TW201940554A

TW201940554A - Curable polysiloxane composition

Info

Publication number: TW201940554A
Application number: TW108106463A
Authority: TW
Inventors: 魏彥虎; 史帝文思威爾; 劉立志
Original assignee: 美商陶氏有機矽公司
Priority date: 2018-03-16
Filing date: 2019-02-26
Publication date: 2019-10-16
Also published as: WO2019177689A1

Abstract

A curable polysiloxane composition comprising from 10 to 95 wt% of a silanol-functional polysiloxane comprising siloxane units (R1R2SiO2/2)a(R3SiO3/2)b, from 5 to 5000 ppm of a UV latent base catalyst, and from 5 to 90 wt% of particulate phosphors, fillers or a combination thereof; wherein a is from 0.1 to 0.9, b is from 0.1 to 0.9, a+b is at least 0.95; R1, R2 and R3 independently represent hydroxyl or C1-C20 organic substituent groups; and the silanol-functional polysiloxane comprises from 5 to 50 mole% silanol groups.

Description

可固化聚矽氧烷組成物Curable polysiloxane composition

本發明係關於一種可固化聚矽氧烷組成物，其包含UV潛伏鹼催化劑。The invention relates to a curable polysiloxane composition, which comprises a UV latent alkali catalyst.

聚矽氧烷材料可用作為用於熱及光穩定的封裝材料及保護材料之工業解決方案，以及在快速擴展的電子產品及光學應用中用於官能性組分（諸如磷光體）之基材。為了高效及高生產量製造，希望且需要這些製劑在溫和條件下快速固化。已為此類目的開發了多種聚矽氧烷組成物。可用於這些應用的某些聚矽氧烷材料（尤其是縮合固化樹脂-線型聚矽氧），一般含有未反應的矽醇，其可用鹼催化劑（通常係胺催化劑）固化。例如，美國申請公開案第2014/357827號揭示用胺催化劑固化之樹脂-線型矽氧烷，但胺催化劑在某些無機顆粒固體（像是磷光體或填料）的存在下時常不能有效地作用。抑制減緩或防止含有這些顆粒固體之組成物固化，該等顆粒固體在前述應用中係必要的及/或非常有用的。美國專利申請公開案第2014/335448號描述一種感光矽氧烷樹脂組成物，其可含有光鹼產生劑作為硬化劑，但組成物不包含填料或磷光體，並沒有解決固化抑制問題。美國專利第6096483號描述用以固化含氫矽基聚矽氧烷及含矽醇交聯劑之組成物的光鹼產生劑，但並沒有解決UV固化的抑制。美國專利申請公開案第2005/266344號描述一種照射可固化組成物，其包含矽氧烷樹脂、光酸或鹼產生劑、及使用具有低Mw及四級銨鹽之矽倍半氧烷樹脂的固化加速催化劑，但樹脂組成物係有限制的。Polysiloxane materials can be used as industrial solutions for thermal and light stable packaging and protection materials, as well as substrates for functional components such as phosphors in rapidly expanding electronics and optical applications. For efficient and high-throughput manufacturing, it is desirable and required that these formulations cure quickly under mild conditions. Various polysiloxane compositions have been developed for this purpose. Certain polysiloxane materials that can be used in these applications (especially condensation-cured resins—linear polysiloxanes) generally contain unreacted silanols, which can be cured with a base catalyst (usually an amine catalyst). For example, U.S. Application Publication No. 2014/357827 discloses resin-linear siloxanes cured with amine catalysts, but amine catalysts often fail to function effectively in the presence of certain inorganic particulate solids, such as phosphors or fillers. Inhibits slowing or preventing solidification of compositions containing these particulate solids, which are necessary and / or very useful in the aforementioned applications. US Patent Application Publication No. 2014/335448 describes a photosensitive siloxane resin composition that may contain a photobase generator as a hardener, but the composition does not contain a filler or a phosphor, and does not solve the problem of curing inhibition. US Patent No. 6,098,483 describes a photobase generator for curing a composition containing a hydrogen-containing silicon-based polysiloxane and a silanol-containing crosslinking agent, but does not address the inhibition of UV curing. U.S. Patent Application Publication No. 2005/266344 describes an irradiation curable composition comprising a siloxane resin, a photoacid or alkali generator, and a silicon sesquioxane resin having a low Mw and a quaternary ammonium salt. A curing acceleration catalyst, but the resin composition is limited.

