TW202033663A - Binary room-temperature condensation curable organopolysiloxane composition exposed to room temperature for condensation curable reaction and having a fast and deep curing - Google Patents
Binary room-temperature condensation curable organopolysiloxane composition exposed to room temperature for condensation curable reaction and having a fast and deep curing Download PDFInfo
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Abstract
Description
本發明涉及一種通過在室溫（23℃±15℃）且含有濕氣的氣氛（大氣）中進行曝露進而進行縮合固化（交聯），進而能夠賦予具有低硬度、高伸長率、優異的光透射率以及屈曲性的矽酮橡膠固化物，且快速固化性、深處固化性良好的二元型室溫縮合固化性有機聚矽氧烷組合物。The present invention relates to a method of condensation curing (crosslinking) by exposure to room temperature (23°C±15°C) and moisture-containing atmosphere (atmosphere), which can impart low hardness, high elongation, and excellent light A silicone rubber cured product with transmittance and flexibility, and a binary room temperature condensation curable organopolysiloxane composition with fast curing and good deep curing.
通過大氣中的濕氣而發生縮合固化反應進而進行交聯的室溫固化性（RTV）矽酮橡膠組合物（即，縮合固化型室溫快速固化性有機聚矽氧烷組合物），由於其易於處理且耐候性和電氣特性優異，因此，用於建築材料用的密封材料和電氣電子領域的黏接劑等的各個領域。這些RTV矽酮橡膠大多設計為將在末端具有矽烷醇基的有機聚矽氧烷作為起始材料。The room temperature curing (RTV) silicone rubber composition (ie, condensation curing type room temperature rapid curing organopolysiloxane composition) that undergoes a condensation curing reaction and then crosslinks by moisture in the atmosphere is due to its It is easy to handle and has excellent weather resistance and electrical properties. Therefore, it is used in various fields such as sealing materials for building materials and adhesives in the electrical and electronic fields. Most of these RTV silicone rubbers are designed with organopolysiloxanes having silanol groups at the ends as starting materials.
關於縮合固化型的室溫快速固化性有機聚矽氧烷組合物，已知，以往為將交聯劑的量減少至極限，且通過水解提高交聯速度的單組分類型或者將交聯劑和固化劑分別進行包裝的雙組分類型。但是，單組分類型的所述組合物僅為從表面上的固化速度快，其達到深處固化需要一定的時間，因此還難以稱之為快速固化性。Regarding the condensation-curable room temperature fast-curing organopolysiloxane composition, it is known that the amount of the crosslinking agent is reduced to the limit, and the crosslinking speed is increased by hydrolysis. Two-component type that is packaged separately with curing agent. However, the one-component type composition only has a fast curing speed from the surface, and it takes a certain time to reach deep curing, so it is difficult to call it fast curing.
在雙組分類型的所述組合物中，雖然深處固化性比較優異，但存在著在雙組分的混合比不為1：1的情況下則操作上繁瑣，而且難以適合自動混合機等的缺點。進一步，為了使其完全固化至深處，需要嚴格地控制交聯劑和固化劑的添加量或添加作為深處固化劑的水。另一方面，在加成固化型的有機聚矽氧烷組合物中，雖然在雙組分的混合比為1：1的情況下其操作性優異，但是通常需要加熱才能使其固化。另外，還存在著在固化催化劑的作用效果受到阻礙的環境下該組合物被限制使用的缺點。In the two-component type of the composition, although the deep curability is relatively excellent, there is a problem that the operation is cumbersome when the mixing ratio of the two components is not 1:1, and it is difficult to be suitable for automatic mixers, etc. Shortcomings. Furthermore, in order to make it completely harden to a deep part, it is necessary to strictly control the addition amount of a crosslinking agent and a curing agent, or add water as a deep part curing agent. On the other hand, in the addition-curing type organopolysiloxane composition, although the two-component mixing ratio is 1:1, the workability is excellent, but it usually requires heating to be cured. In addition, there is a disadvantage that the composition is restricted to be used in an environment where the effect of the curing catalyst is hindered.
為了解決這些問題，在日本特開2002-338811號公報（專利文獻1）中，公開了一種將通過在分子中具有至少2個醯氧基的水解性矽烷或其部分水解物的水解而生成的羧酸與無機質填充劑的中和反應所生成的水作為深處固化劑使用的方法。但是，由於生成羧酸的室溫快速固化性有機聚矽氧烷組合物具有腐蝕金屬的問題，因此，其應用範圍非常狹窄。In order to solve these problems, Japanese Patent Application Laid-Open No. 2002-338811 (Patent Document 1) discloses a method of hydrolyzing a hydrolyzable silane having at least two acyloxy groups in the molecule or a partial hydrolyzate thereof. A method of using the water generated by the neutralization reaction of the carboxylic acid and the inorganic filler as a deep curing agent. However, since the room temperature fast-curing organopolysiloxane composition that generates carboxylic acid has the problem of corrosion of metals, its application range is very narrow.
另外，在日本特開2002-12767號公報（專利文獻2）中，公開了一種通過混合含水的濕式二氧化矽進而直接對組合物供給水分，並將其作為深處固化劑使用的方法。但是，如果直接供給水，則難以控制固化反應的速度，進而更加難以確保組合物的操作性。In addition, Japanese Patent Application Laid-Open No. 2002-12767 (Patent Document 2) discloses a method of mixing water-containing wet silica to directly supply water to the composition and using it as a deep curing agent. However, if water is directly supplied, it is difficult to control the speed of the curing reaction, and it is even more difficult to ensure the operability of the composition.
此外，使其在組合物體系內產生水對促進組合物的快速固化和深處固化有效。在日本專利第2811134號（專利文獻3）中，公開了一種將通過在一個分子中具有至少1個C＝O基團的有機化合物與在一個分子中具有至少一個NH2 基團的有機化合物發生酮亞胺反應所副產的水作為深處固化劑使用的方法。日本專利第2841155號（專利文獻4）公開了一種將由鏈烯氧基矽烷產生的酮化合物與伯胺化合物發生酮化反應所副產的水作為深處固化劑使用的方法。但是，雖然在上述任一方法中都能夠實現快速固化性，但由於為含有填充劑的組合物，因此，缺乏透明性，且由於固化物的硬度較高，進而難以廣泛地應用在光學領域等。In addition, making it generate water in the composition system is effective in promoting rapid curing and deep curing of the composition. In Japanese Patent No. 2811134 (Patent Document 3), it is disclosed that an organic compound having at least one C=O group in one molecule and an organic compound having at least one NH 2 group in one molecule are combined. A method of using the water produced by the ketimine reaction as a deep curing agent. Japanese Patent No. 2841155 (Patent Document 4) discloses a method in which water produced by the ketoneization reaction between a ketone compound produced from an alkenyloxysilane and a primary amine compound is used as a deep curing agent. However, although fast curability can be achieved in any of the above methods, it is a composition containing fillers and therefore lacks transparency, and because the cured product has high hardness, it is difficult to be widely used in the optical field, etc. .
﹙先前技術文獻﹚ ［專利文獻］ 專利文獻1：日本特開2002-338811號公報 專利文獻2：日本特開2002-12767號公報 專利文獻3：日本專利第2811134號公報 專利文獻4：日本專利第2841155號公報﹙Prior technical literature﹚ [Patent Literature] Patent Document 1: Japanese Patent Application Publication No. 2002-338811 Patent Document 2: Japanese Patent Application Publication No. 2002-12767 Patent Document 3: Japanese Patent No. 2811134 Patent Document 4: Japanese Patent No. 2841155
［發明所欲解決之課題］ 因此，本發明的目的在於，提供一種二元型室溫縮合固化性有機聚矽氧烷組合物。該組合物通過利用由具有C=O基團的β-酮酸酯化合物與含有胺基水解性有機矽烷化合物和/或其部分水解縮合物在體系內所生成的水，進而賦予具有高光透射率、低硬度以及屈曲性的固化物，且具有快速固化性和深處固化性。[Problems to be solved by the invention] Therefore, the object of the present invention is to provide a binary room temperature condensation curable organopolysiloxane composition. The composition utilizes water generated in the system from a β-ketoester compound having a C=O group and an amino group-containing hydrolyzable organosilane compound and/or a partial hydrolysis condensate thereof, thereby imparting high light transmittance , Cured product with low hardness and flexibility, fast curing and deep curing.
