [Prior technical literature] [Patent Document]

[專利文獻1] 日本特開2004-359933號公報 [專利文獻2] 日本特開2005-263869號公報 [專利文獻3] 日本特開2006-328231號公報 [專利文獻4] WO2017/110948號(US2018/0355111 A1)[Patent Document 1] Japanese Patent Application Publication No. 2004-359933 [Patent Document 2] Japanese Patent Application Publication No. 2005-263869 [Patent Document 3] Japanese Patent Application Publication No. 2006-328231 [Patent Document 4] WO2017/110948 (US2018/0355111 A1)

發明欲解決之課題 本發明係鑒於上述先前技術的實際情況而進行，其目的係提供一種具有優異的硬化性且折射率較低的硬化性組合物、作為該硬化性組合物的成分有用的硬化性聚倍半矽氧烷化合物、將前述硬化性組合物硬化而成之接著強度較高的硬化物、以及將前述硬化性組合物使用作為光學元件固定材用接著劑或光學元件固定材用密封劑之方法。 在本發明，所謂「硬化性組合物」，係指藉由滿足加熱等的預定條件而變化成為硬化物之組合物。 在本發明，所謂「硬化性聚倍半矽氧烷化合物」，係指藉由滿足加熱等的預定條件而單獨變化成為硬化物之聚倍半矽氧烷化合物、或在前述硬化性組合物達成作為硬化性成分的功能之聚倍半矽氧烷化合物。 用以解決課題之手段The problem to be solved by the invention The present invention was made in view of the actual situation of the above-mentioned prior art, and its object is to provide a curable composition having excellent curability and a low refractive index, and curable polysesquisilica useful as a component of the curable composition. An oxyalkane compound, a cured product with high adhesion strength obtained by curing the curable composition, and a method of using the curable composition as an adhesive for optical element fixing materials or a sealant for optical element fixing materials. In the present invention, "curable composition" refers to a composition that changes into a cured product by satisfying predetermined conditions such as heating. In the present invention, the "curable polysesquioxane compound" refers to a polysesquioxane compound that is individually transformed into a cured product by satisfying predetermined conditions such as heating, or is achieved in the aforementioned curable composition. A polysesquioxane compound that functions as a hardening component. means to solve problems

本發明者等係為了解決上述課題，而針對具有氟烷基的硬化性聚倍半矽氧烷化合物進行專心研討。 其結果發現， (1)由於將氟烷基導入至硬化性聚倍半矽氧烷化合物致使硬化物的接著強度為低落之問題，係能夠藉由使用具有特定重複單元且同時滿足有關分子結構之必要條件(後述必要條件1)及有關分子量之必要條件(後述必要條件2)之硬化性聚倍半矽氧烷化合物(以下有稱為「硬化性聚倍半矽氧烷化合物(A)」之情形)而解決；及 (2)含有硬化性聚倍半矽氧烷化合物(A)之硬化性組合物，因為具有優異的硬化性之特性，所以亦具有能夠不過度地加熱而進行硬化反應之優點。 而且，發現含有硬化性聚倍半矽氧烷化合物(A)及具有254℃以上的沸點之溶劑之硬化性組合物，因為塗佈後即便被放置長時間，黏度變化亦較小，所以具有與剛塗佈後同樣的作業性。 本發明係基於該等見解而完成。In order to solve the above-mentioned problems, the present inventors have intensively studied curable polysilsesquioxane compounds having a fluoroalkyl group. As a result, it was found that (1) The problem that the adhesion strength of the cured product is reduced due to the introduction of a fluoroalkyl group into the curable polysilsesquioxane compound can be solved by using a specific repeating unit that satisfies the necessary conditions for the molecular structure (to be described later) Requirement 1) and a curable polysesquioxane compound (hereinafter referred to as "curable polysesquioxane compound (A)") that require a molecular weight (requirement 2 described below) ;and (2) The curable composition containing the curable polysilsesquioxane compound (A) has excellent curing properties and therefore has the advantage of being able to proceed with the curing reaction without excessive heating. Furthermore, it was discovered that a curable composition containing a curable polysilsesquioxane compound (A) and a solvent having a boiling point of 254° C. or higher has a small change in viscosity even if it is left to stand for a long time after coating, so it has the same characteristics as Same workability right after coating. The present invention was completed based on these findings.

如此，依照本發明，能夠提供下述[1]~[5]的硬化性聚倍半矽氧烷化合物、[6]~[9]的硬化性組合物、[10]、[11]的硬化物、及[12]、[13]之硬化性組合物的使用方法。In this way, according to the present invention, it is possible to provide the curable polysesquioxane compounds of [1] to [5], the curable compositions of [6] to [9], and the cured compositions of [10] and [11]. objects, and methods of using the curable compositions of [12] and [13].

[1] 一種硬化性聚倍半矽氧烷化合物，係具有下述式(a-1)所示的重複單元之硬化性聚倍半矽氧烷化合物，其特徵在於：滿足下述必要條件1及必要條件2。[1] A curable polysesquioxane compound having a repeating unit represented by the following formula (a-1), characterized in that it satisfies the following necessary condition 1 and necessary condition 2.

[R1 表示組成式：Cm H(2m-n+1) Fn 所表示之氟烷基，m表示為1~10的整數，n表示為2以上且(2m+1)以下的整數，D表示將R1 與Si鍵結之連結基(但是伸烷基除外)或單鍵]， [必要條件1] 測定硬化性聚倍半矽氧烷化合物的29 Si-NMR時，能夠在-62ppm以上且小於-52ppm的區域[區域(2)]觀測到1或2個以上的尖峰，能夠在-52ppm以上且小於-45ppm的區域[區域(1)]及-73ppm以上且小於-62ppm的區域[區域(3)]之至少一區域觀測到1或2個以上的尖峰，而且下述式導出之Z2為20~40%，[R 1 represents a fluoroalkyl group represented by the composition formula: C m H (2m-n+1) F n , m represents an integer from 1 to 10, n represents an integer from 2 to (2m+1), D represents the linking group (excluding alkylene group) or single bond that bonds R 1 to Si], [Required condition 1] When measuring 29 Si-NMR of the curable polysilsesquioxane compound, it can be -62 ppm One or two or more peaks are observed in the area between -52ppm and less than -52ppm [Area (2)], and can be observed in the area between -52ppm and less than -45ppm [Area (1)] and the area between -73ppm and less than -62ppm. 1 or 2 or more peaks are observed in at least one area of [Region (3)], and Z2 derived from the following formula is 20~40%,

P1：在區域(1)之積分值 P2：在區域(2)之積分值 P3：在區域(3)之積分值 [必要條件2] 硬化性聚倍半矽氧烷化合物的質量平均分子量(Mw)為4,000~11,000。P1: Integral value in area (1) P2: Integral value in area (2) P3: Integral value in area (3) [Required condition 2] The mass average molecular weight (Mw) of the curable polysilsesquioxane compound is 4,000 to 11,000.

[2] 如[1]所述之硬化性聚倍半矽氧烷化合物，其中式(a-1)所示之重複單元比率係相對於總重複單元為25mol%以上。 [3] 如[1]或[2]所述之硬化性聚倍半矽氧烷化合物，其中進一步具有下述式(a-2)所示之重複單元。[2] The curable polysilsesquioxane compound as described in [1], wherein the ratio of the repeating units represented by formula (a-1) is 25 mol% or more relative to the total repeating units. [3] The curable polysesquioxane compound according to [1] or [2], which further has a repeating unit represented by the following formula (a-2).

[R2 表示未取代之碳數1~10的烷基、或具有取代基、或未取代之碳數6~12的芳基]。 [4] 如[3]所述之硬化性聚倍半矽氧烷化合物，其中式(a-2)所示之重複單元比率係相對於總重複單元為大於0mol%且75mol%以下。 [5] 如[1]至[3]項中任一項所述之硬化性聚倍半矽氧烷化合物，其中測定29 Si-NMR時，能夠在區域(3)觀測到1或2個以上的尖峰且下述式所導出的Z3為60~80%。[R 2 represents an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituent, or an unsubstituted aryl group having 6 to 12 carbon atoms]. [4] The curable polysilsesquioxane compound as described in [3], wherein the ratio of the repeating units represented by formula (a-2) is greater than 0 mol% and less than 75 mol% relative to the total repeating units. [5] The curable polysilsesquioxane compound according to any one of [1] to [3], wherein 1 or 2 or more can be observed in the region (3) when measuring 29 Si-NMR peak and Z3 derived from the following formula is 60~80%.

[6] 一種硬化性組合物，其特徵在於含有下述(A)成分、及具有254℃以上的沸點之溶劑。 (A)成分：如[1]至[5]項中任一項所述之硬化性聚倍半矽氧烷化合物 [7] 如[6]所述之硬化性組合物，係進一步含有下述(B)成分。 (B)成分：在分子內具有氮原子之矽烷偶合劑 [8] 如[6]或[7]所述之硬化性組合物，係進一步含有下述(C)成分。 (C)成分：在分子內具有酸酐結構之矽烷偶合劑 [9] 如[6]至[8]項中任一項所述之硬化性組合物，係進一步含有下述(D)。 (D)成分：平均一次粒徑為5~40nm的微粒 [10] 一種硬化物，係將如前述[6]至[9]項中任一項所述之硬化性組合物硬化而得到。 [11] 如[10]所述之硬化物，係光學元件固定材。 [12] 一種方法，係將如前述[6]至[9]項中任一項所述之硬化性組合物使用作為光學元件固定材用接著劑。 [13] 一種方法，係將如前述[6]至[9]項中任一項所述之硬化性組合物使用作為光學元件固定材用密封劑。 發明效果[6] A curable composition characterized by containing the following component (A) and a solvent having a boiling point of 254°C or higher. (A) Component: Curable polysilsesquioxane compound as described in any one of items [1] to [5] [7] The curable composition according to [6], further containing the following component (B). (B) Component: Silane coupling agent with nitrogen atoms in the molecule [8] The curable composition according to [6] or [7], further containing the following component (C). (C) Component: Silane coupling agent with an acid anhydride structure in the molecule [9] The curable composition according to any one of [6] to [8], further containing the following (D). (D) Component: Microparticles with an average primary particle size of 5~40nm [10] A cured product obtained by curing the curable composition described in any one of the above items [6] to [9]. [11] The hardened material described in [10] is an optical element fixing material. [12] A method of using the curable composition as described in any one of the above items [6] to [9] as an adhesive for optical element fixing materials. [13] A method of using the curable composition as described in any one of the above items [6] to [9] as a sealant for optical element fixing materials. Invention effect

依照本發明，能夠提供一種具有優異的硬化性且折射率較低的硬化性組合物、作為該硬化性組合物的成分有用的硬化性聚倍半矽氧烷化合物、將前述硬化性組合物硬化而成之接著強度較高的硬化物、以及將前述硬化性組合物使用作為光學元件固定材用接著劑或光學元件固定材用密封劑之方法。According to the present invention, it is possible to provide a curable composition having excellent curability and a low refractive index, a curable polysilsesquioxane compound useful as a component of the curable composition, and curing the curable composition. A cured product with high adhesion strength is obtained, and a method of using the curable composition as an adhesive for optical element fixing materials or a sealant for optical element fixing materials.

用以實施發明之形態 以下，將本發明分項成為1)硬化性聚倍半矽氧烷化合物、2)硬化性組合物、3)硬化物、及4)硬化性組合物的使用方法而詳細地說明。Form used to implement the invention Hereinafter, the present invention is divided into 1) curable polysilsesquioxane compound, 2) curable composition, 3) cured product, and 4) usage method of the curable composition and explained in detail.

1)硬化性聚倍半矽氧烷化合物 本發明的硬化性聚倍半矽氧烷化合物[硬化性聚倍半矽氧烷化合物(A)]係具有下述式(a-1)所示的重複單元之硬化性聚倍半矽氧烷化合物，其特徵在於滿足上述必要條件1及必要條件2。1) Hardening polysilsesquioxane compound The curable polysesquioxane compound [curable polysesquioxane compound (A)] of the present invention is a curable polysesquioxane having a repeating unit represented by the following formula (a-1) A compound characterized by satisfying the above-mentioned requirement 1 and requirement 2.

[R1 表示組成式Cm H(2m-n+1) Fn 所表示之氟烷基。m為1~10的整數，n表示2以上且(2m+1)以下的整數。D表示將R1 與Si鍵結之連結基(但是伸烷基除外)或單鍵]。[R 1 represents a fluoroalkyl group represented by the composition formula C m H (2m-n+1) F n . m is an integer from 1 to 10, and n represents an integer from 2 to (2m+1). D represents a linking group (except an alkylene group) or a single bond that bonds R 1 to Si].

式(a-1)中，R1 表示組成式：Cm H(2m-n+1) Fn 所表示之氟烷基。m為1~10的整數，n表示2以上且(2m+1)以下的整數。m係較佳為1~5的整數，更佳為1~3的整數。 藉由使用具有R1 之硬化性聚倍半矽氧烷化合物，能夠得到折射率較低的硬化性組合物。In the formula (a-1), R 1 represents a fluoroalkyl group represented by the composition formula: C m H (2m-n+1) F n . m is an integer from 1 to 10, and n represents an integer from 2 to (2m+1). m is preferably an integer of 1 to 5, more preferably an integer of 1 to 3. By using a curable polysilsesquioxane compound having R 1 , a curable composition with a lower refractive index can be obtained.

作為組成式：Cm H(2m-n+1) Fn 所表示之氟烷基，可舉出CF3 、CF3 CF2 、CF3 (CF2 )2 、CF3 (CF2 )3 、CF3 (CF2 )4 、CF3 (CF2 )5 、CF3 (CF2 )6 、CF3 (CF2 )7 、CF3 (CF2 )8 、CF3 (CF2 )9 等的全氟烷基；CF3 CH2 CH2 、CF3 (CF2 )3 CH2 CH2 、CF3 (CF2 )5 CH2 CH2 、CF3 (CF2 )7 CH2 CH2 等的氫氟烷基。Examples of the fluoroalkyl group represented by the composition formula: C m H (2m-n+1) F n include CF 3 , CF 3 CF 2 , CF 3 (CF 2 ) 2 , CF 3 (CF 2 ) 3 , CF 3 (CF 2 ) 4 , CF 3 (CF 2 ) 5 , CF 3 (CF 2 ) 6 , CF 3 (CF 2 ) 7 , CF 3 (CF 2 ) 8 , CF 3 (CF 2 ) 9 , etc. Fluoroalkyl; CF 3 CH 2 CH 2 , CF 3 (CF 2 ) 3 CH 2 CH 2 , CF 3 (CF 2 ) 5 CH 2 CH 2 , CF 3 (CF 2 ) 7 CH 2 CH 2, etc. Hydrofluorine alkyl.

式(a-1)中，D表示將R1 與Si鍵結之連結基(但是伸烷基除外)或單鍵。 作為D的連結基，可舉出1,4-伸苯基、1,3-伸苯基、1,2-伸苯基、1,5-伸萘基等碳數為6~20的伸芳基。In formula (a-1), D represents a linking group (excluding an alkylene group) or a single bond that bonds R 1 to Si. Examples of the connecting group of D include arylene groups having 6 to 20 carbon atoms such as 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, and 1,5-naphthylene group. base.

硬化性聚倍半矽氧烷化合物(A)可為具有1種(R1 -D)之物(同元聚合物)，亦可為具有2種以上的(R1 -D)之物(共聚物)。 硬化性聚倍半矽氧烷化合物(A)為共聚物時，硬化性聚倍半矽氧烷化合物(A)可為無規共聚物、嵌段共聚物、接枝共聚物、交替共聚物等的任一種，從製造容易性等觀點而言，係以無規共聚物為佳。 又，硬化性聚倍半矽氧烷化合物(A)的結構可為梯型(ladder type)結構、雙層型結構(double-decker)、籠型結構、部分開裂籠型結構、環狀型結構、無規型結構之任一種結構。The curable polysilsesquioxane compound (A) may have one type of (R 1 -D) (homopolymer), or may have two or more types of (R 1 -D) (copolymer). things). When the sclerosing polysesquioxane compound (A) is a copolymer, the sclerosing polysesquioxane compound (A) may be a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer, etc. Of any of them, random copolymers are preferred from the viewpoint of ease of production. In addition, the structure of the curable polysesquioxane compound (A) may be a ladder type structure, a double-decker structure, a cage type structure, a partially cracked cage type structure, or a cyclic type structure. , any kind of random structure.

在硬化性聚倍半矽氧烷化合物(A)所含有之式(a-1)所示的重複單元的比率，係相對於總重複單元，良好為25mol%以上，較佳為25~90mol%，更佳為25~85mol%。 藉由使用式(a-1)所示之重複單元比率係相對於總重複單元為25mol%以上的硬化性聚倍半矽氧烷化合物(A)，能夠得到折射率較低的硬化性組合物。The ratio of the repeating unit represented by the formula (a-1) contained in the curable polysilsesquioxane compound (A) is preferably 25 mol% or more, preferably 25 to 90 mol%, based on the total repeating units. , more preferably 25~85mol%. By using a curable polysilsesquioxane compound (A) in which the repeating unit ratio represented by formula (a-1) is 25 mol% or more relative to the total repeating units, a curable composition with a low refractive index can be obtained .

硬化性聚倍半矽氧烷化合物(A)亦可為進一步具有下述式(a-2)所示的重複單元之物(共聚物)。The curable polysilsesquioxane compound (A) may further have a repeating unit represented by the following formula (a-2) (copolymer).

式(a-2)中，R2 表示未取代之碳數1~10的烷基、或具有取代基、或是未取代之碳數6~12的芳基。In formula (a-2), R 2 represents an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituent, or an unsubstituted aryl group having 6 to 12 carbon atoms.

作為R2 之未取代之碳數1~10的烷基，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、正己基、正辛基、正壬基、正癸基等。Examples of the unsubstituted alkyl group having 1 to 10 carbon atoms in R 2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third butyl. , n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, etc.

作為R2 之未取代之碳數6~12的芳基，可舉出苯基、1-萘基、2-萘基等。 作為R2 之具有取代基之碳數6~12的芳基的取代基，可舉出甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、正戊基、正己基、正庚基、正辛基、異辛基等的烷基；氟原子、氯原子、溴原子等的鹵素原子；甲氧基、乙氧基等的烷氧基。Examples of the unsubstituted aryl group having 6 to 12 carbon atoms in R 2 include phenyl group, 1-naphthyl group, 2-naphthyl group, and the like. Examples of the substituent of the aryl group having a substituent of R 2 having 6 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, di-butyl, isobutyl, Alkyl groups such as tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, etc.; halogen atoms such as fluorine atom, chlorine atom, bromine atom, etc.; methoxy group, ethoxy group, etc. Alkoxy.