先前的公開案並未教示組成物中固體組分之抑制作用的解決方案，並且對於產業所面臨的技術問題並未提供令人滿意的解決方案。The previous publications did not teach a solution to the inhibitory effect of solid components in the composition, and did not provide a satisfactory solution to the technical problems faced by the industry.

本發明提供一種可固化聚矽氧烷組成物，其包含： (a) 10至95 wt%之矽醇官能性聚矽氧烷，其包含矽氧烷單元(R¹ R² SiO_2/2 )_a (R³ SiO_3/2 )_b ，(b) 5至5000 ppm之UV潛伏鹼催化劑，及(c) 5至90 wt%之顆粒磷光體、填料、或其組合；其中a係0.1至0.9，b係0.1至0.9，a+b係至少0.95且不大於1；R¹ 、R² 、及R³ 獨立地表示羥基或C₁ -C₂₀ 有機取代基；及矽醇官能性聚矽氧烷，其包含5至50莫耳%之矽醇基團。The present invention provides a curable polysiloxane composition comprising: (a) 10 to 95 wt% of a silanol-functional polysiloxane containing a silanol unit (R ¹ R ² SiO _2/2 ) _a (R ³ SiO _3/2 ) _b , (b) 5 to 5000 ppm UV latent alkali catalyst, and (c) 5 to 90 wt% particulate phosphor, filler, or a combination thereof; wherein a is 0.1 to 0.9 , B is 0.1 to 0.9, a + b is at least 0.95 and not more than 1; R ¹ , R ² , and R ³ independently represent a hydroxyl group or a C ₁ -C ₂₀ organic substituent; and a silanol-functional polysiloxane It contains 5 to 50 mol% of silanol groups.

除非特別註明，否則百分比為重量百分比(wt%)且溫度使用℃。除非特別註明，否則操作係在室溫(25℃)下進行。「有機取代基(organic substituent group)」包含碳及氫原子，並且亦可含有選自下列之雜原子：氧、氮、矽、硫、磷、溴、氯、及氟。較佳地，有機取代基包含不大於三個氧、氮、及矽原子，較佳地不大於兩個，較佳地不大於一個，較佳地完全沒有。「烴基(hydrocarbyl)」係衍生自脂族或芳族烴之取代基，其可係線型、支鏈、或環狀的，並且其可具有選自氯、氟、甲基、乙基、甲氧基、及乙氧基之一或多個取代基。較佳地，烴基係未經取代。烷基係飽和烴基，其可係直鏈或支鏈的。較佳的是，烷基具有一至六個碳原子、較佳地一或兩個。較佳地，烷基係未經取代。芳基係衍生自芳族烴化合物之取代基，其可係單核或多核，並且其可具有至多三個取代碳原子之氮原子，較佳地不大於兩個、較佳地不大於一個、較佳地完全沒有。芳基可經氯、氟、甲基、乙基、甲氧基、或乙氧基取代。較佳地，芳基係未經取代。Unless otherwise specified, percentages are by weight (wt%) and temperatures are in ° C. Unless otherwise specified, operations are performed at room temperature (25 ° C). An "organic substituent group" includes carbon and hydrogen atoms, and may also contain heteroatoms selected from the group consisting of oxygen, nitrogen, silicon, sulfur, phosphorus, bromine, chlorine, and fluorine. Preferably, the organic substituent contains no more than three oxygen, nitrogen, and silicon atoms, preferably no more than two, preferably no more than one, and preferably none at all. "Hydrocarbyl" is a substituent derived from an aliphatic or aromatic hydrocarbon, which may be linear, branched, or cyclic, and it may have a group selected from chlorine, fluorine, methyl, ethyl, methoxy And one or more substituents of ethoxy. Preferably, the hydrocarbyl is unsubstituted. Alkyl is a saturated hydrocarbon group, which may be straight or branched. Preferably, the alkyl group has one to six carbon atoms, preferably one or two. Preferably, the alkyl group is unsubstituted. Aryl is a substituent derived from an aromatic hydrocarbon compound, which may be mono- or polynuclear, and it may have up to three nitrogen atoms substituted for carbon atoms, preferably no more than two, preferably no more than one, Preferably none at all. Aryl may be substituted with chlorine, fluorine, methyl, ethyl, methoxy, or ethoxy. Preferably, the aryl group is unsubstituted.