［用以解決課題的手段］ 本發明者們為達到上述目的，彙集精心研究的結果，研究出了下述的二元型室溫縮合固化性有機聚矽氧烷組合物、及其該組合物的固化方法以及用該組合物的固化物所進行黏接、塗布或封裝的物品，進而完成了本發明。[Means to solve the problem] In order to achieve the above-mentioned object, the inventors have gathered the results of careful research and developed the following binary type room temperature condensation curable organopolysiloxane composition, and the curing method of the composition and the use of the composition The cured product is bonded, coated or encapsulated, thereby completing the present invention.
因此，本發明為提供下述的二元型室溫縮合固化性有機聚矽氧烷組合物、及其該組合物的固化方法以及用該組合物的固化物所進行黏接、塗布或封裝的物品等的發明。Therefore, the present invention provides the following binary room temperature condensation curable organopolysiloxane composition, a curing method of the composition, and a cured product of the composition for bonding, coating or encapsulation Inventions of objects, etc.
[1] 一種二元型室溫縮合固化性有機聚矽氧烷組合物，其由第一組分和第二組分所組成，其中， 前述第一組分含有： (A)成分：100質量份的分子鏈兩末端以羥基封端的二有機聚矽氧烷；以及 (B)成分：相對於(A)成分100質量份為0.01〜2質量份的β-酮酸酯化合物； 前述第二組分含有： (C)成分：相對於(A)成分100質量份為0.1〜15質量份的在1個分子中具有3個以上已與矽原子鍵合的有機氧基的水解性有機矽烷化合物和/或其部分水解縮合物； (D)成分：相對於(A)成分100質量份為0.1〜5質量份的(C)成分以外的含胺基水解性有機矽烷化合物和/或其部分水解縮合物；以及 (E)成分：相對於(A)成分100質量份為0.001〜5質量份的固化催化劑。[1] A binary type room temperature condensation curable organopolysiloxane composition, which consists of a first component and a second component, wherein, The aforementioned first component contains: (A) Component: 100 parts by mass of diorganopolysiloxane terminated by hydroxyl at both ends of the molecular chain; and (B) component: 0.01 to 2 parts by mass of β-keto acid ester compound relative to 100 parts by mass of (A) component; The aforementioned second component contains: (C) Component: 0.1-15 parts by mass relative to 100 parts by mass of (A) component, hydrolyzable organosilane compound having 3 or more organooxy groups bonded to silicon atoms in one molecule and/or Partially hydrolyzed condensate; (D) component: 0.1 to 5 parts by mass relative to 100 parts by mass of (A) component, an amino group-containing hydrolyzable organosilane compound other than component (C) and/or a partial hydrolysis condensate thereof; and (E) component: 0.001 to 5 parts by mass of curing catalyst relative to 100 parts by mass of (A) component.
[2] 根據[1]所記載的二元型室溫縮合固化性有機聚矽氧烷組合物，其中， 其不含有無機填充劑。[2] The binary room temperature condensation curable organopolysiloxane composition according to [1], wherein It does not contain inorganic fillers.
[3] 根據[1]或[2]所記載的二元型室溫縮合固化性有機聚矽氧烷組合物，其中， 其用於光學。[3] The binary room temperature condensation-curable organopolysiloxane composition according to [1] or [2], wherein It is used in optics.
[4] 根據[1]~[3]中任一項所記載的二元型室溫縮合固化性有機聚矽氧烷組合物，其中， 其能夠提供一種矽酮橡膠固化物，前述矽酮橡膠固化物在23℃/50％RH條件下固化3天後的厚度為2.5mm的固化物在400〜800nm的波長區域內的光透射率為80％以上。[4] The binary room temperature condensation curable organopolysiloxane composition according to any one of [1] to [3], wherein It can provide a cured silicone rubber. The cured silicone rubber has a thickness of 2.5mm after curing for 3 days at 23°C/50%RH. The light transmittance of the cured product in the wavelength range of 400~800nm is Above 80%.
[5] 根據[1]~[4]中任一項所記載的二元型室溫縮合固化性有機聚矽氧烷組合物，其中， (D)成分中的胺基，相對於(B)成分的β-酮酸酯化合物中的羰基為1〜5莫耳當量。[5] The binary room temperature condensation curable organopolysiloxane composition according to any one of [1] to [4], wherein The amine group in the component (D) is 1 to 5 molar equivalents to the carbonyl group in the β-keto acid ester compound of the component (B).
[6] 根據[1]~[5]中任一項所記載的二元型室溫縮合固化性有機聚矽氧烷組合物，其中，第一組分與第二組分的比例以質量比為50:50〜90:10。[6] The binary room temperature condensation curable organopolysiloxane composition according to any one of [1] to [5], wherein the ratio of the first component to the second component is based on the mass ratio It is 50:50~90:10.
[7] 一種物品： 其用根據[1]~[6]中任一項所記載的二元型室溫縮合固化性有機聚矽氧烷組合物的固化物所進行黏接、塗布或封裝。[7] One item: It is bonded, coated, or encapsulated with the cured product of the binary room temperature condensation curable organopolysiloxane composition according to any one of [1] to [6].
[8] 根據[1]〜[6]中的任意一項所記載的二元型室溫縮合固化性有機聚矽氧烷組合物的固化方法， 其包含通過將含有前述(A)成分和前述(B)成分的前述第一組分塗布在第一基材的表面上，且將含有前述(C)成分、前述(D)成分以及前述(E)成分的前述第二組分塗布在第二基材的表面上，並且以第一組分和第二組分相接觸的方式將雙方的基材彼此相向並接觸，進而將前述第一組分和前述第二組分進行貼合並使其固化的步驟。[8] According to the curing method of the binary room temperature condensation curable organopolysiloxane composition described in any one of [1] to [6], It includes applying the aforementioned first component containing the aforementioned (A) component and the aforementioned (B) component on the surface of a first substrate, and adding the aforementioned (C) component, the aforementioned (D) component and the aforementioned (E) ) The aforementioned second component of the component is coated on the surface of the second substrate, and the two substrates are opposed and contacted with each other in a manner that the first component and the second component are in contact, and then the aforementioned first component The step of bonding and curing the aforementioned second component.
［發明的效果］ 具有本發明的快速固化性和深處固化性的二元型室溫縮合固化性有機聚矽氧烷組合物，由於能夠賦予具有高光透射率、低硬度以及屈曲性的固化物，例如，作為用於路燈等的可彎曲的LED用的封裝樹脂等，能夠廣泛地使用，包括光學用途。[Effects of Invention] The binary room-temperature condensation-curable organopolysiloxane composition with fast curing properties and deep curing properties of the present invention can impart a cured product with high light transmittance, low hardness and flexibility, for example, It can be widely used as an encapsulating resin for flexible LEDs such as street lamps, including optical applications.
以下，對本發明進行詳細地說明。Hereinafter, the present invention will be described in detail.
[(A)成分] (A)成分的分子鏈兩端用羥基（矽烷醇基）所封端的二有機聚矽氧烷，為本發明的二元型室溫縮合固化性有機聚矽氧烷組合物的主要成分（基礎聚合物），且以下述通式（1）所表示的為具有代表性。 HO-（R1 2 SiO）n -H （1） （在通式（1）中，R1 分別獨立地為未經取代或經取代的一價烴基，n為10以上的整數。） 作為R1 、可列舉為例如，為碳原子數1〜20、較佳為碳原子數1〜8的烷基，為碳原子數2〜20、較佳為碳原子數2〜8的烯基，為碳原子數6〜20、較佳為碳原子數6〜12的芳基以及這些烴基的一部分或全部的氫原子被氟等的鹵素原子所取代的基團等。作為該烷基，可例示為甲基、乙基、丙基以及環己基等。作為該烯基，可例示為乙烯基和烯丙基等。作為該芳基，可例示為苯基和甲苯基等。作為該鹵素原子取代基，可例示為3,3,3-三氟丙基等。在這些當中，較佳為甲基、乙烯基以及苯基，更佳為甲基。[(A) component] (A) The two organopolysiloxanes of component (A) whose molecular chain ends are capped with hydroxyl groups (silanol groups) are the binary type room temperature condensation curable organopolysiloxane combination of the present invention The main component (base polymer) of the product is representatively represented by the following general formula (1). HO-(R 1 2 SiO) n -H (1) (In the general formula (1), R 1 is each independently an unsubstituted or substituted monovalent hydrocarbon group, and n is an integer of 10 or more.) As R 1. Examples include, for example, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms, and An aryl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and a group in which a part or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine. As this alkyl group, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, etc. are illustrated. As this alkenyl group, a vinyl group, an allyl group, etc. are illustrated. As this aryl group, a phenyl group, a tolyl group, etc. can be illustrated. As the halogen atom substituent, 3,3,3-trifluoropropyl and the like can be exemplified. Among these, methyl, vinyl, and phenyl are preferred, and methyl is more preferred.