該等之中，作為R2 ，因為能容易得到接著強度較高且具有更優異的耐熱性之硬化物，係以未取代之碳數1~10的烷基為佳，以未取代之碳數1~6的烷基為較佳，以未取代之碳數1~3的烷基為特佳。Among these, R 2 is preferably an unsubstituted alkyl group with 1 to 10 carbon atoms, since it is easy to obtain a cured product with higher adhesion strength and more excellent heat resistance. Alkyl groups with 1 to 6 carbon atoms are preferred, and unsubstituted alkyl groups with 1 to 3 carbon atoms are particularly preferred.

硬化性聚倍半矽氧烷化合物(A)係具有式(a-2)所示之重複單元時，硬化性聚倍半矽氧烷化合物(A)可為具有1種R2 之物，亦可為具有2種以上的R2 之物。When the sclerosing polysesquioxane compound (A) has a repeating unit represented by formula (a-2), the sclerosing polysesquioxane compound (A) may have one type of R 2 , or It may have two or more types of R 2 .

硬化性聚倍半矽氧烷化合物(A)係具有式(a-2)所示之重複單元時，其比率係相對於總重複單元，良好為超過0mol%且75mol%以下，較佳為10~75mol%，更佳為15~75mol%。 藉由使用式(a-2)所示之重複單元比率為上述範圍內的硬化性聚倍半矽氧烷化合物(A)，而容易得到接著強度較高且具有更優異的耐熱性之硬化物。When the curable polysilsesquioxane compound (A) has a repeating unit represented by formula (a-2), the ratio is preferably more than 0 mol% and not more than 75 mol% relative to the total repeating units, preferably 10 ~75mol%, more preferably 15~75mol%. By using the curable polysilsesquioxane compound (A) in which the repeating unit ratio represented by formula (a-2) is within the above range, a cured product with higher adhesion strength and more excellent heat resistance can be easily obtained. .

硬化性聚倍半矽氧烷化合物(A)中之式(a-1)或式(a-2)所示之重複單元比率，係例如能夠藉由測定硬化性聚倍半矽氧烷化合物(A)的29 Si-NMR而求取。The ratio of repeating units represented by formula (a-1) or formula (a-2) in the curable polysilsesquioxane compound (A) can be measured, for example, by measuring the curable polysilsesquioxane compound ( A) Obtained from 29 Si-NMR.

因為硬化性聚倍半矽氧烷化合物(A)係對丙酮等的酮系溶劑；苯等的芳香族烴系溶劑；二甲基亞碸等的含硫系溶劑；四氫呋喃等的醚系溶劑；乙酸乙酯等的酯系溶劑；氯仿等的含鹵素系溶劑；及由該等2種以上所構成的混合溶劑等的各種有機溶劑為可溶，所以能夠使用該等溶劑而測定硬化性聚倍半矽氧烷化合物(A)在溶液狀態下的29 Si-NMR。Because the curable polysesquioxane compound (A) is a ketone solvent such as acetone; an aromatic hydrocarbon solvent such as benzene; a sulfur-containing solvent such as dimethylstyrene; an ether solvent such as tetrahydrofuran; Various organic solvents, such as ester solvents such as ethyl acetate; halogen-containing solvents such as chloroform; and mixed solvents composed of two or more of these solvents, are soluble, so the curable polypropylene times can be measured using these solvents. 29 Si-NMR of semisiloxane compound (A) in solution state.

式(a-1)所示之重複單元、式(a-2)所示之重複單元係下述式(a-3)所示之物。The repeating unit represented by formula (a-1) and the repeating unit represented by formula (a-2) are represented by the following formula (a-3).

[G表示(R1 -D)或R2 。R1 、D、R2 係各自表示與上述相同意思。所謂O1/2 ，表示與相鄰的重複單元共有氧原子]。[G represents (R 1 -D) or R 2 . R 1 , D and R 2 each have the same meaning as above. The so-called O 1/2 means that it shares oxygen atoms with adjacent repeating units].

如式(a-3)所示，硬化性聚倍半矽氧烷化合物(A)係具有通常被總稱為T-位置(T-site)之3個氧原子鍵結在矽原子且此外的1個基(G所表示之基)鍵結在矽原子而成之部分結構。 作為在硬化性聚倍半矽氧烷化合物(A)所含有的T-位置，可舉出下述式(a-4)~(a-6)所示之物。As shown in the formula (a-3), the curable polysilsesquioxane compound (A) has three oxygen atoms generally collectively referred to as the T-site (T-site) bonded to the silicon atom and an additional 1 A partial structure formed by bonding a group (the group represented by G) to a silicon atom. Examples of the T-position contained in the curable polysilsesquioxane compound (A) include those represented by the following formulas (a-4) to (a-6).

式(a-4)、(a-5)及(a-6)中，G表示與上述相同意思。R3 表示氫原子或碳數1~10的烷基。作為R3 之碳數1~10的烷基，可舉出甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基等。複數個R3 之間可全部相同亦可相不同。又，上述式(a-4)~(a-6)中，*係鍵結著矽原子。In formulas (a-4), (a-5) and (a-6), G represents the same meaning as above. R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms in R 3 include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl, and the like. A plurality of R 3 's may all be the same or different. Moreover, in the above formulas (a-4) to (a-6), silicon atoms are bonded to the * system.

式(a-4)及式(a-5)所示之T-位置，係含有能夠有助於聚縮合反應之基(R3 -O)。因而，含有多個該等T-位置之聚倍半矽氧烷化合物係具有優異的反應性。又，含有此種聚倍半矽氧烷化合物之組合物係具有優異的硬化性。 另一方面，式(a-5)及式(a-6)所示的T-位置係與2個以上的矽原子(相鄰的T-位置中的矽原子)鍵結著。因而，含有多個該等T-位置之聚倍半矽氧烷化合物係具有較大分子量之傾向。The T-position represented by formula (a-4) and formula (a-5) contains a group (R 3 -O) that can contribute to the polycondensation reaction. Therefore, polysilsesquioxane compounds containing a plurality of these T-positions have excellent reactivity. In addition, a composition containing such a polysesquioxane compound has excellent curing properties. On the other hand, the T-position represented by Formula (a-5) and Formula (a-6) is bonded to two or more silicon atoms (silicon atoms in adjacent T-positions). Therefore, polysilsesquioxane compounds containing multiple such T-positions tend to have larger molecular weights.

因而，含有多個式(a-5)所示的T-位置之聚倍半矽氧烷化合物係具有較大分子量且具有充分的反應性。 本發明係基於該見解而進行。亦即，本發明的硬化性聚倍半矽氧烷化合物(A)係滿足以下的必要條件1之物。Therefore, the polysesquioxane compound containing a plurality of T-positions represented by formula (a-5) has a relatively large molecular weight and sufficient reactivity. The present invention is based on this finding. That is, the curable polysilsesquioxane compound (A) of the present invention satisfies the following requirement 1.

(必要條件1) 在測定硬化性聚倍半矽氧烷化合物的29 Si-NMR時，係能夠在-62ppm以上且小於-52ppm的區域[區域(2)]觀測到1或2個以上的尖峰，而且能夠在-52ppm以上且小於-45ppm的區域[區域(1)]及-73ppm以上且小於-62ppm的區域[區域(3)]之至少一區域觀測到1或2個以上的尖峰且以下述式所導出之Z2為20~40%。 又，所謂「能夠在區域(1)觀測到之尖峰」，係指峰頂係位為區域(1)的範圍。針對「能夠在區域(2)觀測到之尖峰」、「能夠在區域(3)觀測到之尖峰」亦同樣。(Required condition 1) When measuring 29 Si-NMR of the curable polysilsesquioxane compound, one or two or more peaks can be observed in the region of -62 ppm or more and less than -52 ppm [region (2)] , and it is possible to observe 1 or 2 or more peaks and less in at least one of the area between -52ppm and less than -45ppm [area (1)] and the area between -73ppm and less than -62ppm [area (3)] The Z2 derived from the above formula is 20~40%. In addition, the so-called "peak that can be observed in area (1)" refers to the range where the peak top is located in area (1). The same applies to "the peak that can be observed in area (2)" and "the peak that can be observed in area (3)".

P1：在區域(1)之積分值 P2：在區域(2)之積分值 P3：在區域(3)之積分值P1: Integral value in area (1) P2: Integral value in area (2) P3: Integral value in area (3)

在本說明書，所謂「在區域(1)之積分值」、「在區域(2)之積分值」、「在區域(3)之積分值」，係指各自將-52ppm~-45ppm、-62ppm~-52ppm、-73ppm~-62ppm設為積分範圍且計算而得到之值。In this manual, the so-called "integrated value in area (1)", "integrated value in area (2)", and "integrated value in area (3)" mean -52ppm~-45ppm and -62ppm respectively. ~-52ppm, -73ppm~-62ppm are calculated using the integration range.

能夠在區域(1)、區域(2)、區域(3)觀測到之尖峰，係各自源自式式(a-4)、式(a-5)、式(a-6)所示之T-位置中的矽原子之物。The peaks that can be observed in area (1), area (2), and area (3) are derived from T represented by formula (a-4), formula (a-5), and formula (a-6) respectively. -The silicon atom thing in position.

因而，滿足必要條件1之硬化性聚倍半矽氧烷化合物，係相對於T-位置全體，含有20~40%之式(a-5)所示的T-位置之物。 該硬化性聚倍半矽氧烷化合物係如上述，具有較大分子量且具有充分的反應性之物，作為硬化性組合物的硬化性成分為有用的。Therefore, the curable polysilsesquioxane compound that satisfies the requirement 1 contains 20 to 40% of the T-position represented by the formula (a-5) with respect to the entire T-position. This curable polysilsesquioxane compound has a relatively large molecular weight and sufficient reactivity as described above, and is useful as a curable component of a curable composition.

必要條件1中，Z2之值係較佳為24~36%，更佳為27~32%。Z2太小時反應性不充分，Z2太大時儲存安定性低落。Among necessary conditions 1, the value of Z2 is preferably 24~36%, and more preferably 27~32%. When Z2 is too small, the reactivity is insufficient, and when Z2 is too large, storage stability is reduced.

硬化性聚倍半矽氧烷化合物(A)係在測定29 Si-NMR時，能夠在區域(3)觀測到1或2個以上的尖峰且以下述式所導出之Z3係以60~80%為佳。When measuring 29 Si-NMR of the curable polysilsesquioxane compound (A), one or two or more peaks can be observed in the region (3), and Z3 derived from the following formula is 60~80% Better.

Z3為60~80%之硬化性聚倍半矽氧烷化合物(A)，係相對於T-位置全體，含有60~80%之式(a-6)所示的T-位置之物。Z3之值為60~80%的範圍內之硬化性聚倍半矽氧烷化合物(A)，係分子量與反應性的平衡為更優異之物。 因為更容易得到該效果，Z3之值係以64~76%為較佳，以68~73%為更佳。Z3 is 60 to 80% of the curable polysilsesquioxane compound (A), which contains 60 to 80% of the T-position represented by the formula (a-6) with respect to the entire T-position. The curable polysesesquioxane compound (A) whose Z3 value is in the range of 60 to 80% has a better balance between molecular weight and reactivity. Because it is easier to obtain this effect, the Z3 value is preferably 64~76%, and 68~73% is even better.

Z2或Z3之值，係例如能夠在實施例記載的條件下測定29 Si-NMR而得到P1~P3且依照上述式而算出。The value of Z2 or Z3 can be calculated, for example, by measuring 29 Si-NMR under the conditions described in the examples to obtain P1 to P3, and in accordance with the above formula.

硬化性聚倍半矽氧烷化合物(A)係滿足上述必要條件2之物。亦即，硬化性聚倍半矽氧烷化合物(A)的質量平均分子量(Mw)為4,000~11,000，較佳為4,000~8,000，更佳為6,000~7,000。The curable polysilsesquioxane compound (A) satisfies the above-mentioned requirement 2. That is, the mass average molecular weight (Mw) of the curable polysesquioxane compound (A) is 4,000 to 11,000, preferably 4,000 to 8,000, more preferably 6,000 to 7,000.

如上述，滿足必要條件1之硬化性聚倍半矽氧烷化合物係具有較大分子量之傾向。必要條件2係使其分子量的範圍明確化。藉由將質量平均分子量(Mw)在上述範圍內之硬化性聚倍半矽氧烷化合物(A)使用作為硬化性成分，而能夠得到提供接著強度較高且具有優異的耐熱性的硬化物之硬化性組合物。As described above, the curable polysilsesquioxane compound that satisfies the requirement 1 tends to have a larger molecular weight. Necessary condition 2 is to clarify the range of its molecular weight. By using a curable polysilsesquioxane compound (A) having a mass average molecular weight (Mw) within the above range as a curable component, it is possible to obtain a cured product that provides high bonding strength and excellent heat resistance. Hardening composition.

硬化性聚倍半矽氧烷化合物(A)的分子量分布(Mw/Mn)係沒有特別限制，通常1.0~10.0，較佳為1.1~6.0的範圍。藉由將分子量分布(Mw/Mn)在上述範圍內的硬化性聚倍半矽氧烷化合物(A)使用作為硬化性成分，而能夠得到提供具有優異的接著性及耐熱性的硬化物之硬化性組合物。 質量平均分子量(Mw)及數量平均分子量(Mn)係例如能夠藉由將四氫呋喃(THF)作為溶劑之凝膠滲透層析法(GPC)且以標準聚苯乙烯換算值之方式而求取。The molecular weight distribution (Mw/Mn) of the curable polysilsesquioxane compound (A) is not particularly limited, but is usually in the range of 1.0 to 10.0, preferably 1.1 to 6.0. By using a curable polysilsesquioxane compound (A) having a molecular weight distribution (Mw/Mn) within the above range as a curable component, it is possible to obtain a cured product that provides excellent adhesion and heat resistance. sexual compositions. The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent and in terms of standard polystyrene conversion values.

硬化性聚倍半矽氧烷化合物(A)係例如能夠藉由下述式(a-7)所示之化合物(以下有稱為「矽烷化合物(1)」之情形)、或矽烷化合物(1)及以下述式(a-8)所示之化合物(以下有稱為「矽烷化合物(2)」之情形)在聚縮合觸媒的存在下使其聚縮合而製造。The curable polysilsesquioxane compound (A) can be, for example, a compound represented by the following formula (a-7) (hereinafter sometimes referred to as "silane compound (1)"), or a silane compound (1 ) and a compound represented by the following formula (a-8) (hereinafter referred to as "silane compound (2)") are produced by polycondensation in the presence of a polycondensation catalyst.

式(a-7)、(a-8)中，R1 、R2 、D表示與上述相同意思。R4 、R5 係各自獨立地表示碳數1~10的烷基，X1 、X2 係各自獨立地表示鹵素原子，p、q係各自獨立地表示0~3的整數。複數個R4 、R5 、及複數個X1 、X2 係各自可互相相同亦可互相不同。In the formulas (a-7) and (a-8), R 1 , R 2 and D have the same meanings as above. R 4 and R 5 each independently represent an alkyl group having 1 to 10 carbon atoms, X 1 and X 2 each independently represent a halogen atom, and p and q each independently represent an integer of 0 to 3. The plurality of R 4 and R 5 and the plurality of X 1 and X 2 may be the same as each other or different from each other.

作為R4 、R5 之碳數1~10的烷基，可舉出與作為R2 之碳數1~10的烷基已出示之物同樣物。 作為X1 、X2 的鹵素原子，可舉出氯原子、及溴原子等。Examples of the alkyl group having 1 to 10 carbon atoms in R 4 and R 5 include the same ones as those already shown as the alkyl group having 1 to 10 carbon atoms in R 2 . Examples of the halogen atoms of X 1 and X 2 include chlorine atoms, bromine atoms, and the like.