如本文中所使用，「ppm」意指百萬分之一重量份。如本文中所使用，除非另有指示，否則分子量、M_n 、M_w 、及M_z 具有習知意義，且係藉由凝膠滲透層析術判定。在本文中以g/mol之單位記述分子量。組分(a) -矽醇官能性聚矽氧烷As used herein, "ppm" means parts per million by weight. As used herein, unless otherwise indicated, molecular weight, M _n , M _w , and M _z have conventional meanings and are determined by gel permeation chromatography. The molecular weight is described herein in units of g / mol. Component (a)-silanol functional polysiloxane

本發明之聚矽氧烷組成物包含(a)矽醇官能性聚矽氧烷，其包含矽氧烷單元(R¹ R² SiO_2/2 )_a (R³ SiO_3/2 )_b 。R¹ 、R² 、及R³ 獨立地表示羥基或C₁ -C₂₀ 有機取代基，使得R¹ 、R² 、或R³ 可表示一個矽氧烷單元上之羥基及另一個矽氧烷單元上之有機取代基。當R¹ 、R² 、或R³ 表示特定矽原子上之羥基時，該矽氧烷單元係矽醇單元。組分(a)聚矽氧烷相對於Si原子之莫耳數包含5至50莫耳%之矽醇單元，並且所有非羥基取代基皆係C₁ -C₂₀ 有機取代基。較佳地，聚矽氧烷包含至少8莫耳%之矽醇單元，較佳地至少10莫耳%；及同時較佳地不大於40莫耳%、較佳地不大於35莫耳%、較佳地不大於30莫耳%、較佳地不大於25莫耳%、較佳地不大於20莫耳%之矽醇單元。較佳地，R¹ 、R² 、及R³ 獨立地係羥基或C₁ -C₂₀ 經取代或未經取代的烴基。較佳地，當R¹ 、R² 、或R³ 係C₁ -C₂₀ 經取代或未經取代的烴基時，其係烷基、烯基、或芳基；較佳地烷基或芳基；較佳地C₁ -C₁₀ 芳基或C₁ -C₄ 烷基；較佳地甲基、乙基、或苯基；最佳地甲基及苯基之組合。較佳地，R¹ 、R² 、及R³ 獨立地係羥基、或經取代或未經取代的烴基，此類烴基具有1至20個碳原子、較佳地1至10個碳原子、較佳地1至8個碳原子、較佳地1至4個碳原子。在較佳實施例中，R¹ 係羥基或甲基，且R² 及R³ 羥基、苯基或C¹ -C₆ 烷基；較佳地R² 及R³ 係羥基、苯基、或C₁ -C₄ 烷基，較佳地羥基、甲基、或苯基，較佳地羥基或苯基。The polysiloxane composition of the present invention includes (a) a silanol-functional polysiloxane including a siloxane unit (R ¹ R ² SiO _2/2 ) _a (R ³ SiO _3/2 ) _b . R ¹ , R ² , and R ³ independently represent a hydroxyl group or a C ₁ -C ₂₀ organic substituent, so that R ¹ , R ² , or R ³ may represent a hydroxyl group on one siloxane unit and another siloxane unit Organic substituents. When R ¹ , R ² , or R ³ represents a hydroxyl group on a specific silicon atom, the siloxane unit is a silanol unit. The mole number of the component (a) polysiloxane with respect to the Si atom contains 5 to 50 mole% of silanol units, and all non-hydroxy substituents are C ₁ -C ₂₀ organic substituents. Preferably, the polysiloxane contains at least 8 mole% of silanol units, preferably at least 10 mole%; and at the same time preferably not more than 40 mole%, preferably not more than 35 mole%, The silanol unit is preferably not more than 30 mole%, preferably not more than 25 mole%, and preferably not more than 20 mole%. Preferably, R ¹ , R ² , and R ^{3 are} independently a hydroxyl group or a C ₁ -C ₂₀ substituted or unsubstituted hydrocarbon group. Preferably, when R ¹ , R ² , or R ³ is a C ₁ -C ₂₀ substituted or unsubstituted hydrocarbon group, it is an alkyl group, an alkenyl group, or an aryl group; preferably an alkyl group or an aryl group ; Preferably C ₁ -C ₁₀ aryl or C ₁ -C ₄ alkyl; preferably methyl, ethyl, or phenyl; most preferably a combination of methyl and phenyl. Preferably, R ¹ , R ² , and R ^{3 are} independently a hydroxyl group, or a substituted or unsubstituted hydrocarbon group, such a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more It is preferably 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. In a preferred embodiment, R ¹ is hydroxyl or methyl, and R ² and R ^{3 are} hydroxyl, phenyl, or C ¹ -C ₆ alkyl; preferably R ² and R ³ are hydroxyl, phenyl, or C _1- C ₄ alkyl, preferably hydroxy, methyl, or phenyl, preferably hydroxy or phenyl.