表示分子中的二有機矽氧烷單元（R1 2 SiO）的重複數（或聚合度）的n為10以上的整數，但通常也可為10〜2000左右的整數、較佳為50〜1200左右的整數、更佳為100〜1000左右的整數。需要說明的是，在本發明中的聚合度（或分子量），可以作為例如，通過將甲苯等作為展開溶劑的凝膠滲透色譜法（GPC）分析的以聚苯乙烯換算的數均聚合度（或數均分子量）等所求出。N, which represents the number of repetitions (or degree of polymerization) of diorganosiloxane units (R 1 2 SiO) in the molecule, is an integer of 10 or more, but usually it can also be an integer of about 10 to 2000, preferably 50 to 1200 An integer of about 100 to 1000 is more preferable. It should be noted that the degree of polymerization (or molecular weight) in the present invention can be taken as, for example, the number average degree of polymerization in terms of polystyrene (GPC) analyzed by gel permeation chromatography (GPC) using toluene as a developing solvent ( Or number average molecular weight) etc.
該二有機聚矽氧烷在25℃條件下的黏度較佳為10〜1000000mPa·s、更佳為100〜100000mPa·s、尤佳為300〜50000mPa·s。如果所述二有機聚矽氧烷黏度過低，則有可能固化物的硬度加大，進而不能獲得所需的特性；相反，如果所述二有機聚矽氧烷黏度過高，則有可能組合物的黏度增高，進而操作性降低。在此，其黏度可以通過旋轉黏度計（例如，BL型、BH型、BS型、錐板型以及流變儀等）進行測定。The viscosity of the diorganopolysiloxane at 25°C is preferably 10 to 1,000,000 mPa·s, more preferably 100 to 100,000 mPa·s, and particularly preferably 300 to 50,000 mPa·s. If the viscosity of the diorganopolysiloxane is too low, the hardness of the cured product may increase, and the desired characteristics may not be obtained; on the contrary, if the viscosity of the diorganopolysiloxane is too high, it may be combined The viscosity of the material increases, and the operability decreases. Here, its viscosity can be measured by a rotary viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.).
作為(A)成分的較佳具體例可列舉以下的化合物。As a preferable specific example of (A) component, the following compounds are mentioned.
[化學式1]
在本發明的組合物中，(A)成分以含有50〜95質量％為佳、以含有60〜93質量％較佳、以含有70〜90質量％更佳。In the composition of the present invention, the component (A) is preferably 50 to 95% by mass, 60 to 93% by mass, and more preferably 70 to 90% by mass.
[(B)成分] (B)成分的β-酮酸酯化合物通過與後面所述的(D)成分的含有胺基水解性有機矽烷和/或其部分水解縮合物在體系（組合物）內發生反應（酮亞胺反應）而生成水，進而起到作為對本發明的組合物賦予快速固化性和深處固化性的快速固化劑和深處固化劑的作用。其可列舉為例如，以下述通式（2）表示的化合物。[(B) Ingredient] The β-keto acid ester compound of component (B) reacts in the system (composition) with the amino group-containing hydrolyzable organosilane and/or its partial hydrolyzed condensate of component (D) described later (ketimine) Reaction) to generate water, and further serve as a rapid curing agent and a deep curing agent that impart rapid curing properties and deep curing properties to the composition of the present invention. This may be, for example, a compound represented by the following general formula (2).
[化學式2]
作為R2 和R3 ，可列舉為例如，為碳原子數1〜20、較佳為碳原子數1〜8、更佳為碳原子數1〜4的烷基，為碳原子數2〜20、較佳為碳原子數2〜8、更佳為碳原子數2〜4的烯基、為碳原子數6〜20、較佳為碳原子數6〜12、更佳為碳原子數6〜8的芳基以及這些烴基的一部分或全部的氫原子被氟等的鹵素原子所取代的基團等。作為該烷基，可例示為甲基、乙基、丙基以及環己基等。作為該烯基，可例示為乙烯基和烯丙基等。作為該芳基，可例示為苯基和甲苯基等。作為該鹵素原子取代基，可例示為3,3,3-三氟丙基等。作為R3 ，從與(D)成分的反應性的觀點考慮，其較佳為甲基、乙基、正丙基等或乙烯基等，更佳為甲基和乙基。作為(B)成分的具體例，可列舉為乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸丙酯、乙醯乙酸異丙酯、乙醯乙酸丁酯、乙醯乙酸異丁酯、丙醯乙酸甲酯以及丙醯乙酸乙酯。在它們當中，較佳為乙醯乙酸乙酯。Examples of R 2 and R 3 include, for example, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 8, more preferably 1 to 4 carbon atoms, and 2 to 20 carbon atoms. , Preferably carbon number 2~8, more preferably carbon number 2~4 alkenyl group, carbon number 6~20, preferably carbon number 6~12, more preferably carbon number 6~ The aryl group of 8 and groups in which a part or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine. As this alkyl group, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, etc. are illustrated. As this alkenyl group, a vinyl group, an allyl group, etc. are illustrated. As this aryl group, a phenyl group, a tolyl group, etc. can be illustrated. As the halogen atom substituent, 3,3,3-trifluoropropyl and the like can be exemplified. As R 3 , from the viewpoint of reactivity with the component (D), it is preferably a methyl group, an ethyl group, an n-propyl group, or a vinyl group, and more preferably a methyl group and an ethyl group. Specific examples of the component (B) include methyl acetylacetate, ethyl acetylacetate, propyl acetylacetate, isopropyl acetylacetate, butyl acetylacetate, isobutyl acetylacetate, Methyl propylacetate and ethyl propylacetate. Among them, ethyl acetylacetate is preferred.
相對於(A)成分100質量份，(B)成分的混合量為0.01〜2質量份的範圍、較佳為0.05〜2質量份的範圍、更佳為0.1〜1質量份的範圍。如果(B)成分的混合量小於0.01質量份，則固化性變差，進而難以獲得所需的室溫縮合固化性有機聚矽氧烷組合物。另外，如果(B)成分的混合量超過2質量份，則不僅不能獲得所需的物性，而且有可能發生來自組合物的滲出，這在成本上則更為不利。The mixing amount of (B) component is in the range of 0.01 to 2 parts by mass, preferably in the range of 0.05 to 2 parts by mass, and more preferably in the range of 0.1 to 1 part by mass relative to 100 parts by mass of (A) component. If the blending amount of the component (B) is less than 0.01 parts by mass, the curability will deteriorate, and it will be difficult to obtain the desired room temperature condensation-curable organopolysiloxane composition. In addition, if the blending amount of the component (B) exceeds 2 parts by mass, not only the desired physical properties cannot be obtained, but also bleeding from the composition may occur, which is even more disadvantageous in terms of cost.