作為矽烷化合物(1)，可舉出CF3 Si(OCH3 )3 、CF3 CF2 Si(OCH3 )3 、CF3 CF2 CF2 Si(OCH3 )3 、CF3 CF2 CF2 CF2 Si(OCH3 )3 、CF3 CH2 CH2 Si(OCH3 )3 、CF3 CF2 CF2 CF2 CH2 CH2 Si(OCH3 )3 、CF3 CF2 CF2 CF2 CF2 CF2 CH2 CH2 Si(OCH3 )3 、CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 CH2 CH2 Si(OCH3 )3 、CF3 (C6 H4 )Si(OCH3 )3 (4-(三氟甲基)苯基三甲氧基矽烷)、CF3 Si(OCH2 CH3 )3 、CF3 CF2 Si(OCH2 CH3 )3 、CF3 CF2 CF2 Si(OCH2 CH3 )3 、CF3 CF2 CF2 CF2 Si(OCH2 CH3 )3 、CF3 CH2 CH2 Si(OCH2 CH3 )3 、CF3 CF2 CF2 CF2 CH2 CH2 Si(OCH2 CH3 )3 、CF3 CF2 CF2 CF2 CF2 CF2 CH2 CH2 Si(OCH2 CH3 )3 、CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 CH2 CH2 Si(OCH2 CH3 )3 、CF3 (C6 H4 )Si(OCH2 CH3 )3 、4-(三氟甲基)苯基三乙氧基矽烷等的氟烷基三烷氧基矽烷化合物類； CF3 SiCl(OCH3 )2 、CF3 CF2 SiCl(OCH3 )2 、CF3 CF2 CF2 SiCl(OCH3 )2 、CF3 SiBr(OCH3 )2 、CF3 CF2 SiBr(OCH3 )2 、CF3 CF2 CF2 SiBr(OCH3 )2 、CF3 CF2 CF2 CF2 SiCl(OCH3 )2 、CF3 CH2 CH2 SiCl(OCH3 )2 、CF3 CF2 CF2 CF2 CH2 CH2 SiCl(OCH3 )2 、CF3 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl(OCH3 )2 、CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl(OCH3 )2 、CF3 (C6 H4 )SiCl(OCH3 )2 、4-(三氟甲基)苯基氯二甲氧基矽烷、CF3 SiCl(OCH2 CH3 )2 、CF3 CF2 SiCl(OCH2 CH3 )2 、CF3 CF2 CF2 SiCl(OCH2 CH3 )2 、CF3 CF2 CF2 CF2 SiCl(OCH2 CH3 )2 、CF3 CH2 CH2 SiCl(OCH2 CH3 )2 、CF3 CF2 CF2 CF2 CH2 CH2 SiCl(OCH2 CH3 )2 、CF3 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl(OCH2 CH3 )2 、CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl(OCH2 CH3 )2 、CF3 (C6 H4 )SiCl(OCH2 CH3 )2 、4-(三氟甲基)苯基氯二乙氧基矽烷等的氟烷基鹵基二烷氧基矽烷化合物類；CF3 SiCl2 (OCH3 )、CF3 CF2 SiCl2 (OCH3 )、CF3 CF2 CF2 SiCl2 (OCH3 )、CF3 CF2 CF2 CF2 SiCl2 (OCH3 )、CF3 CH2 CH2 SiCl2 (OCH3 )、CF3 CF2 CF2 CF2 CH2 CH2 SiCl2 (OCH3 )、CF3 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl2 (OCH3 )、CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl2 (OCH3 )、CF3 (C6 H4 )SiCl2 (OCH3 )、4-(三氟甲基)苯基二氯甲氧基矽烷、CF3 SiCl2 (OCH2 CH3 )、CF3 CF2 SiCl2 (OCH2 CH3 )、CF3 CF2 CF2 SiCl2 (OCH2 CH3 )、CF3 CF2 CF2 CF2 SiCl2 (OCH2 CH3 )、CF3 CH2 CH2 SiCl2 (OCH2 CH3 )、CF3 CF2 CF2 CF2 CH2 CH2 SiCl2 (OCH2 CH3 )、CF3 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl2 (OCH2 CH3 )2 、CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl2 (OCH2 CH3 )、CF3 (C6 H4 )SiCl2 (OCH2 CH3 )、4-(三氟甲基)苯基二氯乙氧基矽烷等的氟烷基二鹵基烷氧基矽烷化合物類； CF3 SiCl3 、CF3 CF2 SiCl3 、CF3 SiBr3 、CF3 CF2 SiBr3 、CF3 CF2 CF2 SiCl3 、CF3 CF2 CF2 CF2 SiCl3 、CF3 CH2 CH2 SiCl3 、CF3 CF2 CF2 CF2 CH2 CH2 SiCl3 、CF3 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl3 、CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl3 、CF3 (C6 H4 )SiCl3 、4-三氟甲基苯基三氯矽烷、CF3 SiCl3 、CF3 CF2 SiCl3 、CF3 CF2 CF2 SiCl3 、CF3 CF2 CF2 CF2 SiCl3 、CF3 CH2 CH2 SiCl3 、CF3 CF2 CF2 CF2 CH2 CH2 SiCl3 、CF3 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl3 、CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 CH2 CH2 SiCl3 、CF3 (C6 H4 )SiCl3 、4-(三氟甲基)苯基三氯矽烷等的氟烷基三鹵基矽烷化合物類。 矽烷化合物(1)係能夠單獨1種或組合2種以上而使用。Examples of the silane compound (1) include CF 3 Si(OCH 3 ) 3 , CF 3 CF 2 Si(OCH 3 ) 3 , CF 3 CF 2 CF 2 Si(OCH 3 ) 3 and CF 3 CF 2 CF 2 CF. 2 Si(OCH 3 ) 3 , CF 3 CH 2 CH 2 Si(OCH 3 ) 3 , CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 Si(OCH 3 ) 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 Si(OCH 3 ) 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 Si(OCH 3 ) 3 , CF 3 (C 6 H 4 )Si( OCH 3 ) 3 (4-(trifluoromethyl)phenyltrimethoxysilane), CF 3 Si(OCH 2 CH 3 ) 3 , CF 3 CF 2 Si(OCH 2 CH 3 ) 3 , CF 3 CF 2 CF 2 Si(OCH 2 CH 3 ) 3 , CF 3 CF 2 CF 2 CF 2 Si(OCH 2 CH 3 ) 3 , CF 3 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 , CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 , CF 3 (C 6 H 4 )Si(OCH 2 CH 3 ) 3 , 4-(trifluoromethyl)phenyltriethoxysilane, etc. Fluoroalkyltrialkoxysilane compounds; CF 3 SiCl(OCH 3 ) 2 , CF 3 CF 2 SiCl(OCH 3 ) 2 , CF 3 CF 2 CF 2 SiCl(OCH 3 ) 2 , CF 3 SiBr(OCH 3 ) 2 , CF 3 CF 2 SiBr(OCH 3 ) 2 , CF 3 CF 2 CF 2 SiBr(OCH 3 ) 2 , CF 3 CF 2 CF 2 CF 2 SiCl(OCH 3 ) 2 , CF 3 CH 2 CH 2 SiCl (OCH 3 ) 2 , CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl(OCH 3 ) 2 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl (OCH 3 ) 2 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl(OCH 3 ) 2 , CF 3 (C 6 H 4 )SiCl(OCH 3 ) 2 , 4-(trifluoromethyl)phenyl Chlorodimethoxysilane, CF 3 SiCl (OCH 2 CH 3 ) 2 , CF 3 CF 2 SiCl(OCH 2 CH 3 ) 2 , CF 3 CF 2 CF 2 SiCl(OCH 2 CH 3 ) 2 , CF 3 CF 2 CF 2 CF 2 SiCl(OCH 2 CH 3 ) 2 , CF 3 CH 2 CH 2 SiCl(OCH 2 CH 3 ) 2 , CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl (OCH 2 CH 3 ) 2 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl(OCH 2 CH 3 ) 2 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl (OCH 2 CH 3 ) 2 , CF 3 (C 6 H 4 )SiCl(OCH 2 CH 3 ) 2 , 4-(trifluoromethyl)phenyl chloride diethoxysilane and other fluoroalkyl halodialkoxysilane compounds ;CF 3 SiCl 2 (OCH 3 ), CF 3 CF 2 SiCl 2 (OCH 3 ), CF 3 CF 2 CF 2 SiCl 2 (OCH 3 ), CF 3 CF 2 CF 2 CF 2 SiCl 2 (OCH 3 ), CF 3 CH 2 CH 2 SiCl 2 (OCH 3 ), CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 2 (OCH 3 ), CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 2 ( OCH 3 ), CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 2 (OCH 3 ), CF 3 (C 6 H 4 )SiCl 2 (OCH 3 ), 4- (三Fluoromethyl)phenyldichloromethoxysilane, CF 3 SiCl 2 (OCH 2 CH 3 ), CF 3 CF 2 SiCl 2 (OCH 2 CH 3 ), CF 3 CF 2 CF 2 SiCl 2 (OCH 2 CH 3 ), CF 3 CF 2 CF 2 CF 2 SiCl 2 (OCH 2 CH 3 ), CF 3 CH 2 CH 2 SiCl 2 (OCH 2 CH 3 ), CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 2 (OCH 2 CH 3 ), CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 2 (OCH 2 CH 3 ) 2 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 Fluoroalkyl dihalides such as SiCl 2 (OCH 2 CH 3 ), CF 3 (C 6 H 4 )SiCl 2 (OCH 2 CH 3 ), 4-(trifluoromethyl)phenyldichloroethoxysilane, etc. Alkoxysilane compounds; CF 3 SiCl 3 , CF 3 CF 2 SiCl 3 , CF 3 SiBr 3 , CF 3 CF 2 SiBr 3 , CF 3 CF 2 CF 2 SiCl 3 , CF 3 CF 2 CF 2 CF 2 SiCl 3. CF 3 CH 2 CH 2 SiCl 3 , CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 3 , CF 3 (C 6 H 4 )SiCl 3 , 4-trifluoromethylphenyltrichlorosilane, CF 3 SiCl 3 , CF 3 CF 2 SiCl 3 , CF 3 CF 2 CF 2 SiCl 3 , CF 3 CF 2 CF 2 CF 2 SiCl 3 , CF 3 CH 2 CH 2 SiCl 3 , CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 SiCl 3 , CF 3 (C 6 H 4 )SiCl 3 , Fluoroalkyltrihalosilane compounds such as 4-(trifluoromethyl)phenyltrichlorosilane. Silane compound (1) can be used individually by 1 type or in combination of 2 or more types.

該等之中，作為矽烷化合物(1)，係以在氟烷基三烷氧基矽烷化合物類所含有之物為佳。 Among these, the silane compound (1) is preferably one contained in fluoroalkyltrialkoxysilane compounds.

作為矽烷化合物(2)，可舉出甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、乙基三丙氧基矽烷、正丙基三甲氧基矽烷、正丙基三乙氧基矽烷、正丙基三丙氧基矽烷、正丙基三丁氧基矽烷、正丁基三甲氧基矽烷、異丁基三甲氧基矽烷、正戊基三甲氧基矽烷、正己基三甲氧基矽烷、異辛基三乙氧基矽烷等的烷基三烷氧基矽烷化合物類；甲基氯二甲氧基矽烷、甲基氯二乙氧基矽烷、甲基二氯甲氧基矽烷、甲基溴二甲氧基矽烷、乙基氯二甲氧基矽烷、乙基氯二乙氧基矽烷、乙基二氯甲氧基矽烷、乙基溴二甲氧基矽烷、正丙基氯二甲氧基矽烷、正丙基二氯甲氧基矽烷、正丁基氯二甲氧基矽烷、正丁基二氯甲氧基矽烷等的烷基鹵基烷氧基矽烷化合物類；甲基三氯矽烷、甲基三溴矽烷、乙基三氯矽烷、乙基三溴矽烷、正丙基三氯矽烷、正丙基三溴矽烷、正丁基三氯矽烷、異丁基三氯矽烷、正戊基三氯矽烷、正己基三氯矽烷、異辛基三氯矽烷等的烷基三鹵基矽烷合物類等。矽烷化合物(21係能夠單獨1種或組合2種以上而使用。 Examples of the silane compound (2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyl Trimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-propyltrimethoxysilane Alkyltrialkoxysilane compounds such as pentyltrimethoxysilane, n-hexyltrimethoxysilane, isooctyltriethoxysilane, etc.; methyl chloride dimethoxysilane, methyl chloride diethoxy Silane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, ethyl bromide Alkyl halides such as dimethoxysilane, n-propylchlorodimethoxysilane, n-propyldichloromethoxysilane, n-butylchlorodimethoxysilane, n-butyldichloromethoxysilane, etc. Alkoxysilane compounds; methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, ethyltribromosilane, n-propyltrichlorosilane, n-propyltribromosilane, n-butyltrichlorosilane Alkyl trihalosilane compounds such as chlorosilane, isobutyltrichlorosilane, n-pentyltrichlorosilane, n-hexyltrichlorosilane, isooctyltrichlorosilane, etc. The silane compound (21 series) can be used alone or in combination of two or more types.

該等之中，作為矽烷化合物(2)，係以在烷基三烷氧基矽烷化合物類所含有之物為佳。 Among these, the silane compound (2) is preferably one contained in alkyltrialkoxysilane compounds.

使上述矽烷化合物聚縮合之方法係沒有特別限定，能夠利用習知的方法。但是因為在硬化性聚倍半矽氧烷化合物(A)的製造係有以下所示之問題，所以必須特別地對反應條件進行研討。 The method for polycondensing the silane compound is not particularly limited, and a conventional method can be used. However, the production of the curable polysilsesquioxane compound (A) involves the following problems, so the reaction conditions must be particularly studied.

製造硬化性聚倍半矽氧烷化合物(A)時的問題之一，係在上述專利文獻4所示。亦即，觀看上述專利文獻4的表1時，得知隨著具有氟烷基之矽烷化合物的使用比率增加，所得到的聚合物有低分子量化之傾向。 One of the problems in producing the curable polysilsesquioxane compound (A) is shown in the above-mentioned Patent Document 4. That is, when Table 1 of the above-mentioned Patent Document 4 is viewed, it is found that as the usage ratio of the silane compound having a fluoroalkyl group increases, the resulting polymer tends to have a lower molecular weight.

如此，因為矽烷化合物(1)的反應性與矽烷化合物(2)的反應性為大大地不同，所以直接利用有關矽烷化合物(2)的聚縮合反應之先前的見解，係難以得到滿足必要條件1及必要條件2之硬化性聚倍半矽氧烷化合物。In this way, since the reactivity of the silane compound (1) is greatly different from the reactivity of the silane compound (2), it is difficult to directly use the previous knowledge about the polycondensation reaction of the silane compound (2) to obtain the necessary condition 1. and the hardening polysesquioxane compound required for condition 2.

在專利文獻4的實施例，實際上係使用具有氟烷基矽烷化合物而進行聚縮合反應來製造聚合物。但是如上述，在該文獻記載之製造方法，反應所使用的矽烷化合物之混合比率係大大地影響反應，所以無法控制聚合物的分子量。 又，如後述，雖然藉由使用專利文獻4的實施例記載的反應條件，而能夠將反應性較差之矽烷化合物(具有氟烷基之矽烷化合物)使用作為單體，但是即便使用該反應條件，亦難以得到滿足必要條件1及必要條件2之硬化性聚倍半矽氧烷化合物(比較例1~3)。In the Example of Patent Document 4, a polymer is actually produced by using a fluoroalkylsilane compound and performing a polycondensation reaction. However, as mentioned above, in the production method described in this document, the mixing ratio of the silane compound used in the reaction greatly affects the reaction, so the molecular weight of the polymer cannot be controlled. Furthermore, as will be described later, by using the reaction conditions described in the Examples of Patent Document 4, a less reactive silane compound (silane compound having a fluoroalkyl group) can be used as a monomer. However, even if this reaction condition is used, It is also difficult to obtain a curable polysesquioxane compound that satisfies the requirements 1 and 2 (Comparative Examples 1 to 3).

本發明者等係針對使用矽烷化合物(1)之聚縮合反應進行研討之結果，得知藉由在較溫和的條件下花費時間進行聚縮合反應，而能夠得到滿足必要條件1及必要條件2之硬化性聚倍半矽氧烷化合物。 具體而言，係在溶劑中、或無溶劑且使用適量的酸觸媒在預定溫度進行矽烷化合物的聚縮合反應而得到含有製造中間體的反應液之後，添加鹼而將反應液中和，而且藉由進行聚縮合反應而能夠製造硬化性聚倍半矽氧烷化合物(A)。As a result of studies conducted by the present inventors on the polycondensation reaction using the silane compound (1), it was found that by performing the polycondensation reaction under relatively mild conditions for a long time, it is possible to obtain a polycondensation reaction that satisfies the requirements 1 and 2. Hardening polysilsesquioxane compound. Specifically, a polycondensation reaction of a silane compound is performed at a predetermined temperature in a solvent or without a solvent using an appropriate amount of acid catalyst to obtain a reaction liquid containing a production intermediate, and then a base is added to neutralize the reaction liquid, and The curable polysilsesquioxane compound (A) can be produced by performing a polycondensation reaction.

作為溶劑，可舉出水；苯、甲苯、二甲苯等的芳香族烴類；乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸甲酯等的酯類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等的酮類；甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇類等的醇類等。該等溶劑係能夠單獨1種或組合2種以上而使用。 使用溶劑時，其使用量係矽烷化合物的總mol量每1mol通常0.001~10.000升，較佳為0.010~0.9升。Examples of the solvent include water; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; acetone, methyl Ketones such as ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, etc. of alcohols, etc. These solvent systems can be used individually by 1 type or in combination of 2 or more types. When a solvent is used, the usage amount is usually 0.001 to 10.000 liters per 1 mol of the total molar amount of the silane compound, preferably 0.010 to 0.9 liters.

作為酸觸媒，可舉出磷酸、鹽酸、硼酸、硫酸、硝酸等的無機酸；檸檬酸、乙酸、甲磺酸、三氟甲磺酸、苯磺酸、對甲苯磺酸等的有機酸等。該等之中，係以選自磷酸、鹽酸、硼酸、硫酸、檸檬酸、乙酸、及甲磺酸之至少1種為佳。 Examples of the acid catalyst include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, and nitric acid; and organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. . Among these, at least one selected from the group consisting of phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferred.

酸觸媒的使用量係相對於矽烷化合物的總mol量，通常0.01~2.00mol%，較佳為0.05~1.00mol%，更佳為0.10~0.30mol%的範圍。 The usage amount of the acid catalyst is relative to the total molar amount of the silane compound, usually 0.01~2.00mol%, preferably 0.05~1.00mol%, and more preferably 0.10~0.30mol%.

在酸觸媒存在下之反應的反應溫度係通常20~90℃，較佳為25~80℃。 The reaction temperature of the reaction in the presence of acid catalyst is usually 20~90°C, preferably 25~80°C.

在酸觸媒存在下之反應的反應時間係通常1~48小時，較佳為3~24小時。 The reaction time of the reaction in the presence of acid catalyst is usually 1 to 48 hours, preferably 3 to 24 hours.

藉由酸觸媒存在下的反應而得到之製造中間體的質量平均分子量(Mw)係通常800~5,000，較佳為1,200~4,000。 The mass average molecular weight (Mw) of the manufacturing intermediate obtained by reaction in the presence of an acid catalyst is usually 800~5,000, preferably 1,200~4,000.

作為將反應液中和時所使用的鹼，可舉出氨水；三甲胺、三乙胺、吡啶、1,8-二氮雜雙環[5.4.0]-7-十一烯、苯胺、甲吡啶、1,4-二氮雜雙環[2.2.2]辛烷、咪唑等的有機鹼；氫氧化四甲基銨、氫氧化四乙基銨等的有機鹽氫氧化物；甲氧化鈉、乙氧化鈉、第三丁氧化鈉、第三丁氧化鉀等的金屬烷氧化物；氫化鈉、氫化鈣等的金屬氫化物；氫氧化鈉、氫氧化鉀、氫氧化鈣等的金屬氫氧化物；碳酸鈉、碳酸鉀、碳酸鎂等的金屬碳酸鹽；碳酸氫鈉、碳酸氫鉀等的金屬碳酸氫鹽等。 Examples of the base used when neutralizing the reaction liquid include aqueous ammonia; trimethylamine, triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, and picoline , 1,4-diazabicyclo[2.2.2]octane, imidazole and other organic bases; organic salt hydroxides of tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc.; sodium methoxide, ethoxylate Metal alkoxides of sodium, sodium tertbutoxide, potassium tertbutoxide, etc.; metal hydrides of sodium hydride, calcium hydride, etc.; metal hydroxides of sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.; carbonic acid Metal carbonates such as sodium, potassium carbonate, magnesium carbonate, etc.; metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, etc.