相對於組分(a)之聚矽氧烷的平均分子式，下標「a」及「b」分別表示(R¹ R² SiO_2/2 )及(R³ SiO_3/2 )之莫耳分率。下標a係0.1至0.9，下標b係0.1至0.9。a及b之和（「a+b」）係至少0.95且不大於1。較佳地，a係至少0.2、較佳地至少0.3、較佳地至少0.4、較佳地至少0.45；及同時較佳地不大於0.8、較佳地不大於0.7、較佳地不大於0.6。較佳地，b係至少0.2、較佳地至少0.3、較佳地至少0.4；及同時較佳地不大於0.8、較佳地不大於0.7、較佳地不大於0.6、較佳地不大於0.55。較佳地，a+b係至少0.97、較佳地至少0.98、較佳地至少0.99。當a+b小於1時，聚矽氧烷包含除了(R¹ R² SiO_2/2 )及(R³ SiO_3/2 )以外的單元。此類其他單元可係(R⁴ ₃ SiO_1/2 )_c 或(SiO_4/2 )_d ，其中a+b+c+d=1。c及d各自可獨立地係零。組分(a)之聚矽氧烷可具有短伸烷基鏈(-CH₂ -CH₂ -)，其以少量間隔矽氧烷主鏈，尤其是其中(R¹ R² SiO_2/2 )與(R³ SiO_3/2 )連接。Relative to the average molecular formula of the polysiloxane of component (a), the subscripts "a" and "b" represent the mole fractions of (R ¹ R ² SiO _2/2 ) and (R ³ SiO _3/2 ), respectively. rate. The subscript a is 0.1 to 0.9, and the subscript b is 0.1 to 0.9. The sum of a and b ("a + b") is at least 0.95 and not greater than 1. Preferably, a is at least 0.2, preferably at least 0.3, preferably at least 0.4, preferably at least 0.45; and at the same time preferably not more than 0.8, preferably not more than 0.7, preferably not more than 0.6. Preferably, b is at least 0.2, preferably at least 0.3, preferably at least 0.4; and at the same time preferably not more than 0.8, preferably not more than 0.7, preferably not more than 0.6, preferably not more than 0.55 . Preferably, a + b is at least 0.97, preferably at least 0.98, and preferably at least 0.99. When a + b is less than 1, the polysiloxane contains units other than (R ¹ R ² SiO _2/2 ) and (R ³ SiO _3/2 ). Such other units may be (R ⁴ ₃ SiO _1/2 ) _c or (SiO _4/2 ) _d , where a + b + c + d = 1. c and d may each be independently zero. The polysiloxane of component (a) may have a short-chain alkyl chain (-CH ₂ -CH _2- ), which has a small amount of spaced siloxane backbone, especially among them (R ¹ R ² SiO _2/2 ) It is connected to (R ³ SiO _3/2 ).