[(C)成分] (C)成分的水解性有機矽烷化合物和/或其部分水解縮合物為例如，以下述通式（3）表示的在1個分子中具有3個以上（通常為3個或4個）已與矽原子鍵合的有機氧基的水解性有機矽烷化合物和/或其部分水解縮合物，且起著作為本發明組合物的固化劑（交聯劑）的作用。需要說明的是，在本發明中的「部分水解縮合物」其含義為在將該（有機）矽烷化合物部分水解·縮合而生成的分子中，具有至少2個、較佳為3個的殘存水解性基團的（有機）矽氧烷低聚物。 R4 x -Si（OR5 ）4-x （3） （在通式（3）中，R4 為碳原子數1〜10、較佳為碳原子數1〜6的未經取代的一價烴基，R5 分別獨立地為作為R4 或-OR5 的形成碳原子數3〜10的酮肟基的殘基，x為0或1。）[Component (C)] The hydrolyzable organosilane compound and/or its partial hydrolyzed condensate of component (C) is, for example, represented by the following general formula (3) having 3 or more (usually 3) in one molecule Or 4) hydrolyzable organosilane compounds of organooxy groups bonded to silicon atoms and/or partial hydrolysis condensates thereof, and act as a curing agent (crosslinking agent) for the composition of the present invention. It should be noted that the "partially hydrolyzed condensate" in the present invention means that in the molecule formed by the partial hydrolysis and condensation of the (organo)silane compound, there are at least two, preferably three remaining hydrolyzed (Organic) siloxane oligomers with functional groups. R 4 x -Si(OR 5 ) 4-x (3) (In the general formula (3), R 4 is an unsubstituted monovalent one having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms Hydrocarbyl group, R 5 is each independently a residue that forms a ketoxime group having 3 to 10 carbon atoms as R 4 or -OR 5 , and x is 0 or 1.)
作為R4 ，可列舉為例如，甲基、乙基、丙基、異丙基、丁基、異丁基、仲丁基、叔丁基等的烷基；環己基等的環狀烷基；乙烯基、烯丙基等的烯基；苯基、甲苯基等的芳基等。作為R5 ，除了作為所述R4 所示例的未經取代的一價烴基之外，還可列舉為作為-OR5 的形成二甲基酮肟基、甲基乙基酮肟基、甲基異丁基酮肟基等的酮肟基的殘基等。Examples of R 4 include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl; cyclic alkyl groups such as cyclohexyl; Alkenyl groups such as vinyl and allyl; aryl groups such as phenyl and tolyl. As R 5 , in addition to the unsubstituted monovalent hydrocarbon group exemplified as R 4 , there can be exemplified dimethyl ketoxime group, methyl ethyl ketoxime group, methyl group as -OR 5 Residues of ketoxime groups such as isobutyl ketoxime groups.
在這些當中，作為R4 ，較佳為甲基、乙基以及乙烯基，更佳為甲基和乙基。作為R5 ，其分別獨立地較佳為甲基、乙基以及作為-OR5 的形成二甲基酮肟基、甲基乙基酮肟基的殘基。R4 、R5 可為相同也可為不同。x為0或1的整數。作為(C)成分的具體例，可列舉為四甲氧基矽烷、四乙氧基矽烷、矽酸甲酯、矽酸乙酯、四正丙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、苯基三甲氧基矽烷、乙基三甲氧基矽烷以及乙基三乙氧基矽烷等的烷氧基矽烷；甲基三（二甲基酮肟）矽烷、甲基三（甲基乙基酮肟）矽烷、乙基三（甲基乙基酮肟）矽烷、甲基三（甲基異丁基酮肟）矽烷、乙烯基三（甲基乙基酮肟）矽烷以及苯基三（甲基乙基酮肟）矽烷等的酮肟矽烷；甲基三異丙烯氧基矽烷、乙基三異丙烯氧基矽烷、乙烯基三異丙烯氧基矽烷、苯基三異丙烯氧基矽烷等的含有異丙烯氧基的矽烷；甲基三乙醯氧基矽烷、乙基三乙醯氧基矽烷、乙烯基三乙醯氧基矽烷等的乙醯氧基矽烷，以及這些各矽烷的部分水解縮合物（矽氧烷低聚物）等。在它們當中，較佳為甲基三甲氧基矽烷、四乙氧基矽烷以及四正丙氧基矽烷。Among these, as R 4 , methyl, ethyl, and vinyl are preferred, and methyl and ethyl are more preferred. As R 5 , it is each independently preferably a methyl group, an ethyl group, and a residue forming a dimethyl ketoxime group and a methyl ethyl ketoxime group as -OR 5 . R 4 and R 5 may be the same or different. x is an integer of 0 or 1. Specific examples of (C) component include tetramethoxysilane, tetraethoxysilane, methyl silicate, ethyl silicate, tetra-n-propoxysilane, methyltrimethoxysilane, methyl Alkoxysilanes such as triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, phenyl trimethoxysilane, ethyl trimethoxysilane, and ethyl triethoxysilane; Tris (dimethyl ketoxime) silane, methyl tris (methyl ethyl ketoxime) silane, ethyl tris (methyl ethyl ketoxime) silane, methyl tris (methyl isobutyl ketoxime) silane , Vinyl tris (methyl ethyl ketoxime) silane and phenyl tris (methyl ethyl ketoxime) silane and other ketoxime silanes; methyl triisopropenoxy silane, ethyl triisopropenoxy silane, Isopropenoxy-containing silanes such as vinyl triisopropenoxysilane and phenyl triisopropenoxysilane; methyl triethoxysilane, ethyl triethoxysilane, vinyl triacetoxysilane Acetoxysilanes such as oxysilanes, and partial hydrolysis condensates of these silanes (siloxane oligomers), etc. Among them, methyltrimethoxysilane, tetraethoxysilane, and tetra-n-propoxysilane are preferred.
需要說明的是，(C)成分的水解性有機矽烷化合物和/或其部分水解縮合物，在除已與矽原子鍵合的水解性基團外，為不含有在分子中用含有氧原子、氮原子、硫原子等的雜原子的官能性基團取代的一價烴基的這一點上，與後面所述的為(D)成分的含有胺基水解性有機矽烷化合物和/或其部分水解縮合物具有明顯的區別。It should be noted that the hydrolyzable organosilane compound and/or its partially hydrolyzed condensate of component (C), except for the hydrolyzable group bonded to the silicon atom, does not contain oxygen atoms in the molecule, With regard to the monovalent hydrocarbon group substituted with a heteroatomic functional group such as a nitrogen atom, a sulfur atom, etc., it is hydrolyzed and condensed with an amino group-containing hydrolyzable organosilane compound and/or a partial hydrolysis condensation of the component (D) described later There is a clear difference between things.
相對於(A)成分100質量份，(C)成分的混合量為0.1〜15質量份的範圍、較佳為0.1〜12質量份的範圍、更佳為1〜10質量份的範圍。如果(C)成分的混合量小於0.1質量份，則難以獲得賦予具有所需的橡膠彈性的矽酮橡膠固化物的室溫縮合固化性有機聚矽氧烷組合物。另外，如果(C)成分的混合量超過15質量份，則所得到的固化物（矽酮橡膠）的機械特性容易降低，另外，還有可能導致產生組合物的固化速度也變慢等的問題。The mixing amount of the (C) component is in the range of 0.1 to 15 parts by mass relative to 100 parts by mass of the (A) component, preferably in the range of 0.1 to 12 parts by mass, more preferably in the range of 1 to 10 parts by mass. If the blending amount of the component (C) is less than 0.1 parts by mass, it is difficult to obtain a room temperature condensation-curable organopolysiloxane composition that imparts a cured silicone rubber with desired rubber elasticity. In addition, if the blending amount of component (C) exceeds 15 parts by mass, the mechanical properties of the resulting cured product (silicone rubber) are likely to be reduced. In addition, it may also cause problems such as slower curing speed of the composition. .
[(D)成分] (D)成分的含有胺基水解性有機矽烷化合物和/或其部分水解縮合物，通過在體系內（組合物內）與如上所述的(B)成分的β-酮酸酯化合物發生反應（酮亞胺反應）而生成水，進而起到作為對本發明的組合物賦予快速固化性和深處固化性的快速固化劑和深處固化劑的作用。[(D) Ingredient] (D) The amino-hydrolyzable organosilane compound and/or its partial hydrolyzed condensate of component (D) reacts with the β-keto acid ester compound of component (B) in the system (in the composition) ( The ketimine reacts) to generate water, and further functions as a rapid curing agent and a deep curing agent that impart rapid curing properties and deep curing properties to the composition of the present invention.