在反應液之中和所使用的鹼之量，係相對於矽烷化合物的總mol量，通常0.01~2.00mol%，較佳為0.05~1.00mol%，更佳為0.10~0.70mol%的範圍。 The amount of alkali used for neutralization in the reaction solution is usually in the range of 0.01 to 2.00 mol%, preferably 0.05 to 1.00 mol%, and more preferably 0.10 to 0.70 mol% relative to the total molar amount of the silane compound.

又，在反應液之中和所使用的鹼之量(mol)，係以在1步驟所使用的酸觸媒之量(mol)的0.5~5.0倍為佳，較佳為0.8~3.0倍，更佳為1.0~2.0倍。 In addition, the amount (mol) of the base used in the reaction solution is preferably 0.5 to 5.0 times the amount (mol) of the acid catalyst used in the first step, and preferably 0.8 to 3.0 times. More preferably, it is 1.0~2.0 times.

中和後的反應液的pH係通常6.0~8.0，較佳為6.2~7.0，更佳為6.4~6.9。 The pH of the neutralized reaction solution is usually 6.0 to 8.0, preferably 6.2 to 7.0, more preferably 6.4 to 6.9.

中和後之反應的反應溫度，係通常40~90℃，較佳為50~80℃。 The reaction temperature after neutralization is usually 40 to 90°C, preferably 50 to 80°C.

中和後之反應的反應時間，係通常20~200分鐘，較佳為30~150分鐘。The reaction time after neutralization is usually 20 to 200 minutes, preferably 30 to 150 minutes.

上述的製造方法之在酸觸媒存在下的反應，係將水解設為主要的目的，在中和後的反應係將脫水縮合設為主要的目的。 藉由如此而進行矽烷化合物的聚縮合反應，而能夠效率良好地製造目標硬化性聚倍半矽氧烷化合物(A)。In the above-mentioned manufacturing method, the reaction in the presence of an acid catalyst has hydrolysis as its main purpose, and the reaction after neutralization has dehydration and condensation as its main purpose. By proceeding with the polycondensation reaction of the silane compound in this way, the target curable polysilsesquioxane compound (A) can be produced efficiently.

反應結束後，係進行習知的精製處理而能夠將硬化性聚倍半矽氧烷化合物(A)離析。After the reaction is completed, the curable polysesquioxane compound (A) can be isolated by performing a conventional purification process.

本發明的硬化性聚倍半矽氧烷化合物係具備具有氟烷基的重複單元之物，而且具有充分的反應性且具有較大分子量之物。 此種硬化性聚倍半矽氧烷化合物，係使用作為具有優異的硬化性且折射率較低的硬化性組合物的硬化性成分為有用的。The curable polysilsesquioxane compound of the present invention has a repeating unit having a fluoroalkyl group, has sufficient reactivity, and has a relatively large molecular weight. Such a curable polysilsesquioxane compound is useful as a curable component of a curable composition having excellent curability and a low refractive index.

2)硬化性組合物 本發明的硬化性組合物之特徵在於含有下述(A)成分、及具有254℃以上的沸點之溶劑(以下有記載為「溶劑(S1)」之情形)。 (A)成分：本發明的硬化性聚倍半矽氧烷化合物(硬化性聚倍半矽氧烷化合物(A))2) Curing composition The curable composition of the present invention is characterized by containing the following component (A) and a solvent having a boiling point of 254° C. or higher (hereinafter referred to as "solvent (S1)"). (A) Component: Curable polysesquioxane compound of the present invention (curable polysesquioxane compound (A))

在本發明的硬化性組合物，硬化性聚倍半矽氧烷化合物(A)係能夠單獨1種或組合2種以上而使用。In the curable composition of the present invention, the curable polysilsesquioxane compound (A) can be used alone or in combination of two or more types.

本發明的硬化性組合物中的硬化性聚倍半矽氧烷化合物(A)之含量，係將硬化性組合物的固體成分全體作為基準，通常40~80質量%，較佳為50~70質量%。The content of the curable polysilsesquioxane compound (A) in the curable composition of the present invention is usually 40 to 80% by mass, preferably 50 to 70% based on the total solid content of the curable composition. Mass %.

溶劑(S1)的沸點為254℃以上，以254~300℃為佳。在此，沸點係指在1013hPa之沸點(在本說明書為相同)。The boiling point of the solvent (S1) is above 254°C, preferably 254~300°C. Here, the boiling point refers to the boiling point at 1013hPa (the same in this specification).

作為溶劑(S1)，係只要沸點為254℃以上且能夠將硬化性聚倍半矽氧烷化合物(A)溶解之物，就沒有特別限制。 此種溶劑(S1)係揮發速度較慢。因此，因為含有溶劑(S1)之硬化性組合物係在塗佈後即便被放置長時間，黏度變化亦較小，所以能夠與剛塗佈後同樣地將光學元件等良好地裝配。The solvent (S1) is not particularly limited as long as it has a boiling point of 254° C. or higher and can dissolve the curable polysesquioxane compound (A). This type of solvent (S1) evaporates slowly. Therefore, since the viscosity of the curable composition containing the solvent (S1) changes little even if it is left for a long time after application, optical elements and the like can be assembled satisfactorily in the same manner as immediately after application.

作為溶劑(S1)，具體而言係可舉出三丙二醇正丁醚(沸點274℃)、1,6-己二醇二丙烯酸酯(沸點260℃)、二乙二醇二丁醚(沸點256℃)、三乙二醇丁基甲醚(沸點261℃)、聚乙二醇二甲醚(沸點264~294℃)、四乙二醇二甲醚(沸點275℃)、聚乙二醇單甲醚(沸點、290~310℃)等。 該等之中，作為溶劑(S1)，從更容易得到本發明的效果的觀點而言，係以三丙二醇正丁醚、1,6-己二醇二丙烯酸酯為佳。 溶劑(S1)係能夠單獨1種或組合2種以上而使用。Specific examples of the solvent (S1) include tripropylene glycol n-butyl ether (boiling point 274°C), 1,6-hexanediol diacrylate (boiling point 260°C), and diethylene glycol dibutyl ether (boiling point 256°C). ℃), triethylene glycol butyl methyl ether (boiling point 261°C), polyethylene glycol dimethyl ether (boiling point 264~294°C), tetraethylene glycol dimethyl ether (boiling point 275°C), polyethylene glycol monomethyl ether (Boiling point, 290~310℃) etc. Among these, as the solvent (S1), tripropylene glycol n-butyl ether and 1,6-hexanediol diacrylate are preferred from the viewpoint of obtaining the effects of the present invention more easily. The solvent (S1) can be used individually by 1 type or in combination of 2 or more types.

本發明的硬化性組合物亦可含有溶劑(S1)以外的溶劑。作為溶劑(S1)以外的溶劑，係以沸點為200℃以上且小於254℃的溶劑(以下有記載為「溶劑(S2)」之情形)為佳。 作為溶劑(S2)，係只要沸點為200℃以上且小於254℃而且能夠將硬化性聚倍半矽氧烷化合物(A)溶解之物，就沒有特別限制。藉由併用溶劑(S1)與溶劑(S2)，硬化性組合物的硬化性提升。The curable composition of the present invention may contain a solvent other than the solvent (S1). As the solvent other than the solvent (S1), a solvent with a boiling point of 200° C. or more and less than 254° C. (hereinafter referred to as “solvent (S2)”) is preferred. The solvent (S2) is not particularly limited as long as it has a boiling point of 200° C. or more and less than 254° C. and can dissolve the curable polysesquioxane compound (A). By using the solvent (S1) and the solvent (S2) in combination, the curability of the curable composition is improved.

作為溶劑(S2)的具體例，可舉出二乙二醇單丁醚乙酸酯(沸點247℃)、二丙二醇正丁醚(沸點229℃)、苄醇(沸點204.9℃)、二丙二醇甲醚乙酸酯(沸點209℃)、二乙二醇丁基甲醚(沸點212℃)、二丙二醇正丙基醚(沸點212℃)、三丙二醇二甲醚(沸點215℃)、三乙二醇二甲醚(沸點216℃)、二乙二醇單***乙酸酯(沸點217.4℃)、二乙二醇正丁醚(沸點230℃)、乙二醇單苯基醚(沸點245℃)、三丙二醇甲醚(沸點242℃)、丙二醇苯基醚(沸點、243℃)、三乙二醇單甲醚(沸點249℃)等。 該等之中，作為溶劑(S2)，因為容易得到其效果，係以二醇系溶劑為佳，以二乙二醇單丁醚乙酸酯、二丙二醇正丁醚為佳，以二乙二醇單丁醚乙酸酯為較佳。Specific examples of the solvent (S2) include diethylene glycol monobutyl ether acetate (boiling point 247°C), dipropylene glycol n-butyl ether (boiling point 229°C), benzyl alcohol (boiling point 204.9°C), dipropylene glycol methyl Ether acetate (boiling point 209°C), diethylene glycol butyl methyl ether (boiling point 212°C), dipropylene glycol n-propyl ether (boiling point 212°C), tripropylene glycol dimethyl ether (boiling point 215°C), triethylene glycol dimethyl ether Methyl ether (boiling point 216°C), diethylene glycol monoethyl ether acetate (boiling point 217.4°C), diethylene glycol n-butyl ether (boiling point 230°C), ethylene glycol monophenyl ether (boiling point 245°C), tripropylene glycol Methyl ether (boiling point, 242°C), propylene glycol phenyl ether (boiling point, 243°C), triethylene glycol monomethyl ether (boiling point, 249°C), etc. Among them, as the solvent (S2), glycol solvents are preferred because the effect is easily obtained, diethylene glycol monobutyl ether acetate and dipropylene glycol n-butyl ether are preferred, and diethylene glycol solvent is preferred. Alcohol monobutyl ether acetate is preferred.

併用溶劑(S1)與溶劑(S2)時，具體而言係以三丙二醇正丁醚(溶劑(S1))與二乙二醇單丁醚乙酸酯(溶劑(S2))的組合、1,6-己二醇二丙烯酸酯(溶劑(S1))與二乙二醇單丁醚乙酸酯(溶劑(S2))的組合、三丙二醇正丁醚(溶劑(S1))與二丙二醇正丁醚(溶劑(S2))的組合、1,6-己二醇二丙烯酸酯(溶劑(S1))與二丙二醇正丁醚(有機溶劑(S2))的組合為佳。When the solvent (S1) and the solvent (S2) are used together, specifically, a combination of tripropylene glycol n-butyl ether (solvent (S1)) and diethylene glycol monobutyl ether acetate (solvent (S2)), 1, The combination of 6-hexanediol diacrylate (solvent (S1)) and diethylene glycol monobutyl ether acetate (solvent (S2)), tripropylene glycol n-butyl ether (solvent (S1)) and dipropylene glycol n-butyl ether A combination of ether (solvent (S2)) and a combination of 1,6-hexanediol diacrylate (solvent (S1)) and dipropylene glycol n-butyl ether (organic solvent (S2)) is preferred.

本發明的硬化性組合物，係含有固體成分濃度成為較佳50~95質量%、更佳60~85質量%之量的溶劑。藉由固體成分濃度為該範圍內，能夠充分地發揮溶劑(S1)或溶劑(S2)的效果。The curable composition of the present invention contains a solvent having a solid content concentration of preferably 50 to 95% by mass, more preferably 60 to 85% by mass. When the solid content concentration is within this range, the effect of the solvent (S1) or the solvent (S2) can be fully exerted.

在本發明的硬化性組合物所含有之溶劑(S1)與溶劑(S2)的合計量，係相對於總溶劑，通常50~100質量%，較佳為70~100質量%，更佳為90~100質量%。 在本發明的硬化性組合物所含有的溶劑(S1)之含量，係相對於溶劑(S1)與溶劑(S2)的合計量，通常20~100質量%，較佳為30~85質量%，更佳為50~80質量%。 以此種比率含有溶劑(S1)或溶劑(S2)之硬化性組合物，係成為接著性與濕潤擴大性(後述之有關液滴的擴大之特性)能夠適當地平衡之物。The total amount of the solvent (S1) and the solvent (S2) contained in the curable composition of the present invention is usually 50 to 100 mass %, preferably 70 to 100 mass %, and more preferably 90 mass % with respect to the total solvent. ~100 mass%. The content of the solvent (S1) contained in the curable composition of the present invention is usually 20 to 100 mass %, preferably 30 to 85 mass %, based on the total amount of the solvent (S1) and the solvent (S2). More preferably, it is 50~80 mass %. The curable composition containing the solvent (S1) or the solvent (S2) in such a ratio has an appropriate balance between adhesiveness and wet spreadability (characteristics related to the spread of droplets to be described later).

本發明的硬化性組合物亦可含有在分子內具有氮原子之矽烷偶合劑(以下有記載為「矽烷偶合劑(B)」之情形)作為(B)成分。The curable composition of the present invention may contain a silane coupling agent having a nitrogen atom in the molecule (hereinafter referred to as "silane coupling agent (B)") as the component (B).

含有矽烷偶合劑(B)之硬化性組合物，係在塗佈步驟具有優異的作業性且提供具有更優異的接著性、耐剝離性、及耐熱性之硬化物。 在此，所謂在塗佈步驟具有優異的作業性，係指在塗佈步驟，將硬化性組合物從吐出管吐出，隨後提高吐出管時，拉絲量較少、或立刻中斷之情形。藉由使用具有該性質之硬化性組合物，能夠防止樹脂飛濺和液滴擴大引起周圍的污染。The curable composition containing the silane coupling agent (B) has excellent workability in the coating step and provides a cured product with more excellent adhesion, peeling resistance, and heat resistance. Here, the term "excellent workability in the coating step" refers to the case where the curable composition is discharged from the discharge pipe in the coating step and then the discharge pipe is raised, the amount of wire drawing is small, or it is interrupted immediately. By using a curable composition having this property, it is possible to prevent resin splashing and droplet expansion causing surrounding contamination.

作為矽烷偶合劑(B)，係只要在分子內具有氮原子之矽烷偶合劑，就沒有特別限制。例如可舉出下述式(b-1)所表示之三烷氧基矽烷化合物、式(b-2)所表示之二烷氧基烷基矽烷化合物或二烷氧基芳基矽烷化合物等。The silane coupling agent (B) is not particularly limited as long as it has a nitrogen atom in the molecule. Examples thereof include a trialkoxysilane compound represented by the following formula (b-1), a dialkoxyalkylsilane compound represented by the formula (b-2), or a dialkoxyarylsilane compound.

上述式中，Ra 表示甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第三丁氧基等碳數1~6的烷氧基。複數個Ra 彼此可相同亦可不同。 Rb 表示甲基、乙基、正丙基、異丙基、正丁基、第三丁基等碳數1~6的烷基；或苯基、4-氯苯基、4-甲基苯基、1-萘基等具有取代基、或不具有取代基之芳基。In the above formula, R a represents an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy. Plural R a may be the same as or different from each other. R b represents an alkyl group with 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl; or phenyl, 4-chlorophenyl, or 4-methylbenzene group, 1-naphthyl, and other substituted or unsubstituted aryl groups.

Rc 表示具有氮原子之碳數1~10的有機基。又，Rc 亦可進一步與含有其它矽原子之基鍵結。 作為Rc 之碳數1~10的有機基的具體例，可舉出N-2-(胺乙基)-3-胺丙基、3-胺丙基、N-(1,3-二甲基-亞丁基)胺丙基、3-脲丙基、N-苯基-胺丙基等R c represents an organic group having 1 to 10 carbon atoms having a nitrogen atom. In addition, R c may be further bonded to a group containing other silicon atoms. Specific examples of the organic group having 1 to 10 carbon atoms in R c include N-2-(aminoethyl)-3-aminopropyl, 3-aminopropyl, and N-(1,3-dimethyl). (butylene)aminopropyl, 3-ureapropyl, N-phenyl-aminopropyl, etc.

上述式(b-1)或(b-2)所表示的化合物之中，作為Rc 係與含有其它矽原子之基鍵結而成之有機基時的化合物，可舉出透過異三聚氰酸酯骨架而與其它矽原子鍵結來構成異三聚氰酸酯系矽烷偶合劑之物、或透過脲骨架而與其它矽原子鍵結來構成脲系矽烷偶合劑之物。Among the compounds represented by the above formula (b-1) or (b-2), examples of compounds in which R c is an organic group bonded to a group containing other silicon atoms include isocyanuride. The acid ester skeleton is bonded with other silicon atoms to form an isocyanate silane coupling agent, or the urea skeleton is bonded with other silicon atoms to form a urea silane coupling agent.

該等之中，作為矽烷偶合劑(B)，因為容易得到接著強度較高的硬化物，以異三聚氰酸酯系矽烷偶合劑、及脲系矽烷偶合劑為佳，而且，以在分子內具有4個以上之鍵結在矽原子的烷氧基之物為佳。所謂具有4個以上之鍵結在矽原子的烷氧基，係意味著鍵結在相同的矽原子之烷氧基、與鍵結在不同的矽原子之烷氧基的總合計數為4以上。 Among them, as the silane coupling agent (B), isocyanate-based silane coupling agents and urea-based silane coupling agents are preferred because it is easy to obtain a cured product with high adhesion strength. Those with more than 4 alkoxy groups bonded to silicon atoms are preferred. The term “having 4 or more alkoxy groups bonded to silicon atoms” means that the total number of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is 4 or more. .

作為具有4個以上之鍵結在矽原子的烷氧基之異三聚氰酸酯系矽烷偶合劑，可舉出下述式(b-3)所表示之化合物；作為具有4個以上之鍵結在矽原子的烷氧基之脲系矽烷偶合劑，可舉出下述式(b-4)所表示之化合物。 Examples of the isocyanurate-based silane coupling agent having four or more alkoxy groups bonded to a silicon atom include compounds represented by the following formula (b-3); Examples of urea-based silane coupling agents having an alkoxy group bonded to a silicon atom include compounds represented by the following formula (b-4).

Figure 108135111-A0305-02-0024-1
Figure 108135111-A0305-02-0024-1

Figure 108135111-A0305-02-0024-2
Figure 108135111-A0305-02-0024-2

式中，Ra表示與上述相同意思。t1~t5係各自獨立地表示1~10的整數，以1~6的整數為佳，以3為特佳。 In the formula, R a represents the same meaning as above. t1~t5 each independently represent an integer from 1 to 10, with integers from 1 to 6 being preferred, and 3 being particularly preferred.