較佳地，R¹ R² SiO_2/2 單元係以線型聚合物之形式存在，其具有30至200個單元；較佳地至少50個、較佳地至少70個、較佳地至少80個；較佳地不大於170個、較佳地不大於150個、較佳地不大於140個、較佳地不大於130個。較佳地，聚矽氧烷係嵌段共聚物，其藉由將包含R¹ R² SiO_2/2 單元之線型聚矽氧烷與一或多個R³ SiO_3/2 單元偶合來製備。這類嵌段共聚物之實例可見於美國專利第8,957,147號中。簡要地，這些嵌段共聚物係含有「線型」R¹ R² SiO_2/2 矽氧基單元與「樹脂」R³ SiO_3/2 矽氧基單元組合之有機聚矽氧烷。這些有機矽氧烷共聚物係「嵌段」共聚物，與「隨機」共聚物形成對照。這些有機聚矽氧烷含有R¹ R² SiO_2/2 及R³ SiO_3/2 矽氧基單元，其中R¹ R² SiO_2/2 單元主要地鍵結在一起以形成聚合鏈，其在本文中稱為「線型嵌段」。R³ SiO_3/2 單元主要地彼此鍵結以形成支鏈聚合鏈，其稱為「非線型嵌段」。當提供固體形式之嵌段共聚物時，大量的這些非線型嵌段可進一步聚集以形成「奈米域(nano-domain)」。更具體而言，R¹ R² SiO_2/2 單元排列成線型嵌段，每個線型嵌段平均具有10至400個R¹ R² SiO_2/2 單元，而三矽氧基單元R³ SiO_3/2 排列成非線型嵌段，其分子量至少為500 g/mol且至少30%之非線型嵌段彼此交聯。Preferably, the R ¹ R ² SiO _2/2 units are in the form of a linear polymer, which has 30 to 200 units; preferably at least 50, preferably at least 70, and preferably at least 80 ; Preferably not more than 170, preferably not more than 150, preferably not more than 140, and preferably not more than 130. Preferably, the polysiloxane block copolymer is prepared by coupling a linear polysiloxane containing R ¹ R ² SiO _2/2 units with one or more R ³ SiO _3/2 units. An example of such a block copolymer can be found in U.S. Patent No. 8,957,147. Briefly, these block copolymers are organic polysiloxanes containing a combination of "linear" R ¹ R ² SiO _2/2 siloxy units and "resin" R ³ SiO _3/2 siloxy units. These organosiloxane copolymers are "block" copolymers, as opposed to "random" copolymers. These organic polysiloxanes contain R ¹ R ² SiO _2/2 and R ³ SiO _3/2 siloxy units, where the R ¹ R ² SiO _2/2 units are mainly bonded together to form a polymer chain, which is Referred to herein as a "linear block." The R ³ SiO _3/2 units are mainly bonded to each other to form a branched polymeric chain, which is called a “non-linear block”. When the block copolymer is provided in solid form, a large number of these non-linear blocks can be further aggregated to form a "nano-domain". More specifically, the R ¹ R ² SiO _2/2 units are arranged into linear blocks, each linear block having an average of 10 to 400 R ¹ R ² SiO _2/2 units, and the trisiloxy unit R ³ SiO _{3/2 is} arranged as a non-linear block having a molecular weight of at least 500 g / mol and at least 30% of the non-linear blocks are cross-linked to each other.

以組分(a)聚矽氧烷及組分(c)顆粒（磷光體+填料）之重量和計，組分(a)之存在量係10至95 wt%之本發明聚矽氧烷組成物，亦即不包括催化劑及可能存在之任何溶劑。較佳地，組分(a)之存在量相對於組分(a)聚矽氧烷及組分(c)顆粒（磷光體+填料）之重量和係至少15 wt%、較佳地至少20 wt%、較佳地至少25 wt%；及同時較佳地不大於85 wt%、較佳地不大於75 wt%、較佳地不大於70 wt%、較佳地不大於65 wt%、較佳地不大於60 wt%、較佳地不大於55 wt%、較佳地不大於50 wt%。組分(b) - UV潛伏鹼催化劑Based on the weight of component (a) polysiloxane and component (c) particles (phosphor + filler), the component (a) is present in an amount of 10 to 95 wt% of the present polysiloxane composition It does not include catalysts and any solvents that may be present. Preferably, component (a) is present in an amount of at least 15 wt%, preferably at least 20, relative to the weight and sum of component (a) polysiloxane and component (c) particles (phosphor + filler). wt%, preferably at least 25 wt%; and at the same time preferably no more than 85 wt%, preferably no more than 75 wt%, preferably no more than 70 wt%, preferably no more than 65 wt%, more It is preferably not more than 60 wt%, preferably not more than 55 wt%, and preferably not more than 50 wt%. Component (b)-UV Latent Base Catalyst