作為(D)成分的含有胺基水解性有機矽烷化合物，可適合使用公知的所述化合物，具體而言，可例示為γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、3-（2-胺基乙基胺基）丙基三甲氧基矽烷、3-（2-胺基乙基胺基）丙基三乙氧基矽烷、3-（2-胺基乙基胺基）丙基（甲基）二甲氧基矽烷、3-（2-胺基乙基胺基）丙基（甲基）二乙氧基矽烷等。在它們當中，較佳為γ-胺基丙基三乙氧基矽烷、3-（2-胺基乙基胺基）丙基三甲氧基矽烷等的含胺基烷基的烷氧基矽烷類。As the amino group-containing hydrolyzable organosilane compound of the component (D), known compounds can be suitably used. Specifically, γ-aminopropyltrimethoxysilane and γ-aminopropyltriethyl can be exemplified Oxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-amino) Ethylamino)propyl(methyl)dimethoxysilane, 3-(2-aminoethylamino)propyl(methyl)diethoxysilane, etc. Among them, preferred are alkoxysilanes containing amino alkyl groups such as γ-aminopropyltriethoxysilane and 3-(2-aminoethylamino)propyltrimethoxysilane. .
相對於(A)成分100質量份，(D)成分為混合0.1~5質量份，尤佳為混合1~5質量份。如果(D)成分的混合量小於0.1質量份，則不能獲得所需的固化性。另外，如果(D)成分的混合量超過5質量份，則有可能所獲得的固化物其機械特性容易降低，另外，在成本方面也不利。With respect to 100 parts by mass of the (A) component, the (D) component is mixed by 0.1 to 5 parts by mass, and particularly preferably is mixed by 1 to 5 parts by mass. If the blending amount of the component (D) is less than 0.1 parts by mass, the desired curability cannot be obtained. In addition, if the mixing amount of the component (D) exceeds 5 parts by mass, the mechanical properties of the obtained cured product may be easily reduced, and it is also disadvantageous in terms of cost.
需要說明的是，相對於前面所述的(B)成分的β-酮酸酯化合物中的羰基，(D)成分的混合量較佳為(D)成分中的胺基在1~5莫耳當量的範圍內。It should be noted that, relative to the carbonyl group in the β-keto acid ester compound of the component (B), the mixing amount of the component (D) is preferably such that the amine group in the component (D) is 1 to 5 mol Within the range of equivalent.
[(E)成分] (E)成分的固化催化劑可以單獨使用一種、也可以作為二種以上的混合物進行使用。作為(E)成分的固化催化劑，可例示為，錫、鈦、鋯、鐵、銻、鉍以及錳等的金屬的有機羧酸鹽或醇鹽；有機鈦酸鹽以及有機鈦螯合物。更為具體說來，可例示為二月桂酸二丁基錫、二辛酸二丁基錫、二月桂酸二辛基錫、二新癸酸二甲基錫、二新癸酸二辛基錫等的二羧酸二烷基錫鹽，二甲醇二丁基錫、二乙醇二丁基錫等的二烷基錫二醇鹽，馬來酯二丁基錫，辛酸亞錫等的錫化合物；四丁基鈦酸鹽、二異丙氧基雙（乙醯丙酮）鈦、二異丙氧基雙（乙醯乙酸乙酯）鈦等的鈦化合物；二丁胺、月桂胺等的胺化合物及其鹽，四甲基胍、四甲基胍基丙基三甲氧基矽烷等的胍化合物及其鹽等。由於本發明的組合物的快速固化性和深處固化性等的固化特性優異，因此，其較佳為添加錫化合物，其中，較佳為添加二烷基錫二醇鹽、二羧酸二烷基錫鹽。相對於(A)成分100質量份，其添加量為0.001〜5質量份、較佳為0.01〜1.5質量份、尤佳為0.01〜1質量份。[(E) Ingredient] (E) The curing catalyst of the component may be used alone or as a mixture of two or more kinds. Examples of the curing catalyst of the component (E) include organic carboxylates or alkoxides of metals such as tin, titanium, zirconium, iron, antimony, bismuth, and manganese; organic titanates and organic titanium chelate compounds. More specifically, examples include dicarboxylic acids such as dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin dilaurate, dimethyltin dineodecanoate, and dioctyltin dineodecanoate. Dialkyltin salts, dialkyltin glycol salts such as dibutyltin dimethoxide, dibutyltin diethanol, and tin compounds such as dibutyltin maleate and stannous octoate; tetrabutyl titanate, diisopropoxy Titanium compounds such as base bis(acetacetone) titanium, diisopropoxy bis(ethyl acetate) titanium; amine compounds such as dibutylamine, laurylamine and their salts, tetramethylguanidine, tetramethyl Guanidine compounds such as guanidinopropyltrimethoxysilane and their salts. Since the composition of the present invention has excellent curing characteristics such as rapid curing and deep curing properties, it is preferable to add tin compounds, and among them, it is preferable to add dialkyltin glycol salts and dicarboxylic acid dioxanes. Base tin salt. The addition amount is 0.001 to 5 parts by mass, preferably 0.01 to 1.5 parts by mass, and particularly preferably 0.01 to 1 part by mass relative to 100 parts by mass of component (A).
如果(E)成分的混合量小於0.001質量份，則組合物不能獲得足夠的固化性。另外，如果(E)成分的混合量超過5質量份，則有可能導致產生在價格上不利和固化速度降低等的問題。If the blending amount of the (E) component is less than 0.001 parts by mass, the composition cannot obtain sufficient curability. In addition, if the blending amount of the component (E) exceeds 5 parts by mass, it may cause problems such as disadvantages in price and reduction in curing speed.
[其它成分] 另外，在本發明中可以根據需要，適當地混合上述成分以外的其它成分（任意成分）。作為其它成分（任意成分），只要在不損害本發明的目的的範圍內，可以添加公知的添加劑。例如，可列舉為作為潤濕劑（分散劑）或觸變改進劑的聚醚、作為增塑劑的非反應性二甲基矽油、作為溶劑的異石蠟烴、作為交聯密度改進劑的三甲基甲矽烷氧基單元[(CH3 )3 SiO1/2 單元]（M單元）和由SiO4/2 單元（Q單元）組成的三維網狀有機聚矽氧烷樹脂等。[Other components] In the present invention, other components (optional components) other than the above-mentioned components can be appropriately mixed as necessary. As other components (optional components), well-known additives can be added as long as they do not impair the purpose of the present invention. For example, polyether as a wetting agent (dispersant) or thixotropy modifier, non-reactive simethicone as a plasticizer, isoparaffin hydrocarbon as a solvent, and three as a crosslink density improver Methyl silyloxy unit [(CH 3 ) 3 SiO 1/2 unit] (M unit) and three-dimensional network organopolysiloxane resin composed of SiO 4/2 unit (Q unit).
進一步，根據需要，也可添加螢光增白劑等的著色劑，殺真菌劑，抗菌劑，作為滲油的非反應性苯基矽油，甲苯、二甲苯、溶劑揮發油、環己烷、甲基環己烷以及低沸點異石蠟烴等的溶劑。這些任意成分可以添加第一組分和/或第二組分的任意一種。Furthermore, if necessary, coloring agents such as fluorescent brighteners, fungicides, antibacterial agents, non-reactive phenyl silicone oils as oil bleeding, toluene, xylene, solvent volatile oil, cyclohexane, methyl Solvents such as cyclohexane and low-boiling isoparaffin hydrocarbons. Any one of the first component and/or the second component can be added to these optional components.
需要說明的是，從保持光透射率以及固化物的低硬度性、高伸長率、屈曲性等的特性的觀點考慮，本發明的二元型室溫縮合固化性有機聚矽氧烷組合物較佳為在組合物中不含有所謂的非填充料類的組合物，即不含有：二氧化矽類微粉末、氧化鈦等的金屬氧化物微粒，碳酸鈣微粉末等的金屬碳酸鹽微粒，炭黑等的無機填充劑（無機填充料）。It should be noted that the binary room temperature condensation curable organopolysiloxane composition of the present invention is relatively high from the viewpoint of maintaining the light transmittance and the properties of the cured product such as low hardness, high elongation, and flexibility. It is preferable that the composition does not contain so-called non-filler-based composition, that is, it does not contain: silica fine powder, metal oxide particles such as titanium oxide, metal carbonate particles such as calcium carbonate fine powder, and carbon Black inorganic filler (inorganic filler).