作為式(b-3)所表示之化合物的具體例，可舉出1,3,5-N-參(3-三甲氧矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-三乙氧矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-三異丙氧矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-三丁氧矽烷基丙基)異三聚氰酸酯等的1,3,5-N-參[(三(碳數1~6)烷氧基)矽烷基(碳數1~10)烷基]異三聚氰酸酯；1,3,5,-N-參(3-二甲氧基甲基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二甲氧基乙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二甲氧基異丙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二甲氧基正丙基矽烷基丙基)異三聚氰酸 酯、1,3,5,-N-參(3-二甲氧基苯基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二乙氧基甲基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二乙氧基乙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二乙氧基異丙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二乙氧基正丙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二乙氧基苯基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二異丙氧基甲基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二異丙氧基乙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二異丙氧基異丙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二異丙氧基正丙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二異丙氧基苯基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二丁氧基甲基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二丁氧基乙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二丁氧基異丙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二丁氧基正丙基矽烷基丙基)異三聚氰酸酯、1,3,5,-N-參(3-二丁氧基苯基矽烷基丙基)異三聚氰酸酯等的1,3,5-N-參[(二(碳數1~6)烷氧基)矽烷基(碳數1~10)烷基]異三聚氰酸酯等。 Specific examples of the compound represented by formula (b-3) include 1,3,5-N-trimethoxysilylpropyl)isocyanurate, 1,3,5, -N-Shen(3-triethoxysilylpropyl)isocyanurate, 1,3,5,-N-Shen(3-triisopropoxysilylpropyl)isocyanurate , 1,3,5-N-parasan(3-tributoxysilylpropyl)isocyanurate and other 1,3,5-N-parasan[(tris(carbon number 1~6)alkane Oxy)silyl (carbon number 1~10)alkyl]isocyanurate; 1,3,5,-N-(3-dimethoxymethylsilylpropyl)isocyanurate Acid ester, 1,3,5-N-Shen(3-dimethoxyethylsilylpropyl)isocyanurate, 1,3,5-N-Shen(3-dimethoxy 1,3,5,-N-(3-dimethoxyn-propylsilylpropyl)isocyanuric acid Ester, 1,3,5-N-Phenyl(3-dimethoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-Phenyl(3-diethoxy Methylsilylpropyl)isocyanurate, 1,3,5,-N-(3-diethoxyethylsilylpropyl)isocyanurate, 1,3,5 ,-N-Shen(3-diethoxyisopropylsilylpropyl)isocyanurate, 1,3,5,-N-Shen(3-diethoxyisopropylsilylpropyl)isocyanurate (3-Diethoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-Phenyl(3-diethoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-Phenyl (3-Diisopropoxymethylsilylpropyl)isocyanurate, 1,3,5,-N-(3-diisopropoxyethylsilylpropyl)isotrimeric Cyanate ester, 1,3,5-N-Shen(3-diisopropoxyisopropylsilylpropyl)isocyanurate, 1,3,5-N-Shen(3- Diisopropoxy n-propylsilylpropyl)isocyanurate, 1,3,5,-N-(3-diisopropoxyphenylsilylpropyl)isocyanuric acid Ester, 1,3,5,-N-Shen(3-dibutoxymethylsilylpropyl)isocyanurate, 1,3,5,-N-Shen(3-dibutoxy Ethylsilylpropyl)isocyanurate, 1,3,5,-N-(3-dibutoxyisopropylsilylpropyl)isocyanurate, 1,3, 5,-N-Shen(3-dibutoxyn-propylsilylpropyl)isocyanurate, 1,3,5,-N-Shen(3-dibutoxyphenylsilylpropyl)isocyanurate 1,3,5-N-paras[(di(carbon number 1~6)alkoxy)silyl(carbon number 1~10)alkyl]isocyanuric acid, etc. Ester etc.

作為式(b-4)所表示之化合物的具體例，可舉出N,N’-雙(3-三甲氧矽烷基丙基)脲、N,N’-雙(3-三乙氧矽烷基丙基)脲、N,N’-雙(3-三丙氧矽烷基丙基)脲、N,N’-雙(3-三丁氧矽烷基丙基)脲、N,N’-雙(2-三甲氧矽烷基乙基)脲等的N,N’-雙[(三(碳數1~6)烷氧基矽烷基)(碳數1~10)烷基]脲；N,N’-雙(3-二甲氧基甲基矽烷基丙基)脲、N,N’-雙(3-二甲氧基乙基矽烷基丙基)脲、N,N’-雙(3-二乙氧基甲基矽烷基丙基)脲等的N,N’-雙((二(碳數1~6)烷氧基(碳數1~6)烷基矽烷基(碳數1~10)烷基)脲；N,N’-雙(3-二甲氧基苯基矽烷基丙基)脲、N,N’-雙(3-二乙氧基苯基矽烷基丙基)脲等的N,N’-雙[(二(碳數1~6)烷氧基)(碳數6~20)芳基矽烷基(碳數1~10)烷基]脲等。 Specific examples of the compound represented by formula (b-4) include N,N'-bis(3-trimethoxysilylpropyl)urea and N,N'-bis(3-triethoxysilyl) Propyl)urea, N,N'-bis(3-trippropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N'-bis( N,N'-bis[(tris(carbon number 1~6)alkoxysilyl)(carbon number 1~10)alkyl]urea such as 2-trimethoxysilylethyl)urea; N,N' -Bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis(3-di N,N'-bis((di(carbon number 1~6)alkoxy(carbon number 1~6)alkylsilyl(carbon number 1~10)) such as ethoxymethylsilylpropyl)urea Alkyl) urea; N,N'-bis(3-dimethoxyphenylsilylpropyl)urea, N,N'-bis(3-diethoxyphenylsilylpropyl)urea, etc. N,N'-bis[(bis(carbon number 1~6)alkoxy)(carbon number 6~20)arylsilyl(carbon number 1~10)alkyl]urea, etc.

矽烷偶合劑(B)係能夠單獨1種或組合2種以上而使用。 Silane coupling agent (B) can be used individually by 1 type or in combination of 2 or more types.

該等之中，作為矽烷偶合劑(B)，係以使用1,3,5-N-參(3-三甲氧矽烷基丙基)異三聚氰酸酯、1,3,5-N-參(3-三乙氧矽烷基丙基)異三聚氰酸酯(以下稱為「異三聚氰酸酯化合物」)、N,N’-雙(3-三甲氧矽烷基丙基)脲、N,N’-雙(3-三乙氧矽烷基丙基)脲(以下稱為「脲化合物」)、及上述異三聚氰酸酯化合物與脲化合物的組合為佳。Among these, as the silane coupling agent (B), 1,3,5-N-trimethoxysilylpropylisocyanurate, 1,3,5-N- Ginseng(3-triethoxysilylpropyl)isocyanurate (hereinafter referred to as "isocyanurate compound"), N,N'-bis(3-trimethoxysilylpropyl)urea , N,N'-bis(3-triethoxysilylpropyl)urea (hereinafter referred to as "urea compound"), and a combination of the above isocyanurate compound and a urea compound are preferred.

將上述異三聚氰酸酯化合物與脲化合物組合而使用時，兩者的使用比例係(異三聚氰酸酯化合物)與(脲化合物)之質量比，以100：1~100：200為佳，以100：10~100：110為較佳。藉由採用此種比例而將異三聚氰酸酯化合物與脲化合物組合而使用，能夠得到提供接著強度較高且具有更優異的耐熱性的硬化物之硬化性組合物。When the above-mentioned isocyanate compound and urea compound are combined and used, the usage ratio of the two is the mass ratio of (isocyanurate compound) to (urea compound), which is 100:1~100:200. The best is 100:10~100:110. By combining the isocyanurate compound and the urea compound in such a ratio, it is possible to obtain a curable composition that provides a cured product with high bonding strength and more excellent heat resistance.

本發明的硬化性組合物係含有矽烷偶合劑(B)[(B)成分]時，(B)成分的含量係沒有特別限定，其量係上述(A)成分與(B)成分的質量比[(A)成分：(B)成分]，良好為100：0.1~100：90，較佳為100：0.3~100：60，較佳為100：1~100：50，更佳為100：3~100：40，特佳是成為100：5~100：30之量。 採用此種比例而含有(A)成分與(B)成分之硬化性組合物的硬化物，係成為接著強度較高且具有更優異的耐熱性之物。When the curable composition of the present invention contains the silane coupling agent (B) [component (B)], the content of the component (B) is not particularly limited, and the amount is the mass ratio of the component (A) to the component (B). [(A) Component: (B) Component], preferably 100:0.1~100:90, more preferably 100:0.3~100:60, more preferably 100:1~100:50, more preferably 100:3 ~100:40, the best is 100:5~100:30. The cured product of the curable composition containing the component (A) and the component (B) in such a ratio has higher bonding strength and more excellent heat resistance.

本發明的硬化性組合物亦可含有在分子內具有酸酐結構之矽烷偶合劑(以下有記載為「矽烷偶合劑(C)」之情形)作為(C)成分。 含有矽烷偶合劑(C)之硬化性組合物，係在塗佈步驟具有優異的作業性且提供接著強度較高且具有更優異的耐剝離性及耐熱性之硬化物。The curable composition of the present invention may contain a silane coupling agent (hereinafter referred to as "silane coupling agent (C)") having an acid anhydride structure in the molecule as the component (C). The curable composition containing the silane coupling agent (C) has excellent workability in the coating step and provides a cured product with high adhesion strength and more excellent peeling resistance and heat resistance.

作為矽烷偶合劑(C)，可舉出2-(三甲氧矽烷基)乙基琥珀酸酐、2-(三乙氧基矽烷基)乙基琥珀酸酐、3-(三甲氧矽烷基)丙基琥珀酸酐、3-(三乙氧基矽烷基)丙基琥珀酸酐等的三(碳數1~6)烷氧矽烷基(碳數2~8)烷基琥珀酸酐；2-(二甲氧基甲基矽烷基)乙基琥珀酸酐等的二(碳數1~6)烷氧基甲基矽烷基(碳數2~8)烷基琥珀酸酐；2-(甲氧基二甲基矽烷基)乙基琥珀酸酐等的(碳數1~6)烷氧基二甲基矽烷基(碳數2~8)烷基琥珀酸酐；Examples of the silane coupling agent (C) include 2-(trimethoxysilyl)ethylsuccinic anhydride, 2-(triethoxysilyl)ethylsuccinic anhydride, and 3-(trimethoxysilyl)propylsuccinic anhydride. Acid anhydride, tris(carbon number 1~6)alkoxysilyl(carbon number 2~8)alkylsuccinic anhydride such as 3-(triethoxysilyl)propylsuccinic anhydride; 2-(dimethoxymethyl Bis(C1~6)alkoxymethylsilyl(C2~8)alkylsuccinic anhydride such as silyl)ethylsuccinic anhydride; 2-(methoxydimethylsilyl)ethyl (C1~6) alkoxydimethylsilyl (C2~8) alkylsuccinic anhydride such as succinic anhydride;

2-(三氯矽烷基)乙基琥珀酸酐、2-(三溴矽烷基)乙基琥珀酸酐等的三鹵基矽烷基(碳數2~8)烷基琥珀酸酐；2-(二氯甲基矽烷基)乙基琥珀酸酐等的二鹵基甲基矽烷基(碳數2~8)烷基琥珀酸酐；2-(氯二甲基矽烷基)乙基琥珀酸酐等的鹵基二甲基矽烷基(碳數2~8)烷基琥珀酸酐等。矽烷偶合劑(C)係能夠單獨1種或組合2種以上而使用。Trihalosilyl (carbon number 2~8) alkylsuccinic anhydride such as 2-(trichlorosilyl)ethylsuccinic anhydride and 2-(tribromosilyl)ethylsuccinic anhydride; 2-(dichloromethyl dihalomethylsilyl (carbon number 2~8) alkylsuccinic anhydride, etc.; 2-(chlorodimethylsilyl)ethylsuccinic anhydride, etc. halodimethyl Silyl (carbon number 2~8) alkyl succinic anhydride, etc. Silane coupling agent (C) can be used individually by 1 type or in combination of 2 or more types.

該等之中，作為矽烷偶合劑(C)，係以三(碳數1~6)烷氧矽烷基(碳數2~8)烷基琥珀酸酐為佳，以3-(三甲氧矽烷基)丙基琥珀酸酐或3-(三乙氧基矽烷基)丙基琥珀酸酐為特佳。Among these, as the silane coupling agent (C), tris(carbon number 1 to 6)alkoxysilyl(carbon number 2 to 8)alkyl succinic anhydride is preferred, and 3-(trimethoxysilyl) Propyl succinic anhydride or 3-(triethoxysilyl)propyl succinic anhydride is particularly preferred.

本發明的硬化性組合物係含有矽烷偶合劑(C)[(C)成分]時，(C)成分的含量係沒有特別限定，其量係上述(A)成分與(C)成分的質量比[(A)成分：(C)成分]，良好為100：0.1~100：30，較佳為100：0.3~100：20，較佳為100：0.5~100：15，更佳是成為100：1~100：10之量。 採用此種比例含有(C)成分之硬化性組合物的硬化物係成為接著強度較高之物。When the curable composition of the present invention contains the silane coupling agent (C) [component (C)], the content of the component (C) is not particularly limited, and the amount is the mass ratio of the component (A) to the component (C). [(A) Component: (C) Component], preferably 100:0.1~100:30, more preferably 100:0.3~100:20, more preferably 100:0.5~100:15, more preferably 100: 1~100: The amount of 10. The cured product using the curable composition containing the component (C) in such a proportion has a high bonding strength.

本發明的硬化性組合物亦可含有平均一次粒徑為5~40nm的微粒(以下有記載為「微粒(D)」之情形)作為(D)成分。含有微粒(D)之硬化性組合物，係在塗佈步驟具有優異的作業性。因為更容易得到該效果，微粒(D)的平均一次粒徑係較佳為5~30nm，更佳為5~20nm。The curable composition of the present invention may contain fine particles (hereinafter referred to as "fine particles (D)") with an average primary particle diameter of 5 to 40 nm as the component (D). The curable composition containing fine particles (D) has excellent workability in the coating step. Since it is easier to obtain this effect, the average primary particle size of the fine particles (D) is preferably 5 to 30 nm, more preferably 5 to 20 nm.

微粒(D)的平均一次粒徑係能夠藉由使用穿透式電子顯微鏡觀察微粒的形狀而求取。The average primary particle diameter of the fine particles (D) can be determined by observing the shape of the fine particles using a transmission electron microscope.

微粒(D)的比表面積係較佳為10~500m2 /g，更佳為20~300m2 /g。藉由比表面積為上述範圍內，容易得到在塗佈步驟具有更優異的作業性之硬化性組合物。 The specific surface area of the fine particles (D) is preferably 10 to 500 m 2 /g, more preferably 20 to 300 m 2 /g. When the specific surface area is within the above range, a curable composition having more excellent workability in the coating step can be easily obtained.

比表面積係能夠使用BET多點法而求取。 The specific surface area can be obtained using the BET multi-point method.

微粒(D)的形狀可為球狀、鏈狀、針狀、板狀、片狀、棒狀、纖維狀等的任一種，以球狀為佳。在此，所謂球狀，係意味著除了包含正球狀之外，也能包含旋轉橢圓體、卵形、糖球狀、繭狀等能夠近似球體的多面體形狀之大略球狀。 The shape of the fine particles (D) may be any of spherical, chain-like, needle-like, plate-like, flaky, rod-like, fibrous, etc., with spherical shape being preferred. Here, the term "spherical" means not only a perfect sphere but also a roughly spherical shape that can approximate a spherical polyhedral shape such as a spheroid, an oval, a sugar sphere, and a cocoon.

作為微粒(D)的構成成分，係沒有特別限制，可舉出金屬；金屬氧化物；礦物；碳酸鈣、碳酸鎂等的金屬碳酸鹽；硫酸鈣、硫酸鋇等的金屬硫酸鹽；氫氧化鋁等的金屬氫氧化物；矽酸鋁、矽酸鈣、矽酸鎂等的金屬矽酸鹽；氧化矽等的無機成分；聚矽氧；丙烯酸系聚合物等的有機成分等。 The constituent components of the fine particles (D) are not particularly limited, and examples thereof include metals; metal oxides; minerals; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; and aluminum hydroxide. Metal hydroxides such as aluminum silicate, calcium silicate, magnesium silicate, etc.; inorganic components such as silicon oxide; organic components such as polysiloxane; acrylic polymers, etc.

又，所使用的微粒(D)亦可為表面經改性之物。 In addition, the fine particles (D) used may be surface-modified.

所謂金屬，係指屬於在周期表之第1族(H除外)、第2~11族、第12族(Hg除外)、第13族(B除外)、第14族(C及Si除外)、第15族(N、P、As及Sb除外)、或第16族(O、S、Se、Te及Po除外)之元素。 The so-called metals refer to those belonging to Group 1 (except H), Group 2 to 11, Group 12 (except Hg), Group 13 (except B), Group 14 (except C and Si), Elements of Group 15 (except N, P, As and Sb), or Group 16 (except O, S, Se, Te and Po).

作為金屬氧化物，可舉出例如氧化鈦、氧化鋁、水鋁礦(boehmite)、氧化鉻、氧化鎳、氧化銅、氧化鋯、氧化銦、氧化鋅、及該等複合氧化物等。金屬氧化物的微粒亦包含由該等金屬氧化物所構成之溶膠(sol)粒子。 Examples of metal oxides include titanium oxide, aluminum oxide, boehmite, chromium oxide, nickel oxide, copper oxide, zirconium oxide, indium oxide, zinc oxide, and these composite oxides. The fine particles of metal oxides also include sol particles composed of these metal oxides.

作為礦物，可舉出膨潤石(smectite)、膨土等。 Examples of minerals include smectite, bentonite, and the like.

作為膨潤石，可舉出例如蒙脫石(montmorillonite)、貝得石(beidellite)、鋰膨潤石(hectorite)、皂石(saponite)、矽鎂石(stevensite)、矽鐵石(nontronite)、鋅蒙脫石(sauconite)等。 Examples of the bentonite include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, and hectorite. sauconite, etc.

作為氧化矽，可舉出乾式氧化矽、濕式氧化矽、表面改性氧化矽(表面經改性之氧化矽)等。 Examples of silicon oxide include dry silicon oxide, wet silicon oxide, surface-modified silicon oxide (surface-modified silicon oxide), and the like.