本發明之聚矽氧烷組成物亦包含(b) UV潛伏鹼催化劑。潛伏鹼催化劑之較佳的一般結構係如下所示：其中NB1代表環狀或非環狀三級胺，NB2代表一級或二級胺，且Ar代表經取代或未經取代的芳基。較佳地，Ar包含5至20個碳原子、較佳地6至15個；較佳的Ar基團包括苯基、2-硝苯基、4-硝苯基、2-甲氧苯基、4-甲氧苯基、2-羥苯基、4-羥苯基、萘基、蒽基、及9-氧硫基。The polysiloxane composition of the present invention also includes (b) a UV latent base catalyst. The preferred general structure of a latent base catalyst is as follows: NB1 represents a cyclic or acyclic tertiary amine, NB2 represents a primary or secondary amine, and Ar represents a substituted or unsubstituted aryl group. Preferably, Ar contains 5 to 20 carbon atoms, preferably 6 to 15; preferred Ar groups include phenyl, 2-nitrophenyl, 4-nitrophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, naphthyl, anthracenyl, and 9-oxysulfide base.

較佳地，各NB1及NB2包含5至30個碳原子、較佳地6至25個。相對離子係形成鹽之任何陰離子，該鹽在聚矽氧烷組成物中係穩定的。較佳的相對離子包括(Ph)₄ B^- （Ph=苯基）、BF₄ ^- 、B(C₆ F₅ )₄ ^- 、PF₆ ^- 、SbF₆ ^- 、ClO₄ ^- 、羧酸鹽、及苯基乙醛酸鹽。較佳的氮鹼（NB1、NB2）包括下列者：DBU：1,8-二氮雜雙環[5.4.0]十一-7-烯；DBN：1,5-二氮雜雙環[4.3.0]壬-5-烯；TBD：1,5,7-三氮雜雙環[4.4.0]癸-5-烯；PS：質子海綿；PD：吡啶衍生物，其中G代表吡啶環之任何位置中的任何取代基；胺：烷基胺，其中R、R'、及R”獨立地係氫或C₁ -C₃₀ 烴基；2B-TMG：2-三級丁基-1,1,3,3-四甲基胍；6-DBA-DBU：6-二丁胺基-DBU。Preferably, each of NB1 and NB2 contains 5 to 30 carbon atoms, preferably 6 to 25. The salt is stable to any anion in the ionic system that forms a salt. Preferred counterions include _{^{(Ph) 4 B - (Ph}} = _{^{phenyl), BF 4 -, B (}} C 6 F 5) 4 -, PF 6 -, SbF 6 -, ClO 4 -, carboxylates, and Phenylglyoxylate. Preferred nitrogen bases (NB1, NB2) include the following: DBU: 1,8-diazabicyclo [5.4.0] undec-7-ene; DBN: 1,5-diazabicyclo [4.3.0] non-5-ene; TBD: 1,5,7 -Triazabicyclo [4.4.0] dec-5-ene; PS: proton sponge; PD: pyridine derivative, where G represents any substituent in any position of the pyridine ring; amine: alkylamine, where R, R 'and R "are independently hydrogen or C ₁ -C ₃₀ hydrocarbon group; 2B-TMG: 2-tertiary butyl-1,1,3,3-tetramethylguanidine; 6-DBA-DBU: 6- Dibutylamino-DBU.