>組合物的製造方法> 本發明的二元型室溫縮合固化性有機聚矽氧烷組合物，首先通過按照常規的方法將應該混合在第一組分和第二組分中的上述各種成分和根據需要的其它成分分別混合至均勻，進而分別單獨地製造了第一組分和第二組分，且在使用時混合第一組分和第二組分。其較佳為將第一組分和第二組分在避免潮濕的氣氛中進行儲存。當固化本發明的組合物時，將這些第一組分和第二組分以適當的混合比例混合至均勻，且通過將混合物置於室溫（23℃±15℃）且含有濕氣的氣氛（大氣）中通常曝露10分鐘~5天內，進而能夠完全地固化至所述組合物的深處。因此，本發明的組合物其快速固化性和深處固化性優異。>Production method of composition> In the binary room temperature condensation-curable organopolysiloxane composition of the present invention, the above-mentioned various components that should be mixed in the first component and the second component and other components as required are firstly mixed according to a conventional method. After mixing until uniform, the first component and the second component are separately manufactured, and the first component and the second component are mixed during use. It is preferable to store the first component and the second component in an atmosphere that avoids moisture. When curing the composition of the present invention, the first component and the second component are mixed in an appropriate mixing ratio until uniform, and by placing the mixture at room temperature (23°C±15°C) and an atmosphere containing moisture (Atmosphere) usually exposed for 10 minutes to 5 days, and then can be completely cured to the depth of the composition. Therefore, the composition of the present invention is excellent in rapid curability and deep curability.
另外，作為將本發明的二元型室溫縮合固化性有機聚矽氧烷組合物作為黏接劑、塗布劑或封裝劑等將其塗布在各種基材上且使其固化時的該組合物的固化方法的一實施例，例如，也可使用如下的手法，即，通過將含有(A)成分和(B)成分的第一組分塗布在第一基材的表面上，且將含有(C)成分、(D)成分以及(E)成分的第二組分塗布在第二基材的表面上，並且以第一組分和第二組分相接觸的方式將雙方的基材彼此相向並接觸，進而將第一組分和第二組分進行貼合並使其固化的方法等的手法。In addition, as the binary type room temperature condensation-curable organopolysiloxane composition of the present invention as an adhesive, coating agent, encapsulant, etc., it is applied to various substrates and cured. An example of the curing method of, for example, the following method can also be used, that is, by coating the first component containing (A) component and (B) component on the surface of the first substrate, and containing ( The second component of component C), component (D), and component (E) is coated on the surface of the second substrate, and the substrates of both sides face each other in such a way that the first component and the second component are in contact And contact, and then the first component and the second component are bonded and cured.
本發明的二元型室溫縮合固化性有機聚矽氧烷組合物能夠賦予具有優異的光透射率的同時還能具有低硬度性、高伸長率、優異的屈曲性的矽酮橡膠固化物。由本發明的二元型室溫縮合固化性有機聚矽氧烷組合物所獲得的矽酮橡膠固化物在2.5mm的厚度條件下其在400〜800nm的波長區域內的光透射率為80％以上。另外，由本發明的二元型室溫縮合固化性有機聚矽氧烷組合物所獲得的矽酮橡膠固化物，具有屈曲性，例如，即使將在外表面上具有3mm厚的矽酮橡膠固化物層的基板（例如，蛇型LED基板）連同該矽酮橡膠固化物層一同向內側彎曲180°，在外表面上的矽酮橡膠固化物層也不會產生裂紋。The binary type room temperature condensation-curable organopolysiloxane composition of the present invention can provide a cured silicone rubber that has excellent light transmittance and also has low hardness, high elongation, and excellent flexibility. The cured silicone rubber obtained from the binary room temperature condensation-curable organopolysiloxane composition of the present invention has a light transmittance of 80% or more in the wavelength region of 400~800nm under the condition of a thickness of 2.5mm . In addition, the cured silicone rubber obtained from the binary room temperature condensation-curable organopolysiloxane composition of the present invention has flexibility, for example, even if it has a 3mm thick silicone rubber cured layer on the outer surface The substrate (for example, the snake-shaped LED substrate) and the cured silicone rubber layer are bent 180° inwardly, and the cured silicone rubber layer on the outer surface will not crack.
將本發明的組合物進行固化而成的矽酮橡膠固化物，能夠廣泛地應用，包括需要高光透射率、低硬度以及屈曲性的光學用途。特別是，作為用於路燈等的可彎折的LED用封裝樹脂等有用。The cured silicone rubber obtained by curing the composition of the present invention can be widely used, including optical applications requiring high light transmittance, low hardness, and flexibility. In particular, it is useful as a bendable LED encapsulating resin used for street lamps and the like.
（實施例） 以下，表示對本發明進行具體地說明的實施例和比較例，但本發明不限於下述的實施例。需要說明的是，其黏度為在25℃條件下通過旋轉黏度計所測定的值。(Example) Hereinafter, examples and comparative examples to specifically explain the present invention are shown, but the present invention is not limited to the following examples. It should be noted that the viscosity is a value measured by a rotary viscometer at 25°C.
[第一組分A的調製] 在減壓條件下，將60質量份的用羥基（矽烷醇基）封端分子鏈兩末端的在25℃條件下的黏度為20000mPa·s的二甲基聚矽氧烷（在上述通式（1）中，R1 為甲基，n相當於約為615）和20質量份的用羥基（矽烷醇基）封端分子鏈兩末端的在25℃條件下的黏度為1500mPa·s的二甲基聚矽氧烷（在上述通式（1）中，R1 為甲基，n相當於約為305）以及0.2質量份的乙醯乙酸乙酯混合60分鐘，進而獲得了第一組分A。[Preparation of the first component A] Under reduced pressure, 60 parts by mass of dimethyl polymer with a viscosity of 20,000 mPa·s at 25°C and a hydroxyl group (silanol group) terminated at both ends of the molecular chain Siloxane (in the above general formula (1), R 1 is a methyl group, n is equivalent to about 615) and 20 parts by mass of the two ends of the molecular chain terminated with hydroxyl groups (silanol groups) at 25°C Dimethyl polysiloxane with a viscosity of 1500 mPa·s (in the above general formula (1), R 1 is a methyl group, and n is equivalent to about 305) and 0.2 parts by mass of ethyl acetone are mixed for 60 minutes , And then obtained the first component A.
[第一組分B的調製] 在減壓條件下，將60質量份的用羥基（矽烷醇基）封端分子鏈兩末端的在25℃條件下的黏度為20000mPa·s的二甲基聚矽氧烷（在上述通式（1）中，R1 為甲基，n相當於約為615）和20質量份的用羥基（矽烷醇基）封端分子鏈兩末端的在25℃條件下的黏度為1500mPa·s的二甲基聚矽氧烷（在上述通式（1）中，R1 為甲基，n相當於約為305）以及0.3質量份的乙醯乙酸乙酯混合60分鐘，進而獲得了第一組分B。[Preparation of the first component B] Under reduced pressure, 60 parts by mass of dimethyl polymer with a viscosity of 20,000 mPa·s at 25°C and a hydroxy group (silanol group) terminated at both ends of the molecular chain Siloxane (in the above general formula (1), R 1 is a methyl group, n is equivalent to about 615) and 20 parts by mass of the two ends of the molecular chain terminated with hydroxyl groups (silanol groups) at 25°C Dimethyl polysiloxane with a viscosity of 1500 mPa·s (in the above general formula (1), R 1 is a methyl group, and n is equivalent to about 305) and 0.3 parts by mass of ethyl acetate are mixed for 60 minutes , And then obtained the first component B.
[第二組分A的調製] 在常壓（1個大氣壓）條件下，將20質量份的用三甲基甲矽烷氧基封端分子鏈兩末端的在25℃條件下的黏度為100mPa·s的二甲基聚矽氧烷（非反應性二甲基矽油）、3質量份的四乙氧基矽烷、3質量份的γ-胺基丙基三乙氧基矽烷以及0.03質量份的二新癸酸二甲基錫混合20分鐘，進而獲得了第二組分A。[Modulation of the second component A] Under normal pressure (1 atm), 20 parts by mass of dimethylpolysiloxane with a viscosity of 100mPa·s at 25°C, with both ends of the molecular chain terminated with trimethylsilyloxy groups (Non-reactive dimethyl silicone oil), 3 parts by mass of tetraethoxysilane, 3 parts by mass of γ-aminopropyl triethoxysilane, and 0.03 parts by mass of dimethyl tin dineodecanoate mixed 20 Minutes, and then obtain the second component A.