微粒(D)係能夠單獨1種或組合2種以上而使用。該等之中，因為容易得到具有優異的透明性之硬化物，作為微粒(D)，係以氧化矽、金屬氧化物、礦物為佳，以氧化矽為較佳。The microparticles (D) can be used individually by 1 type or in combination of 2 or more types. Among these, since it is easy to obtain a cured product having excellent transparency, silicon oxide, metal oxide, and mineral are preferred as the fine particles (D), and silicon oxide is more preferred.

氧化矽之中，因為容易得到在塗佈步驟具有更優異的作業性之硬化性組合物，係以表面改性氧化矽為佳，以疏水性表面改性氧化矽為較佳。 作為疏水性表面改性氧化矽，可舉出使三甲基矽烷基等三個碳數1~20的三烷基矽烷基、二甲基矽烷基等二個碳數1~20的烷基矽烷基；辛基矽烷基等的碳數1~20的烷基矽烷基鍵結在表面而成之氧化矽；及使用聚矽氧油處理表面而成之氧化矽等。 疏水性表面改性氧化矽係例如能夠藉由使用具有三個碳數1~20的三烷基矽烷基、二個碳數1~20的烷基矽烷基、碳數1~20的烷基矽烷基等之矽烷偶合劑對氧化矽粒子進行表面改性、或使用聚矽氧油處理氧化矽粒子而得到。又，亦能夠直接使用市售之表面改性氧化矽。Among silicon oxides, surface-modified silicon oxide is preferred, and hydrophobic surface-modified silicon oxide is preferred because it is easy to obtain a curable composition that has better workability in the coating step. Examples of the hydrophobic surface-modified silica include three trialkylsilyl groups having 1 to 20 carbon atoms, such as trimethylsilyl group, and two alkylsilane groups having 1 to 20 carbon atoms, such as dimethylsilyl group. Silicon oxide formed by bonding alkylsilyl groups with 1 to 20 carbon atoms such as octylsilyl group to the surface; and silicon oxide formed by treating the surface with polysiloxane oil. The hydrophobic surface modified silica system can be produced by using, for example, three trialkylsilyl groups having 1 to 20 carbon atoms, two alkylsilyl groups having 1 to 20 carbon atoms, or an alkylsilane group having 1 to 20 carbon atoms. It is obtained by surface modification of oxidized silicon particles with a silane coupling agent such as a base, or by treating oxidized silicon particles with polysiloxane oil. In addition, commercially available surface-modified silicon oxide can also be used directly.

本發明的硬化性組合物係含有微粒(D)[(D)成分]時，(D)成分的含量係沒有特別限定，其量係上述(A)成分與(D)成分的質量比[(A)成分：(D)成分]，良好為100：0.1~100：90，較佳為100：0.2~100：60，較佳為100：0.3~100：50，較佳為100：0.5~100：40，較佳是成為100：0.8~100：30之量。藉由在上述範圍使用(D)成分，而能夠進一步顯現添加(D)成分之效果。When the curable composition of the present invention contains fine particles (D) [(D) component], the content of component (D) is not particularly limited, and the amount is the mass ratio of the above-mentioned component (A) to component (D) [( A) Ingredients: (D) Ingredients], good is 100:0.1~100:90, more preferably 100:0.2~100:60, more preferably 100:0.3~100:50, more preferably 100:0.5~100 : 40, preferably 100:0.8~100:30. By using component (D) within the above range, the effect of adding component (D) can be further expressed.

本發明的硬化性組合物亦可含有平均一次粒徑為大於0.04μm且8μm以下的微粒(以下有記載為「微粒(E)」之情形)作為(E)成分。藉由使用含有微粒(E)之硬化性組合物，能夠形成具有優異的耐剝離性之硬化物。 因為更容易得到該效果，微粒(E)的平均一次粒徑係良好為0.06~7μm，較佳為0.3~6μm，更佳為0.5~4μm。The curable composition of the present invention may contain fine particles (hereinafter referred to as "fine particles (E)") with an average primary particle diameter of more than 0.04 μm and not more than 8 μm as the component (E). By using a curable composition containing fine particles (E), a cured product having excellent peeling resistance can be formed. Since this effect is more easily obtained, the average primary particle size of the fine particles (E) is preferably 0.06 to 7 μm, more preferably 0.3 to 6 μm, and more preferably 0.5 to 4 μm.

微粒(E)的平均一次粒徑，係能夠藉由使用雷射繞射‧散射式粒度分布測定裝置(例如股份公司堀場製作所製、製品名「LA-920」)等，藉由雷射散射法而進行測定粒度分布來求取。The average primary particle diameter of fine particles (E) can be measured by the laser scattering method using a laser diffraction and scattering particle size distribution measuring device (for example, manufactured by Horiba Manufacturing Co., Ltd., product name "LA-920"). It is obtained by measuring the particle size distribution.

微粒(E)的形狀可為球狀、鏈狀、針狀、板狀、片狀、棒狀、纖維狀等的任一種，以球狀為佳。在此，所謂球狀，係意味著除了包含正球狀之外，也能包含旋轉橢圓體、卵形、糖球狀、繭狀等能夠近似球體的多面體形狀之大略球狀。The shape of the fine particles (E) may be any of spherical, chain-like, needle-like, plate-like, flaky, rod-like, fibrous, etc., with spherical shape being preferred. Here, the term "spherical" means not only a perfect sphere but also a roughly spherical shape that can approximate a spherical polyhedral shape such as a spheroid, an oval, a sugar sphere, and a cocoon.

作為微粒(E)的構成成分，可舉出作為微粒(D)的構成成分已例示之物同樣物。 微粒(E)係能夠單獨1種或組合2種以上而使用。該等之中，因為容易得到上述效果，作為微粒(E)，係以選自由經聚矽氧被覆表面之金屬氧化物、氧化矽及聚矽氧所組成群組之至少一種微粒為佳，以氧化矽、聚矽氧為較佳。Examples of the constituent components of the fine particles (E) include the same ones as those exemplified as the constituent components of the fine particles (D). The microparticles (E) can be used individually by 1 type or in combination of 2 or more types. Among them, since the above-mentioned effect is easily obtained, the fine particles (E) are preferably at least one selected from the group consisting of metal oxides, silicon oxide and polysiloxane with a surface coated with polysiloxane. Silicon oxide and polysiloxane are preferred.

本發明的硬化性組合物係含有微粒(E)[(E)成分]時，(E)成分的含量係沒有特別限定，其量係(A)成分與(E)成分的質量比[(A)成分：(E)成分]，良好為100：0.1~100：40，較佳為100：0.2~100：30，較佳為100：0.3~100：20，較佳為100：0.5~100：15，更佳是成為100：0.8~100：12之量。藉由在上述範圍使用(E)成分，能夠進一步顯現添加(E)成分之效果。When the curable composition of the present invention contains fine particles (E) [(E) component], the content of (E) component is not particularly limited, and the amount is the mass ratio of (A) component to (E) component [(A) ) ingredient: (E) ingredient], a good range is 100:0.1~100:40, a preferred range is 100:0.2~100:30, a preferred range is 100:0.3~100:20, a preferred range is 100:0.5~100: 15, preferably 100:0.8~100:12. By using component (E) within the above range, the effect of adding component (E) can be further expressed.

本發明的硬化性組合物係在不阻礙本發明的目的之範圍，亦可含有上述(A)~(E)成分以外的其它成分((F)成分)。 作為(F)成分，可舉出抗氧化劑、紫外線吸收劑、光安定劑等。The curable composition of the present invention may contain other components (component (F)) other than the above-mentioned components (A) to (E) within a range that does not hinder the object of the present invention. Examples of the component (F) include antioxidants, ultraviolet absorbers, light stabilizers, and the like.

抗氧化劑係為了防止加熱時的氧化劣化而添加。作為抗氧化劑，可舉出磷系抗氧化劑、酚系抗氧化劑、硫系抗氧化劑等。Antioxidants are added to prevent oxidative deterioration during heating. Examples of antioxidants include phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, and the like.

作為磷系抗氧化劑，可舉出亞磷酸酯類、氧雜磷雜菲氧化物(oxa phosphaphenanthrene oxide)類等。作為酚系抗氧化劑，可舉出單酚類、雙酚類、高分子型酚類等。作為硫系抗氧化劑，可舉出3,3’-硫代二丙酸二月桂酯、3,3’-硫代二丙酸二肉豆蔻酯、3,3’-硫代二丙酸二硬脂酸酯等。Examples of phosphorus-based antioxidants include phosphites, oxa phosphaphenanthrene oxides, and the like. Examples of phenolic antioxidants include monophenols, bisphenols, polymeric phenols, and the like. Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and disulfide 3,3'-thiodipropionate. Fatty acid esters, etc.

該等抗氧化劑係能夠單獨1種或組合2種以上而使用。抗氧化劑的使用量係相對於(A)成分，通常10質量%以下。These antioxidants can be used individually by 1 type or in combination of 2 or more types. The amount of antioxidant used is usually 10% by mass or less based on component (A).

紫外線吸收劑係為了使所得到的硬化物之耐光性提升而添加。 作為紫外線吸收劑，可舉出水楊酸類、二苯基酮類、苯并***類、受阻胺類等。 紫外線吸收劑係能夠單獨1種或組合2種以上而使用。 紫外線吸收劑的使用量係相對於(A)成分，通常10質量%以下。The ultraviolet absorber is added in order to improve the light resistance of the obtained cured product. Examples of ultraviolet absorbers include salicylates, benzophenones, benzotriazoles, hindered amines, and the like. The ultraviolet absorber system can be used individually by 1 type or in combination of 2 or more types. The usage amount of the ultraviolet absorber is usually 10% by mass or less based on component (A).

光安定劑係為了使所得到的硬化物的耐光性提升之目的而添加。 作為光安定劑，例如可舉出聚[{6-(1,1,3,3,-四甲基丁基)胺-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶)亞胺}六亞甲基{(2,2,6,6-四甲基-4-哌啶)亞胺}]等的受阻胺類等。 該等光安定劑係能夠單獨1種或組合2種以上而使用。 (F)成分的總使用量係相對於(A)成分，通常20質量%以下。The light stabilizer is added for the purpose of improving the light resistance of the obtained hardened material. Examples of the light stabilizer include poly[{6-(1,1,3,3,-tetramethylbutyl)amine-1,3,5-triazine-2,4-diyl}{( 2,2,6,6-Tetramethyl-4-piperidine)imine}hexamethylene{(2,2,6,6-tetramethyl-4-piperidine)imine}], etc. Amines, etc. These light stabilizers can be used individually by 1 type or in combination of 2 or more types. The total usage amount of component (F) is usually 20% by mass or less based on component (A).

本發明的硬化性組合物，係例如能夠藉由將上述(A)成分、溶劑(S1)、及依照需要之該等以外的成分以預定比率混合且除氣來調製。混合方法、除氣方法係沒有特別限定，能夠利用習知的方法。The curable composition of the present invention can be prepared, for example, by mixing the above-mentioned component (A), the solvent (S1), and other components as necessary at a predetermined ratio and deaeration. The mixing method and the degassing method are not particularly limited, and conventional methods can be used.

本發明的硬化性組合物係含有硬化性聚倍半矽氧烷化合物(A)。因而，本發明的硬化性組合物係具有優異的硬化性且折射率較低。又，本發明的硬化性組合物係作為接著強度較高的硬化物的形成材料為有用的。The curable composition of the present invention contains a curable polysilsesquioxane compound (A). Therefore, the curable composition of the present invention has excellent curability and a low refractive index. Furthermore, the curable composition of the present invention is useful as a material for forming a cured product with high adhesive strength.

本發明的硬化性組合物在25℃之折射率(nD)係通常為1.380~1.434，良好為1.380~1.430，較佳為1.380~1.428，更佳為1.380~1.425。 硬化性組合物的折射率(nD)係能夠使用實施例記載的方法而測定。The refractive index (nD) of the curable composition of the present invention at 25°C is usually 1.380~1.434, preferably 1.380~1.430, more preferably 1.380~1.428, more preferably 1.380~1.425. The refractive index (nD) of the curable composition can be measured using the method described in the Examples.

而且，本發明的硬化性組合物係含有溶劑(S1)。因而，本發明的硬化性組合物係塗佈後即便被放置長時間之後，亦能夠與剛塗佈後同樣地進行光學元件的裝配等的作業。 例如，在本發明的硬化性組合物係塗佈後，即便經過通常20分鐘以上、較佳為30分鐘以上、更佳為60分鐘以上後，亦能夠進行與剛塗佈後同樣的作業。Furthermore, the curable composition of the present invention contains a solvent (S1). Therefore, even if the curable composition of the present invention is left to stand for a long time after application, operations such as assembling optical elements can be performed in the same manner as immediately after application. For example, even after usually 20 minutes or more, preferably 30 minutes or more, more preferably 60 minutes or more after application of the curable composition of the present invention, the same operation as immediately after application can be performed.

3)硬化物 本發明的硬化物係將本發明的硬化性組合物硬化而得到之物。作為使本發明的硬化性組合物硬化之方法，可舉出加熱硬化。使其硬化時之加熱溫度係通常為100~200℃，加熱時間係通常從10分鐘起至20小時，較佳為30分鐘起至10小時。3) Hardened material The cured material of the present invention is obtained by curing the curable composition of the present invention. An example of a method for curing the curable composition of the present invention is heat curing. The heating temperature when hardening is usually 100~200°C, and the heating time is usually from 10 minutes to 20 hours, preferably from 30 minutes to 10 hours.

本發明的硬化物係接著強度較高且具有優異的耐熱性之物。本發明的硬化物具有該等特性係例如能夠如以下地進行而確認。亦即，將本發明的硬化性組合物以預定量塗佈在矽晶片的鏡面且使塗佈面載置在被接著物上，而且進行壓黏及加熱處理使其硬化。將其放置在預先加熱至預定溫度(例如23℃、100℃)之黏結強度試驗機(bond tester)的測定載物台上30秒鐘，從被接著物起算50μm的高度之位置，對接著面在水平方向(剪切方向)施加應力來測定試片與被接著物的接著力。The hardened material of the present invention has high bonding strength and excellent heat resistance. It can be confirmed that the cured material of the present invention has these characteristics, for example, as follows. That is, the curable composition of the present invention is coated on the mirror surface of the silicon wafer in a predetermined amount, the coated surface is placed on the adherend, and pressure bonding and heat treatment are performed to cure it. Place it on the measurement stage of a bond tester that has been preheated to a predetermined temperature (for example, 23°C, 100°C) for 30 seconds, and place it at a height of 50 μm from the adherend, and connect the two surfaces. Apply stress in the horizontal direction (shearing direction) to measure the adhesion force between the test piece and the adherend.

本發明的硬化物之接著力係在23℃以60N/4mm2 以上為佳，以80N/4mm2 以上為較佳，以100N/4mm2 以上為特佳。又，硬化物的接著力係在100℃以30N/4mm2 以上為佳，以40N/4mm2 以上為較佳，以50N/4mm2 以上為更佳，以60N/4mm2 以上為特佳。在本說明書，所謂「4mm2 」係意味著2mm×2mm(1邊為2mm的正方形)。The adhesion force of the hardened material of the present invention is preferably 60N/4mm 2 or more at 23° C., preferably 80N/4mm 2 or more, and particularly preferably 100N/4mm 2 or more. In addition, the adhesion force of the hardened material at 100°C is preferably 30N/4mm 2 or more, more preferably 40N/4mm 2 or more, more preferably 50N/4mm 2 or more, and particularly preferably 60N/4mm 2 or more. In this specification, "4mm 2 " means 2mm×2mm (a square with one side of 2mm).

因為具有上述特性，所以本發明的硬化物係能夠適合使用作為光學元件固定材。Since it has the above characteristics, the cured material system of the present invention can be suitably used as an optical element fixing material.

4)硬化性組合物的使用方法 本發明的方法係將本發明的硬化性組合物使用作為光學元件固定材用接著劑或光學元件固定材用密封劑之方法。作為光學元件，可舉出LED、LD等的發光元件、受光元件、複合光學元件、光積體電路等。4) How to use the curable composition The method of the present invention is a method of using the curable composition of the present invention as an adhesive for optical element fixing materials or a sealant for optical element fixing materials. Examples of optical elements include light-emitting elements such as LEDs and LDs, light-receiving elements, composite optical elements, optical integrated circuits, and the like.

>光學元件固定材用接著劑> 本發明的硬化性組合物係能夠適合使用作為光學元件固定材用接著劑。作為將本發明的硬化性組合物使用作為光學元件固定材用接著劑之方法，係將該組合物塗佈在作為接著對象之材料(光學元件及其基板等)的一方或雙方的接著面且壓黏之後，使其加熱硬化來使作為接著對象之材料彼此堅固地接著之方法。本發明的硬化性組合物的塗佈量係沒有特別限定，藉由使其硬化而能夠使作為接著對象之材料彼此堅固地接著之量即可。通常，硬化性組合物的塗膜之厚度為0.5~5μm，較佳是成為1~3μm之量。>Adhesives for optical element fixing materials> The curable composition of the present invention can be suitably used as an adhesive for optical element fixing materials. As a method of using the curable composition of the present invention as an adhesive for optical element fixing materials, the composition is applied to one or both bonding surfaces of materials to be bonded (optical elements, substrates, etc.) and After pressing and bonding, it is heated and hardened to firmly bond the materials to be bonded to each other. The coating amount of the curable composition of the present invention is not particularly limited, as long as it is an amount that can firmly bond materials to be adhered to each other by curing the composition. Normally, the thickness of the coating film of the curable composition is 0.5 to 5 μm, preferably 1 to 3 μm.

作為用以將光學元件接著之基板材料，可舉出鈉鈣玻璃、耐熱性硬質玻璃等的玻璃類；陶瓷；藍寶石；鐵、銅、鋁、金、銀、白金、鉻、鈦及該等金屬的合金、不鏽鋼(SUS302、SUS304、SUS304L、SUS309等)等的金屬類；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物、聚苯乙烯、聚碳酸酯、聚甲基戊烯、聚碸、聚醚醚酮、聚醚碸、聚苯硫醚(polyphenylene sulfide)、聚醚醯亞胺、聚醯亞胺、聚醯胺、丙烯酸樹脂、降莰烯系樹脂、環烯烴樹脂、玻璃環氧樹脂等的合成樹脂等。Examples of substrate materials for bonding optical elements include glasses such as soda-lime glass and heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium, and metals thereof Alloys, stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.) and other metals; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate Copolymer, polystyrene, polycarbonate, polymethylpentene, polystyrene, polyether ether ketone, polyether sulfide, polyphenylene sulfide (polyphenylene sulfide), polyetherimide, polyimide, polyether Synthetic resins such as amide, acrylic resin, norbornene resin, cycloolefin resin, glass epoxy resin, etc.