[第二組分B的調製] 在常壓（1個大氣壓）條件下，將20質量份的用三甲基甲矽烷氧基封端分子鏈兩末端的在25℃條件下的黏度為100mPa·s的二甲基聚矽氧烷（非反應性二甲基矽油）、4質量份的四乙氧基矽烷、3質量份的γ-胺基丙基三乙氧基矽烷以及0.03質量份的二新癸酸二甲基錫混合20分鐘，進而獲得了第二組分B。[Modulation of the second component B] Under normal pressure (1 atm), 20 parts by mass of dimethylpolysiloxane with a viscosity of 100mPa·s at 25°C, with both ends of the molecular chain terminated with trimethylsilyloxy groups (Non-reactive dimethyl silicone oil), 4 parts by mass of tetraethoxysilane, 3 parts by mass of γ-aminopropyltriethoxysilane, and 0.03 parts by mass of dimethyl tin dineodecanoate mixed 20 Minutes, and then the second component B was obtained.
[實施例1] 將上述第一組分A和上述第二組分A以4：1（質量）的混合比混合5分鐘，且在獲得組合物1之後，以將該組合物1形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，進而獲得了組合物1的固化物。[Example 1] The above-mentioned first component A and the above-mentioned second component A were mixed at a mixing ratio of 4:1 (mass) for 5 minutes, and after obtaining the composition 1, the composition 1 was formed into a thickness of 2.5 mm After curing for 3 days under the conditions of 23° C./50% RH, a cured product of composition 1 was obtained.
[實施例2] 將上述第一組分B和上述第二組分A以4：1（質量）的混合比混合5分鐘，且在獲得組合物2之後，以將該組合物2形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，進而獲得了組合物2的固化物。[Example 2] The above-mentioned first component B and the above-mentioned second component A were mixed for 5 minutes at a mixing ratio of 4:1 (mass), and after obtaining the composition 2, the composition 2 was formed into a thickness of 2.5 mm After curing for 3 days under the conditions of 23° C./50% RH, a cured product of composition 2 was obtained.
[實施例3] 將上述第一組分A和上述第二組分B以4：1（質量）的混合比混合5分鐘，且在獲得組合物3之後，以將組合物3形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，進而獲得了組合物3的固化物。[Example 3] The above-mentioned first component A and the above-mentioned second component B were mixed at a mixing ratio of 4:1 (mass) for 5 minutes, and after the composition 3 was obtained, the composition 3 was formed into a thickness of 2.5 mm at 23 After curing for 3 days under the condition of °C/50% RH, a cured product of composition 3 was obtained.
[實施例4] 將上述第一組分B和上述第二組分B以4：1（質量）的混合比混合5分鐘，且在獲得組合物4之後，以將該組合物4形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，進而獲得了組合物4的固化物。[Example 4] The above-mentioned first component B and the above-mentioned second component B were mixed at a mixing ratio of 4:1 (mass) for 5 minutes, and after the composition 4 was obtained, the composition 4 was formed into a thickness of 2.5 mm. After curing for 3 days under the conditions of 23° C./50% RH, a cured product of composition 4 was obtained.
[比較例1] 雖然嘗試著將上述第一組分A中未添加乙醯乙酸乙酯者作為第一組分，且將該第一組分和上述第二組分A以4：1（質量）的混合比混合5分鐘，且在獲得組合物5之後，以將該組合物5形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，但組合物5未能夠充分固化。[Comparative Example 1] Although I tried to use the above first component A without adding ethyl acetate as the first component, and the first component and the above second component A were mixed at a mixing ratio of 4:1 (mass) After 5 minutes, and after obtaining the composition 5, the composition 5 was cured for 3 days under the conditions of 23° C./50% RH so that the thickness of the composition 5 was 2.5 mm, but the composition 5 was not sufficiently cured.
[比較例2] 雖然嘗試著將上述第二組分A中未添加γ-胺基丙基三乙氧基矽烷者作為第二組分，且將上述第一組分A和該第二組分以4：1（質量）的混合比混合5分鐘，且在獲得組合物6之後，以將該組合物6形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，但組合物6未能夠充分固化。[Comparative Example 2] Although trying to use the above second component A without adding γ-aminopropyltriethoxysilane as the second component, and the above first component A and the second component at 4:1 ( The mixing ratio of mass) was mixed for 5 minutes, and after the composition 6 was obtained, the composition 6 was cured for 3 days under the conditions of 23°C/50% RH so that the thickness of the composition 6 was 2.5 mm, but the composition 6 failed Fully cured.
評估項目evaluation items
i）固化性 將第一組分和第二組分以4：1（質量）混合比進行混合的組合物1-6分別放入在200mL聚丙烯製容器中，且在23℃/50％RH條件下測定了直至該組合物1〜6完全停止流動所需的時間（即，固化時間）。將具體的測定方法表述如下。 將裝入該組合物1〜6的聚丙烯製容器傾斜90°，並測定了該組合物直至不再流動所需的時間。i) Curability The first component and the second component were mixed at a mixing ratio of 4:1 (mass), and the composition 1-6 was put into a 200 mL polypropylene container, and the measurement was carried out at 23°C/50%RH. The time required until the compositions 1 to 6 completely stop flowing (ie, curing time). The specific measurement method is described below. The polypropylene container filled with the compositions 1 to 6 was tilted by 90°, and the time required for the composition to stop flowing was measured.
ii）橡膠物性 根據JISK6249標準，對上述組合物1〜6的固化物進行了硬度（Durometer. A）、斷裂伸長率（％）、拉伸強度（MPa）以及密度（g/cm3 ）的測定。ii) Rubber physical properties According to JISK6249 standard, the hardness (Durometer. A), elongation at break (%), tensile strength (MPa) and density (g/cm 3 ) of the cured products of the above compositions 1 to 6 were measured .
iii）光透射率 使用日商日立高新技術科學公司製造的分光光度計U-3310，對上述組合物1〜6的固化物進行了在400nm、500nm以及800nm下的光透射率（％）的測定。iii) Light transmittance Using a spectrophotometer U-3310 manufactured by Nissho Hitachi High-Technologies Corporation, the light transmittance (%) of the cured products of the above compositions 1 to 6 was measured at 400 nm, 500 nm, and 800 nm.
iv）彎曲試驗 將上述組合物1〜6以3mm的厚度分別封裝在蛇型LED基板上，且在23℃/50％RH的環境條件下固化了3天。之後，將蛇形LED基板彎曲為180°且通過目視對上述組合物1〜6的固化物進行了是否發生了裂紋的確認。其評估標準如下。 ○：在固化物上完全未發生裂紋 ×：在固化物上產生了裂紋iv) Bend test The above compositions 1 to 6 were respectively encapsulated on a snake-shaped LED substrate with a thickness of 3 mm, and cured for 3 days under an environmental condition of 23° C./50% RH. After that, the serpentine LED substrate was bent to 180°, and the cured products of the above-mentioned compositions 1 to 6 were checked visually whether cracks occurred. The evaluation criteria are as follows. ○: No cracks occurred on the cured product at all ×: Cracks occurred in the cured product
結果 在表1中示出了通過上述方法對組合物1〜6及其固化物的評估結果。result Table 1 shows the evaluation results of compositions 1 to 6 and their cured products by the above-mentioned method.
[表1]
與含有第一組分A的組合物的流動停止時間（固化時間）相比較，含有第一組分B的組合物的流動停止時間（固化時間）短。這是因為在第一組分B中與(D)成分中的γ-胺基丙基三乙氧基矽烷反應的(B)成分中的乙醯乙酸乙酯的含量大於在第一組分A中的含量，進而所副產的水分子也多的緣故。Compared with the flow stop time (curing time) of the composition containing the first component A, the flow stop time (curing time) of the composition containing the first component B is short. This is because the content of ethyl acetate in the component (B) that reacts with the γ-aminopropyltriethoxysilane in component (D) in the first component B is greater than that in the first component A In addition, the amount of by-product water molecules is also more.
需要說明的是，即使改變第一組分A和第一組分B的組合以及改變第二組分A和第二組分B的組合，也能夠確認到橡膠物性和光透射率為所希望的值。It should be noted that even if the combination of the first component A and the first component B and the combination of the second component A and the second component B are changed, the rubber properties and light transmittance can be confirmed to the desired value .