使其加熱硬化時的加熱溫度，亦取決於所使用的硬化性組合物等，通常100~200℃。加熱時間係通常10分鐘至20小時，較佳為30分鐘至10小時。The heating temperature when heating and hardening also depends on the curable composition used, etc., but is usually 100 to 200°C. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

>光學元件固定材用密封劑> 本發明的硬化性組合物係能夠適合使用作為光學元件固定材用密封劑。作為將本發明的硬化性組合物使用作為光學元件固定材用密封劑之方法，例如可舉出將該組合物成形為所需要的形狀而得到內包光學元件之成形體之後，藉由使該物加熱硬化，來製造光學元件密封體之方法等。 作為將本發明的硬化性組合物成形為所需要的形狀之方法，係沒有特別限定，能夠採用通常的轉移成型法、澆鑄法等習知的造模法。>Sealant for optical component fixing materials> The curable composition of the present invention can be suitably used as a sealant for optical element fixing materials. As a method of using the curable composition of the present invention as a sealing agent for optical element fixing materials, for example, the composition is molded into a desired shape to obtain a molded body containing an optical element, and then the Methods for manufacturing optical element seals by heating and hardening materials. The method for molding the curable composition of the present invention into a desired shape is not particularly limited, and conventional molding methods such as ordinary transfer molding and casting can be used.

加熱硬化時的加熱溫度亦取決於所使用的硬化性組合物等，通常100~200℃。加熱時間係通常10分鐘至20小時，較佳為30分鐘至10小時。The heating temperature during heat curing also depends on the curable composition used, etc., but is usually 100 to 200°C. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

因為所得到的光學元件密封體係使用本發明的硬化性組合物，所以具有優異的耐熱性且接著強度較高。 [實施例]Since the obtained optical element sealing system uses the curable composition of the present invention, it has excellent heat resistance and high bonding strength. [Example]

以下，舉出實施例而更詳細地說明本發明。但是本發明係完全不被以下的實施例限定。各例中的份及%係只要未預先告知，就是質量基準。Hereinafter, an Example is given and this invention is demonstrated in more detail. However, the present invention is not limited to the following examples at all. The parts and % in each example are based on quality unless notified in advance.

(實施例1) 在300mL的茄子型燒瓶添加3,3,3-三氟丙基三甲氧基矽烷17.0g(77.7mmo1)、及甲基三乙氧基矽烷32.33g(181.3mmol)後，將其邊攪拌邊添加將35%鹽酸0.0675g(HCl的量為0.65mmol，相對於矽烷化合物的合計量為0.25mol%)溶解在蒸餾水14.0g而得到的水溶液，將全部內容物在30℃攪拌2小時，其次升溫至70℃攪拌20小時。邊繼續攪拌內容物，邊在此添加28%氨水0.0394g(NH3 的量為0.65mmol)與乙酸丙酯46.1g的混合溶液使反應液的pH成為6.9，而且直接在70℃攪拌60分鐘。 將反應液放冷至室溫為止後，在此，添加乙酸丙酯50g及水100g而進行分液處理，來得到含有反應生成物之有機層。在該有機層添加硫酸鎂而進行乾燥處理。將硫酸鎂過濾分開而除去後，使用蒸發器將有機層濃縮，其次，藉由將所得到的濃縮物進行真空乾燥來得到硬化性聚倍半矽氧烷化合物(1)。(Example 1) After adding 17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane and 32.33 g (181.3 mmol) of methyltriethoxysilane to a 300 mL eggplant-shaped flask, While stirring, an aqueous solution obtained by dissolving 0.0675g of 35% hydrochloric acid (the amount of HCl is 0.65mmol, 0.25mol% relative to the total amount of silane compounds) in 14.0g of distilled water was added, and the entire contents were stirred at 30°C for 2 hours, then raise the temperature to 70°C and stir for 20 hours. While continuing to stir the contents, a mixed solution of 0.0394 g of 28% ammonia water (the amount of NH 3 is 0.65 mmol) and 46.1 g of propyl acetate was added to adjust the pH of the reaction solution to 6.9, and the mixture was further stirred at 70° C. for 60 minutes. After the reaction liquid was left to cool to room temperature, 50 g of propyl acetate and 100 g of water were added and liquid separation was performed to obtain an organic layer containing a reaction product. Magnesium sulfate was added to this organic layer and dried. After filtering and removing magnesium sulfate, the organic layer was concentrated using an evaporator, and then the obtained concentrate was vacuum-dried to obtain the curable polysesesquioxane compound (1).

在硬化性聚倍半矽氧烷化合物(1)100份，添加平均一次粒徑為7nm的氧化矽填料20份、平均一次粒徑為0.8μm的聚矽氧填料10份。而且，添加作為溶劑之二乙二醇單丁醚乙酸酯：三丙二醇正丁醚=40：60(質量比)的混合溶劑30份後，將全部內容物進行攪拌。 使用三輥磨機進行分散處理後，添加1,3,5-N-參[3-(三甲氧矽烷基)丙基]異三聚氰酸酯30份、3-(三甲氧矽烷基)丙基琥珀酸酐3份、及作為溶劑之二乙二醇單丁醚乙酸酯：三丙二醇正丁醚=40：60(質量比)的混合溶劑，而且藉由將全部內容物充分地混合、除氣來得到固體成分濃度82%的硬化性組合物(1)。To 100 parts of the curable polysesquioxane compound (1), 20 parts of silica filler with an average primary particle diameter of 7 nm and 10 parts of polysiloxane filler with an average primary particle diameter of 0.8 μm were added. Furthermore, after adding 30 parts of a mixed solvent of diethylene glycol monobutyl ether acetate: tripropylene glycol n-butyl ether = 40:60 (mass ratio) as a solvent, the entire contents were stirred. After dispersion treatment using a three-roller mill, 30 parts of 1,3,5-N-san[3-(trimethoxysilyl)propyl]isocyanurate and 3-(trimethoxysilyl)propyl were added. 3 parts of succinic anhydride, and a mixed solvent of diethylene glycol monobutyl ether acetate: tripropylene glycol n-butyl ether = 40:60 (mass ratio) as a solvent, and thoroughly mix and remove all contents. The curable composition (1) with a solid content concentration of 82% was obtained.

(實施例2) 除了將添加28%氨水與乙酸丙酯的混合溶液後的攪拌時間變更成為120分鐘以外，係與實施例1同樣地進行而得到硬化性聚倍半矽氧烷化合物(2)、及硬化性組合物(2)。(Example 2) The curable polysesesquioxane compound (2) and the curable combination were obtained in the same manner as in Example 1, except that the stirring time after adding the mixed solution of 28% ammonia water and propyl acetate was changed to 120 minutes. Object(2).

(實施例3) 除了將添加28%氨水與乙酸丙酯的混合溶液後的攪拌時間變更成為90分鐘以外，係與實施例1同樣地進行而得到硬化性聚倍半矽氧烷化合物(3)、及硬化性組合物(3)。(Example 3) The curable polysesquioxane compound (3) and the curable combination were obtained in the same manner as in Example 1, except that the stirring time after adding the mixed solution of 28% ammonia water and propyl acetate was changed to 90 minutes. Object (3).

(實施例4) 除了將添加28%氨水與乙酸丙酯的混合溶液後的攪拌時間變更成為50分鐘以外，係與實施例1同樣地進行而得到硬化性聚倍半矽氧烷化合物(4)、及硬化性組合物(4)。(Example 4) The curable polysesquioxane compound (4) and the curable combination were obtained in the same manner as in Example 1, except that the stirring time after adding the mixed solution of 28% ammonia water and propyl acetate was changed to 50 minutes. Object (4).

(實施例5) 除了將添加28%氨水與乙酸丙酯的混合溶液後的攪拌時間變更成為40分鐘以外，係與實施例1同樣地進行而得到硬化性聚倍半矽氧烷化合物(5)、及硬化性組合物(5)。(Example 5) The curable polysesquioxane compound (5) and the curable combination were obtained in the same manner as in Example 1, except that the stirring time after adding the mixed solution of 28% ammonia water and propyl acetate was changed to 40 minutes. Object(5).

(比較例1) 依照WO2017/110948號之實施例8的方法而得到硬化性聚倍半矽氧烷化合物(6)。 其次，在硬化性聚倍半矽氧烷化合物(6)100份，添加平均一次粒徑為7nm的氧化矽填料20份、平均一次粒徑為0.8μm的聚矽氧填料10份。而且，添加作為溶劑之二乙二醇單丁醚乙酸酯30份之後，將全部內容物進行攪拌。 使用三輥磨機進行分散處理後，添加1,3,5-N-參[3-(三甲氧矽烷基)丙基]異三聚氰酸酯10份、3-(三甲氧矽烷基)丙基琥珀酸酐3份、及使用E型黏度計在25℃、200s-1 的條件下測定時的黏度成為4.5Pa‧s之二乙二醇單丁醚乙酸酯，而且藉由將全部內容物充分地混合且除氣來得到硬化性組合物(6)。 又，在WO2017/110948號的段落(0115)，係以鹽酸的使用量之方式記載「相對於矽烷化合物的合計量為0.25mol%」，但是從添加量計算時，正確為「相對於矽烷化合物的合計量為約1.6mol%」。在以下的比較例2、3亦同樣。(Comparative Example 1) According to the method of Example 8 of WO2017/110948, a curable polysilsesquioxane compound (6) was obtained. Next, 20 parts of silica filler with an average primary particle diameter of 7 nm and 10 parts of polysiloxane filler with an average primary particle diameter of 0.8 μm were added to 100 parts of the curable polysesquioxane compound (6). Furthermore, after adding 30 parts of diethylene glycol monobutyl ether acetate as a solvent, the entire contents were stirred. After dispersion treatment using a three-roller mill, add 10 parts of 1,3,5-N-san[3-(trimethoxysilyl)propyl]isocyanurate and 3-(trimethoxysilyl)propyl 3 parts of succinic anhydride and diethylene glycol monobutyl ether acetate have a viscosity of 4.5 Pa‧s when measured using an E-type viscometer at 25°C and 200 s -1 , and by adding all the contents Mix thoroughly and degas to obtain curable composition (6). Furthermore, in paragraph (0115) of WO2017/110948, the amount of hydrochloric acid used is stated as "0.25 mol% relative to the total amount of silane compounds", but when calculated from the added amount, it is correctly stated as "relative to the silane compounds." The total amount is about 1.6 mol%." The same applies to the following Comparative Examples 2 and 3.

(比較例2) 依照WO2017/110948號之實施例9的方法而得到硬化性聚倍半矽氧烷化合物(7)。 其次，使用與比較例1同樣的方法來得到硬化性組合物(7)。(Comparative example 2) The curable polysilsesquioxane compound (7) was obtained according to the method of Example 9 of WO2017/110948. Next, the same method as Comparative Example 1 was used to obtain curable composition (7).

(比較例3) 依照WO2017/110948號之實施例10的方法而得到硬化性聚倍半矽氧烷化合物(8)。 其次，使用與比較例1同樣的方法來得到硬化性組合物(8)。(Comparative example 3) The curable polysilsesquioxane compound (8) was obtained according to the method of Example 10 of WO2017/110948. Next, the same method as Comparative Example 1 was used to obtain curable composition (8).

(比較例4) 在300mL的茄子型燒瓶添加甲基三乙氧基矽烷71.37g(400mmol)後，將其邊攪拌邊添加將35%鹽酸0.1g(相對於矽烷化合物的合計量為0.25mol%)溶解在蒸餾水21.6g而得到的水溶液，將全部內容物在30℃攪拌2小時，其次升溫至70℃攪拌5小時。 邊繼續攪拌內容物，邊在此添加乙酸丙酯140g、及28%氨水0.12g(相對於矽烷化合物的合計量，NH3 為0.5mol%)且在70℃攪拌3小時。 將反應液冷卻至室溫為止後，使用純化水將有機層洗淨至水層的pH成為7為止。 藉由使用蒸發器將有機層濃縮且將濃縮物進行真空乾燥，來得到硬化性聚倍半矽氧烷化合物(9)。 其次，使用與實施例1同樣的來得到硬化性組合物(9)。(Comparative Example 4) After adding 71.37 g (400 mmol) of methyltriethoxysilane to a 300 mL eggplant-shaped flask, 0.1 g of 35% hydrochloric acid (0.25 mol% based on the total amount of silane compounds) was added while stirring. ) was dissolved in 21.6 g of distilled water, the entire contents were stirred at 30°C for 2 hours, and then the temperature was raised to 70°C and stirred for 5 hours. While continuing to stir the contents, 140 g of propyl acetate and 0.12 g of 28% ammonia water (0.5 mol% of NH 3 relative to the total amount of silane compounds) were added, and the mixture was stirred at 70° C. for 3 hours. After the reaction liquid was cooled to room temperature, the organic layer was washed with purified water until the pH of the aqueous layer became 7. The organic layer is concentrated using an evaporator and the concentrate is vacuum-dried to obtain the curable polysesquioxane compound (9). Next, the same procedure as in Example 1 was used to obtain curable composition (9).

(比較例5) 除了將添加28%氨水與乙酸丙酯的混合溶液後的攪拌時間變更成為240分鐘以外，係與實施例1同樣地進行而得到硬化性聚倍半矽氧烷化合物(10)、及硬化性組合物(10)。(Comparative example 5) The curable polysesquioxane compound (10) and the curable combination were obtained in the same manner as in Example 1, except that the stirring time after adding the mixed solution of 28% ammonia water and propyl acetate was changed to 240 minutes. Things (10).

使用實施例、及比較例所得到的硬化性聚倍半矽氧烷化合物(1)~(10)、及硬化性組合物(1)~(10)，各自進行以下的測定、試驗。將結果顯示在表1。The following measurements and tests were performed using the curable polysilsesquioxane compounds (1) to (10) and the curable compositions (1) to (10) obtained in the Examples and Comparative Examples. The results are shown in Table 1.

[質量平均分子量測定] 硬化性聚倍半矽氧烷化合物的質量平均分子量(Mw)係在以下的裝置及條件下進行測定。 裝置名：HLC-8220GPC、TOSOH股份公司製 管柱：依次將TSKgel GMHXL、TSKgelGMHXL、及TSKgel2000HXL連結而成 溶劑：四氫呋喃 標準物質：聚苯乙烯 注入量：20μl 測定溫度：40℃ 流速：0.6ml/分鐘 檢測器：差示折射計[Measurement of mass average molecular weight] The mass average molecular weight (Mw) of the curable polysilsesquioxane compound is measured under the following equipment and conditions. Device name: HLC-8220GPC, manufactured by TOSOH Co., Ltd. Column: TSKgel GMHXL, TSKgelGMHXL, and TSKgel2000HXL are connected in sequence. Solvent: Tetrahydrofuran Standard material: polystyrene Injection volume: 20μl Measuring temperature: 40℃ Flow rate: 0.6ml/minute Detector: Differential Refractometer

[29 Si-NMR測定] 裝置：Bruker BioSpin公司製 AV-50029 Si-NMR共振頻率：99.352MHz 探測器：5mmϕ溶液探測器 測定溫度：室溫(25℃) 試料轉數：20kHz 測定法：反門控去偶法(inverse gated decoupling method)29 Si　偏折角(flip angle)：90°29 Si　90°脈衝寬度：8.0μs 重複時間：5s 累計次數：9200次 觀測寬度：30kHz[ 29 Si-NMR measurement] Device: AV-500 29 Si-NMR manufactured by Bruker BioSpin Co., Ltd. Resonance frequency: 99.352MHz Detector: 5mmϕ solution detector Measurement temperature: Room temperature (25℃) Sample rotation speed: 20kHz Measurement method: Reverse Inverse gated decoupling method (inverse gated decoupling method) 29 Si flip angle: 90° 29 Si 90° pulse width: 8.0μs repetition time: 5s cumulative number: 9200 times observation width: 30kHz

>29 Si-NMR試料製造方法> 為了緩和時間縮短，係添加Fe(acac)3 作為緩和試藥且測定。 聚倍半矽氧烷濃度：15% Fe(acac)3 濃度：0.6% 測定溶劑：丙酮 內部標準：TMS> 29 Si-NMR sample preparation method > In order to shorten the relaxation time, Fe(acac) 3 is added as a relaxation reagent and measured. Polysesquioxane concentration: 15% Fe(acac) 3 concentration: 0.6% Determination solvent: acetone Internal standard: TMS

>波形處理解析> 針對傅立葉轉換(Fourier transformation)後的光譜之各尖峰，依照峰頂的位置而求取化學位移且進行積分。>Waveform processing analysis> For each peak of the spectrum after Fourier transformation, the chemical shift is calculated according to the position of the peak top and integrated.

[折射率測定] 將硬化性組合物吐出至水平面上，藉由使其在25℃壓黏筆式折射計(ATAGO公司製、PEN-RI)的測定面而測定折射率(nD)。[Refractive index measurement] The curable composition was discharged onto a horizontal surface, and the refractive index (nD) was measured by pressing the measurement surface of a pen refractometer (manufactured by ATAGO, PEN-RI) at 25°C.

[硬化性評價] [Hardening evaluation]

使用流變計(Anton Paar公司製、MCR302)且使用20mm的平行板在試驗起始溫度80℃、升溫速度5℃/分鐘、剪切應變1%、頻率1Hz的條件下測定剪切應力。將剪切應力成為2000Pa之溫度設為硬化溫度。 The shear stress was measured using a rheometer (MCR302 manufactured by Anton Paar Co., Ltd.) and a 20 mm parallel plate under the conditions of a test starting temperature of 80° C., a temperature increase rate of 5° C./min, a shear strain of 1%, and a frequency of 1 Hz. The temperature at which the shear stress becomes 2000 Pa is defined as the hardening temperature.

[黏度評價] [Viscosity evaluation]

使用流變計(Anton Paar公司製、MCR301)且使用半徑50mm、錐角0.5°的圓錐/平板(cone and plate)，各自測定在25℃、剪切速度為2s-1、及剪切速度為200s-1的黏度。從所得到的測定值求取觸變指數(剪切速度為2s-1的黏度/剪切速度為200s-1的黏度)。 A rheometer (MCR301 manufactured by Anton Paar Co., Ltd.) was used and a cone and plate (cone and plate) with a radius of 50 mm and a cone angle of 0.5° were used, and the measurements were performed at 25°C, a shear speed of 2 s -1 , and a shear speed of 200s -1 viscosity. The thixotropic index (viscosity at a shear rate of 2 s -1 /viscosity at a shear rate of 200 s -1 ) was calculated from the obtained measured values.

[接著強度測定] [Adhesion strength measurement]

將硬化性組合物以各自厚度為約2μm之方式塗佈在一邊為2mm的正方形(面積為4mm2)的矽晶片之鏡面上，使塗佈面載置在被接著物(鍍銀銅板)上且壓黏。隨後，在170℃進行加熱處理2小時且硬化而得到附有試片的被接著物。將該附有試片的被接著物放置在預先在預定溫度(23℃、100℃)加熱之黏結強度試驗機(Dage公司製、Series 4000)的測定載物台上30秒鐘，而且從被接著物起100μm的高度之位置，以速度200um/s對接著面於水平方向(剪切方向)施加應力，來測定在23℃及100℃之試片與被接著物的接著強度(N/4mm2)。 The curable composition is coated on the mirror surface of a square silicon wafer with a side of 2 mm (area 4 mm 2 ) so that each thickness is about 2 μm, and the coated surface is placed on the adherend (silver-plated copper plate). And sticky. Subsequently, heat treatment was performed at 170° C. for 2 hours and hardened to obtain an adherend with a test piece attached. The adherend with the test piece attached was placed on the measurement stage of an adhesive strength testing machine (Series 4000, manufactured by Dage Corporation) that was previously heated at a predetermined temperature (23°C, 100°C) for 30 seconds, and was removed from the adherend. Then, lift the object from a height of 100 μm, apply stress to the bonding surface in the horizontal direction (shear direction) at a speed of 200 μm/s, and measure the bonding strength (N/4mm) between the test piece and the adherend at 23°C and 100°C. 2 ).

[耐龜裂性評價] [Crack resistance evaluation]

將硬化性組合物以各自厚度為約2μm之方式塗佈在一邊為0.5mm的正方形(面積為0.25mm2)的矽晶片之鏡面上，使塗佈面載置在被接著物(鍍銀銅板)上且壓黏。隨後，在170℃進行加熱處理2小時且硬化而得到附有試片的被接著物。使用數位顯微鏡(VHX-1000、KEYENCE製)且觀察從玻璃晶片擠出之樹脂部(圓角(fillet)部)，而且計算具有龜裂之試樣的數目，將龜裂產生率為0%以上且小於25%評定為「A」，將25%以上且小於50%評定為「B」，將50%以上至100%評定為「C」。 The curable composition is coated on the mirror surface of a square silicon wafer with a side of 0.5 mm (area 0.25 mm 2 ) so that each thickness is about 2 μm, and the coated surface is placed on the adherend (silver-plated copper plate) ) and press it to stick. Subsequently, heat treatment was performed at 170° C. for 2 hours and hardened to obtain an adherend with a test piece attached. Using a digital microscope (VHX-1000, manufactured by KEYENCE), the resin part (fillet part) extruded from the glass wafer was observed, and the number of samples with cracks was counted, and the crack occurrence rate was set to 0% or more. And less than 25% is evaluated as "A", more than 25% and less than 50% is evaluated as "B", and more than 50% to 100% is evaluated as "C".

[耐剝離性評價] 將硬化性組合物以0.4mmϕ左右塗佈在LED導線框架(益能達(ENOMOTO)公司製、5050D/G PKG LEADFRAME)上，而且壓黏在一邊為0.5mm之正方形(面積為0.25mm2 )的藍寶石晶片。隨後，在170℃加熱處理2小時使其硬化之後，將密封劑(信越化學工業公司製、LPS-3419)流入杯內，在120℃加熱1小時且在150℃加熱1小時而得到試片。 將該試片曝露在85℃、85%RH的環境168小時之後，藉由預熱160℃且最高溫度成為260℃之加熱時間1分鐘的IR回流(回流爐：相模理工公司製、製品名「WL-15-20DNX型」)進行處理。隨後，使用熱循環試驗機，將在-40℃及+100℃各放置30分鐘之試驗設為1循環且實施500循環。隨後，進行將密封劑除去操作且調查此時元件是否一起剝落。針對各硬化性組合物各自進行該試驗100次。計算元件一起剝落之次數，剝離產生率為25%以下時評定為「A」，大於25%且50%以下時評定為「B」，大於50%時評定為「C」。[Evaluation of Peeling Resistance] The curable composition was applied to an LED lead frame (5050D/G PKG LEADFRAME manufactured by ENOMOTO Co., Ltd.) with an area of approximately 0.4mmφ, and was pressed onto a square with a side of 0.5mm ( A sapphire chip with an area of 0.25mm 2 ). Subsequently, after hardening by heat treatment at 170° C. for 2 hours, a sealant (LPS-3419 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was poured into the cup, and heated at 120° C. for 1 hour and 150° C. for 1 hour to obtain a test piece. After the test piece was exposed to an environment of 85°C and 85%RH for 168 hours, it was preheated to 160°C and reached a maximum temperature of 260°C using IR reflow for 1 minute with a heating time of 1 minute (reflow oven: manufactured by Sagami Riko Co., Ltd., product name " WL-15-20DNX type") for processing. Then, using a thermal cycle testing machine, a test in which each of -40°C and +100°C was left for 30 minutes was set as one cycle and 500 cycles were performed. Subsequently, the sealant was removed and it was investigated whether the components were peeled off together at this time. This test was performed 100 times for each curable composition. Counting the number of times components peel off together, the peeling rate is rated as "A" when it is less than 25%, "B" when it is greater than 25% and less than 50%, and "C" when it is greater than 50%.

[表1]   硬化性聚倍半矽氧烷化合物 硬化性組合物 硬化物 含F原子的 單體之比率 [添加量] 質量平均 分子量 [Mw] 29 Si-NMR測定 折射率 硬化性 [硬化溫度] 黏度評價 [觸變指數] 接著強度 (N/4mm2 ) 耐龜裂性 耐剝離性 Z2值 Z3值 23℃ 100℃ 實施例1 30mol% 5900 28% 70% 1.425 186℃ 4.2 140.2 72.5 A A 實施例2 30mol% 7100 25% 73% 1.424 189℃ 3.8 143.7 74.3 A A 實施例3 30mol% 6500 28% 71% 1.425 186℃ 4.3 135.0 66.2 A A 實施例4 30mol% 5800 27% 71% 1.424 191℃ 4.3 127.4 70.9 A A 實施例5 30mol% 5500 27% 71% 1.424 193℃ 4.7 134.1 72.5 A A 比較例1 30mol% 3500 16% 84% 1.416 204℃ 4.5 115 85 A A 比較例2 20mol% 4600 16% 84% 1.421 203℃ 5.1 110 86 A A 比較例3 10mol% 5300 17% 83% 1.423 203℃ 4.2 118 88 A A 比較例4 0mol% 9500 17% 83% 1.435 202℃ 5.1 136 90 A A 比較例5 30mol% 13000 20% 79% 1.423 200℃ 3.8 88.8 55.9 A A [Table 1] Hardening polysilsesquioxane compound hardening composition hardened matter Ratio of monomers containing F atoms [added amount] Mass average molecular weight [Mw] 29 Si-NMR measurement refractive index Hardenability [hardening temperature] Viscosity evaluation [thixotropy index] Subsequent strength (N/4mm 2 ) Crack resistance Peel resistance Z2 value Z3 value 23℃ 100℃ Example 1 30mol% 5900 28% 70% 1.425 186℃ 4.2 140.2 72.5 A A Example 2 30mol% 7100 25% 73% 1.424 189℃ 3.8 143.7 74.3 A A Example 3 30mol% 6500 28% 71% 1.425 186℃ 4.3 135.0 66.2 A A Example 4 30mol% 5800 27% 71% 1.424 191℃ 4.3 127.4 70.9 A A Example 5 30mol% 5500 27% 71% 1.424 193℃ 4.7 134.1 72.5 A A Comparative example 1 30mol% 3500 16% 84% 1.416 204℃ 4.5 115 85 A A Comparative example 2 20mol% 4600 16% 84% 1.421 203℃ 5.1 110 86 A A Comparative example 3 10mol% 5300 17% 83% 1.423 203℃ 4.2 118 88 A A Comparative example 4 0mol% 9500 17% 83% 1.435 202℃ 5.1 136 90 A A Comparative example 5 30mol% 13000 20% 79% 1.423 200℃ 3.8 88.8 55.9 A A

從表1得知以下情形。得知以實施例1~5所得到的硬化性聚倍半矽氧烷化合物(1)~(5)，29 Si-NMR測定的結果係Z2的值在20~40%的範圍內。又，硬化性聚倍半矽氧烷化合物(1)~(5)的質量平均分子量係任一者均在4000~11000的範圍內。 含有該等硬化性聚倍半矽氧烷化合物之硬化性組合物(1)~(5)係折射率(nD)為較低且在較低的溫度充分地硬化。又，硬化性組合物(1)~(5)的硬化物之接著強度為較高。From Table 1, we know the following situation. It was found that the curable polysilsesquioxane compounds (1) to (5) obtained in Examples 1 to 5 had a Z2 value in the range of 20 to 40% as measured by 29 Si-NMR. Moreover, any of the mass average molecular weights of the curable polysilsesquioxane compounds (1) to (5) is in the range of 4,000 to 11,000. The curable compositions (1) to (5) containing these curable polysilsesquioxane compounds have a low refractive index (nD) and are sufficiently cured at a low temperature. In addition, the bonding strength of the cured products of the curable compositions (1) to (5) is relatively high.

另一方面，比較例1~3係各自使用專利文獻4之實施例8~10的硬化性聚倍半矽氧烷化合物(硬化性聚倍半矽氧烷化合物(6)~(8)之物。 在專利文獻4的實施例，為了補足具有氟烷基之矽烷化合物的反應性較低而使用多量的酸觸媒。但是在該方法，係只能夠得到Z2值較小的硬化性聚倍半矽氧烷化合物。又，依照3,3,3-三氟丙基三甲氧基矽烷的添加量增加，硬化性聚倍半矽氧烷化合物的質量平均分子量降低。 由於該等原因，相較於實施例1~5的硬化性組合物(1)~(5)，比較例1~3的硬化性組合物(6)~(8)係在硬化性、硬化物的接著強度為較差。On the other hand, Comparative Examples 1 to 3 are those using the curable polysesquioxane compounds (curable polysesquioxane compounds (6) to (8) of Examples 8 to 10 of Patent Document 4, respectively). . In the Example of Patent Document 4, a large amount of acid catalyst is used to compensate for the low reactivity of the silane compound having a fluoroalkyl group. However, in this method, only a curable polysesesquioxane compound with a small Z2 value can be obtained. Furthermore, as the added amount of 3,3,3-trifluoropropyltrimethoxysilane increases, the mass average molecular weight of the curable polysesquioxane compound decreases. For these reasons, compared with the curable compositions (1) to (5) of Examples 1 to 5, the curable compositions (6) to (8) of Comparative Examples 1 to 3 are inferior in curability and cured product. The bonding strength is poor.

比較例4所得到的硬化性聚倍半矽氧烷化合物(9)，係不具有源自3,3,3-三氟丙基三甲氧基矽烷的重複單元。 因此，硬化性組合物(9)的折射率(nD)係成為較大的值。又，因為硬化性聚倍半矽氧烷化合物(9)之Z2值較小，所以硬化性組合物(9)的硬化性不充分。The curable polysilsesquioxane compound (9) obtained in Comparative Example 4 does not have repeating units derived from 3,3,3-trifluoropropyltrimethoxysilane. Therefore, the refractive index (nD) of the curable composition (9) becomes a large value. In addition, since the Z2 value of the curable polysilsesquioxane compound (9) is small, the curable composition (9) has insufficient curability.

比較例5所得到的硬化性聚倍半矽氧烷化合物(10)，係分子量太大之物。該結果，相較於實施例1~5的硬化性組合物(1)~(5)，硬化性組合物(10)係在硬化性、硬化物的接著強度為較差。The curable polysilsesquioxane compound (10) obtained in Comparative Example 5 has a molecular weight that is too large. This result shows that compared to the curable compositions (1) to (5) of Examples 1 to 5, the curable composition (10) is inferior in curability and bonding strength of the cured product.

無。without.

無。without.

Claims (13)

一種硬化性聚倍半矽氧烷化合物，係具有下述式(a-1)所示的重複單元之硬化性聚倍半矽氧烷化合物，其特徵在於：滿足下述必要條件1及必要條件2，R1-D-SiO3/2 (a-1)[R1表示組成式：CmH(2m-n+1)Fn所表示之氟烷基，m表示為1~10的整數，n表示為2以上且(2m+1)以下的整數，D表示將R1與Si鍵結之連結基(但是伸烷基除外)或單鍵]，[必要條件1]測定硬化性聚倍半矽氧烷化合物的29Si-NMR時，能夠在-62ppm以上且小於-52ppm的區域[區域(2)]觀測到1或2個以上的尖峰，能夠在-52ppm以上且小於-45ppm的區域[區域(1)]及-73ppm以上且小於-62ppm的區域[區域(3)]之至少一區域觀測到1或2個以上的尖峰，而且下述式導出之Z2為20~40%，
Figure 108135111-A0305-02-0042-3
 P1：在區域(1)之積分值P2：在區域(2)之積分值P3：在區域(3)之積分值[必要條件2]硬化性聚倍半矽氧烷化合物的質量平均分子量(Mw)為4,000~11,000。 A curable polysesquioxane compound having a repeating unit represented by the following formula (a-1), characterized in that it satisfies the following necessary conditions 1 and 1 2. R 1 -D-SiO 3/2 (a-1)[R 1 represents the composition formula: C m H (2m-n+1) F n represents the fluoroalkyl group, m represents an integer from 1 to 10 , n represents an integer of 2 or more and (2m+1) or less, D represents a connecting group (but not an alkylene group) or a single bond that bonds R 1 to Si], [Required condition 1] Measurement of curable polyethylene In the 29 Si-NMR of the semisiloxane compound, one or two or more sharp peaks can be observed in the region between -62 ppm and less than -52 ppm [region (2)], and can be observed in the region between -52 ppm and less than -45 ppm. 1 or 2 or more peaks are observed in at least one of the areas [Area (1)] and the area above -73ppm and less than -62ppm [Area (3)], and Z2 derived from the following formula is 20~40%,
Figure 108135111-A0305-02-0042-3
 P1: Integrated value in area (1) P2: Integrated value in area (2) P3: Integrated value in area (3) [Required condition 2] Mass average molecular weight (Mw) of the curable polysilsesquioxane compound ) is 4,000~11,000. 如請求項1所述之硬化性聚倍半矽氧烷化合物，其中式(a-1)所示 之重複單元比率係相對於總重複單元為25mol%以上。 The hardening polysilsesquioxane compound as described in claim 1, which is represented by formula (a-1) The repeating unit ratio is 25 mol% or more relative to the total repeating units. 如請求項1所述之硬化性聚倍半矽氧烷化合物，其中進一步具有下述式(a-2)所示之重複單元，R2SiO3/2 (a-2)[R2表示未取代之碳數1~10的烷基、或具有取代基、或未取代之碳數6~12的芳基]。 The curable polysilsesquioxane compound according to claim 1, which further has a repeating unit represented by the following formula (a-2), R 2 SiO 3/2 (a-2) [R 2 represents not A substituted alkyl group having 1 to 10 carbon atoms, or a substituent, or an unsubstituted aryl group having 6 to 12 carbon atoms]. 如請求項3所述之硬化性聚倍半矽氧烷化合物，其中式(a-2)所示之重複單元比率係相對於總重複單元為大於0mol%且75mol%以下。 The curable polysilsesquioxane compound according to claim 3, wherein the ratio of the repeating units represented by formula (a-2) is greater than 0 mol% and less than 75 mol% relative to the total repeating units. 如請求項1所述之硬化性聚倍半矽氧烷化合物，其中測定29Si-NMR時，能夠在區域(3)觀測到1或2個以上的尖峰且下述式所導出的Z3為60~80%，
Figure 108135111-A0305-02-0043-4
 The curable polysilsesquioxane compound according to claim 1, wherein when measuring 29 Si-NMR, one or more peaks can be observed in the region (3) and Z3 derived from the following formula is 60 ~80%,
Figure 108135111-A0305-02-0043-4
 一種硬化性組合物，其特徵在於含有下述(A)成分、及具有254℃以上的沸點之溶劑，(A)成分：如請求項1至5中任一項所述之硬化性聚倍半矽氧烷化合物。 A curable composition characterized by containing the following component (A): the curable polysesquiene according to any one of claims 1 to 5, and a solvent having a boiling point of 254°C or higher. Siloxane compounds. 如請求項6所述之硬化性組合物，係進一步含有下述(B)成分，(B)成分：在分子內具有氮原子之矽烷偶合劑。 The curable composition according to claim 6 further contains the following component (B): a silane coupling agent having a nitrogen atom in the molecule. 如請求項6所述之硬化性組合物，係進一步含有下述(C)成分，(C)成分：在分子內具有酸酐結構之矽烷偶合劑。 The curable composition according to Claim 6 further contains the following (C) component: (C) component: a silane coupling agent having an acid anhydride structure in the molecule. 如請求項6所述之硬化性組合物，係進一步含有下述(D)，(D)成分：平均一次粒徑為5~40nm的微粒。 The curable composition according to claim 6 further contains the following (D), component (D): microparticles with an average primary particle size of 5 to 40 nm. 一種硬化物，係將如請求項6至9中任一項所述之硬化性組合物硬化而得到。 A hardened product obtained by hardening the curable composition according to any one of claims 6 to 9. 如請求項10項所述之硬化物，係光學元件固定材。 The hardened object described in claim 10 is an optical element fixing material. 一種接著方法，係將如請求項6至9中任一項所述之硬化性組合物使用作為光學元件固定材用接著劑。 An adhesive method using the curable composition according to any one of claims 6 to 9 as an adhesive for optical element fixing materials. 一種密封方法，係將如請求項6至9中任一項所述之硬化性組合物使用作為光學元件固定材用密封劑。 A sealing method using the curable composition according to any one of claims 6 to 9 as a sealant for optical element fixing materials.
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