在組合物5或組合物6中，由於未添加乙醯乙酸乙酯或γ-胺基丙基三乙氧基矽烷，因此其固化性差，即使經過3天也未能夠得到固化物，進而無法測定其橡膠物性。因此，也不能測定光透射率，並且未能實施彎曲試驗。In composition 5 or composition 6, since ethyl acetoxyacetate or γ-aminopropyl triethoxysilane was not added, the curability was poor, and the cured product could not be obtained even after 3 days, so it could not be measured Its rubber properties. Therefore, the light transmittance could not be measured, and the bending test could not be performed.
以下，亦記載了已使用其它的(C)成分之實施例和比較例。Hereinafter, examples and comparative examples using other (C) components are also described.
[第二組分C的調製] 在常壓下將20質量份的分子鏈兩末端用三甲基甲矽烷氧基封端的在25℃條件下黏度為100mPa·s的二甲基聚矽氧烷（非反應性二甲基矽油）、3質量份的四正丙氧基矽烷、2質量份的γ-胺基丙基三乙氧基矽烷以及0.03質量份的二新癸酸二甲基錫混合20分鐘，進而得到了第二組分C。[Modulation of the second component C] Dimethyl polysiloxane (non-reactive dimethyl silicone oil) with a viscosity of 100 mPa·s at 25°C with 20 parts by mass of the molecular chain terminated at both ends of the molecular chain under normal pressure with trimethylsilyloxy groups , 3 parts by mass of tetra-n-propoxysilane, 2 parts by mass of γ-aminopropyltriethoxysilane, and 0.03 parts by mass of dimethyl tin dineodecanoate were mixed for 20 minutes to obtain the second group Points C.
[第二組分D的調製] 在常壓下將20質量份的分子鏈兩末端用三甲基甲矽烷氧基封端的在25℃條件下黏度為100mPa·s的二甲基聚矽氧烷（非反應性二甲基矽油）、3質量份的四正丙氧基矽烷、3質量份的γ-胺基丙基三乙氧基矽烷以及0.03質量份的二新癸酸二甲基錫混合20分鐘，進而得到了第二組分D。[Modulation of the second component D] Dimethyl polysiloxane (non-reactive dimethyl silicone oil) with a viscosity of 100 mPa·s at 25°C with 20 parts by mass of the molecular chain terminated at both ends of the molecular chain under normal pressure with trimethylsilyloxy groups , 3 parts by mass of tetra-n-propoxysilane, 3 parts by mass of γ-aminopropyl triethoxysilane, and 0.03 parts by mass of dimethyl tin dineodecanoate were mixed for 20 minutes to obtain the second group Points D.
[實施例5] 將上述第一組分A和上述第二組分C以4：1（質量）的混合比混合5分鐘，且在獲得組合物7之後，以將該組合物7形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，進而獲得了組合物7的固化物。[Example 5] The first component A and the second component C were mixed for 5 minutes at a mixing ratio of 4:1 (mass), and after obtaining the composition 7, the composition 7 was formed into a thickness of 2.5 mm. After curing for 3 days under the conditions of 23° C./50% RH, a cured product of composition 7 was obtained.
[實施例6] 將上述第一組分B和上述第二組分C以4：1（質量）的混合比混合5分鐘，且在獲得組合物8之後，以將該組合物8形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，進而獲得了組合物8的固化物。[Example 6] The above-mentioned first component B and the above-mentioned second component C were mixed at a mixing ratio of 4:1 (mass) for 5 minutes, and after the composition 8 was obtained, the composition 8 was formed into a thickness of 2.5 mm. After curing for 3 days under the conditions of 23° C./50% RH, a cured product of composition 8 was obtained.
[實施例7] 將上述第一組分A和上述第二組分D以4：1（質量）的混合比混合5分鐘，且在獲得組合物9之後，以將該組合物9形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，進而獲得了組合物9的固化物。[Example 7] Mix the first component A and the second component D at a mixing ratio of 4:1 (mass) for 5 minutes, and after obtaining the composition 9, the composition 9 is formed into a thickness of 2.5 mm After curing for 3 days under the conditions of 23° C./50% RH, a cured product of composition 9 was obtained.
[實施例8] 將上述第一組分B和上述第二組分D以4：1（質量）的混合比混合5分鐘，且在獲得組合物10之後，以將該組合物10形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，進而獲得了組合物10的固化物。[Example 8] Mix the first component B and the second component D at a mixing ratio of 4:1 (mass) for 5 minutes, and after obtaining the composition 10, the composition 10 is formed into a thickness of 2.5 mm After curing for 3 days under the conditions of 23° C./50% RH, a cured product of composition 10 was obtained.
[比較例3] 雖然嘗試著將上述第一組分A中未添加乙醯乙酸乙酯者作為第一組分，且將該第一組分和上述第二組分C以4：1（質量）的混合比混合5分鐘，且在獲得組合物11之後，以將該組合物11形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，但該組合物11未能夠充分固化。[Comparative Example 3] Although I tried to use the above first component A without adding ethyl acetate as the first component, and the first component and the above second component C were mixed at a mixing ratio of 4:1 (mass) After 5 minutes, and after obtaining the composition 11, the composition 11 was cured for 3 days under the conditions of 23° C./50% RH so that the composition 11 had a thickness of 2.5 mm, but the composition 11 was not sufficiently cured.
[比較例4] 雖然嘗試著將上述第二組分C中未添加γ-胺基丙基三乙氧基矽烷者作為第二組分，且將上述第一組分A和該第二組分以4：1（質量）的混合比混合5分鐘，且在獲得組合物12之後，以將該組合物12形成厚度為2.5mm的方式在23℃/50％RH的條件下固化3天，但該組合物12未能夠充分固化。[Comparative Example 4] Although trying to use the above second component C without adding γ-aminopropyltriethoxysilane as the second component, and the above first component A and the second component at 4:1 ( The mixing ratio of mass) was mixed for 5 minutes, and after the composition 12 was obtained, the composition 12 was cured for 3 days under the conditions of 23° C./50% RH so that the thickness of the composition 12 was 2.5 mm, but the composition 12 was not Can be fully cured.
結果 在表2中示出了通過上述方法對組合物7〜12及其固化物進行了評估的結果。result Table 2 shows the results of evaluating compositions 7 to 12 and their cured products by the above method.
[表2]
與含有第一組分A的組合物的流動停止時間（固化時間）相比較，含有第一組分B的組合物的流動停止時間（固化時間）短。這是因為在第一組分B中與(D)成分中的γ-胺基丙基三乙氧基矽烷反應的(B)成分中的乙醯乙酸乙酯的含量比在第一組分A中的含量多，進而所副產的水分子也多的緣故。Compared with the flow stop time (curing time) of the composition containing the first component A, the flow stop time (curing time) of the composition containing the first component B is short. This is because the content of ethyl acetate in the component (B) that reacts with the γ-aminopropyltriethoxysilane in component (D) in the first component B is higher than that in the first component A. There are more water molecules in the by-product.
需要說明的是，即使改變第一組分A和第一組分B的組合以及變更第二組分C和第二組分D的組合，也能夠確認到橡膠物性和光透射率為所希望的值。It should be noted that even if the combination of the first component A and the first component B is changed, and the combination of the second component C and the second component D is changed, the rubber properties and light transmittance can be confirmed to the desired value .
在組合物11或組合物12中，由於未添加乙醯乙酸乙酯或γ-胺基丙基三乙氧基矽烷，因此其固化性差，即使經過3天也未能夠得到固化物，進而無法測定其橡膠物性。所以，也不能測定其光透射率，並且未能實施彎曲試驗。In composition 11 or composition 12, since ethyl acetoxyacetate or γ-aminopropyl triethoxysilane was not added, the curability was poor, and the cured product could not be obtained even after 3 days, so it could not be measured Its rubber properties. Therefore, the light transmittance could not be measured, and the bending test could not be performed.
即使在第二組分中使用四正丙氧基矽烷（第二組分C和第二組分D）去代替四乙氧基矽烷（第二組分A和第二組分B）時，也能夠確認到橡膠物性和光透射率為所希望的值。Even when tetra-n-propoxysilane (second component C and second component D) is used in the second component instead of tetraethoxysilane (second component A and second component B), It can be confirmed that the rubber properties and the light transmittance have the desired values.
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