典型的UV潛伏鹼催化劑之實例係NB-DBU：2-硝苄基-DBU；IRGACURE 369（現可以OMNIRAD 369商購得自IGM Resins B.V., Waalwijk, The Netherlands）：2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮-1；NB-DOA：2-硝苄基-1',1'-二辛基胺甲酸酯；AP-DBU：苯乙酮-DBU。 An example of a typical UV latent base catalyst is NB-DBU: 2-nitrobenzyl-DBU; IRGACURE 369 (commercially available from OMNIRAD 369 from IGM Resins BV, Waalwijk, The Netherlands): 2-benzyl-2-di Methylamino-1- (4-morpholinylphenyl) -butanone-1; NB-DOA: 2-nitrobenzyl-1 ', 1'-dioctylcarbamate; AP-DBU: benzene Ethyl Ketone-DBU.

較佳地，UV潛伏鹼催化劑（以ppm重量計），以組分(a)聚矽氧烷、組分(b)催化劑、及組分(c)顆粒之重量和計，係至少100 ppm、較佳地至少200 ppm、較佳地至少300 ppm、較佳地至少400 ppm；及同時較佳地不大於4000 ppm、較佳地不大於3000、較佳地不大於2000、較佳地不大於1500 ppm。組分(c)顆粒磷光體、填料或其組合Preferably, the UV latent alkali catalyst (based on ppm by weight) is at least 100 ppm based on the weight of the component (a) polysiloxane, component (b) catalyst, and component (c) particles, Preferably at least 200 ppm, preferably at least 300 ppm, preferably at least 400 ppm; and at the same time preferably not more than 4000 ppm, preferably not more than 3000, preferably not more than 2000, preferably not more than 1500 ppm. Component (c) particulate phosphor, filler or combination thereof

本發明之聚矽氧烷組成物包含(c)顆粒磷光體、填料、或其組合。The polysiloxane composition of the present invention includes (c) a particulate phosphor, a filler, or a combination thereof.

「磷光體(phosphor)」係一種類型之波長轉換器，其在第一波長下吸收光，且在不同於第一波長之第二波長下回應性地發射光。例如，釹摻雜之釔-鋁-石榴石(Nd:YAG)磷光體（YAG係釔鋁石榴石(yttrium aluminum garnet) (Y₃ Al₅ O₁₂ )），當暴露於白光、或除黃光外之一部分白光時，將回應性地發射黃光。磷光體包括多種含有金屬之材料，諸如各種金屬及稀土金屬之氧化物、氮化物、氧氮化物、硫化物、硒化物、鹵化物、矽酸鹽。A "phosphor" is a type of wavelength converter that absorbs light at a first wavelength and emits light responsively at a second wavelength different from the first wavelength. For example, a neodymium-doped yttrium-aluminum-garnet (Nd: YAG) phosphor (Yttrium aluminum garnet (Y ₃ Al ₅ O ₁₂ )), when exposed to white light or yellow light When a part of the light is white, it emits yellow light in response. Phosphors include various materials containing metals, such as oxides, nitrides, oxynitrides, sulfides, selenides, halides, and silicates of various metals and rare earth metals.

合適的顆粒磷光體之實例包含下列之至少一者：YAG (Y₃ Al₅ O₁₂ )；Ce:YAG；Zn₂ SiO₄ :Mn（矽鋅礦）；ZnS:Ag+(Zn,Cd)S:Ag；ZnS:Ag+ZnS:Cu+Y₂ O₂ S:Eu；ZnO:Zn；KCl；ZnS:Ag,Cl或ZnS:Zn；(KF,MgF₂ ):Mn；(Zn,Cd)S:Ag或(Zn,Cd)S:Cu；Y₂ O₂ S:Eu+Fe₂ O₃ , ZnS:Cu,Al；ZnS:Ag+Co-on-Al₂ O₃ ；(KF,MgF₂ ):Mn；(Zn,Cd)S:Cu,Cl；ZnS:Cu或ZnS:Cu,Ag；MgF₂ :Mn；(Zn,Mg)F₂ :Mn；Zn₂ SiO₄ :Mn,As；ZnS:Ag+(Zn,Cd)S:Cu；Gd₂ O₂ S:Tb；Y₂ O₂ S:Tb；Y₃ Al₅ O₁₂ :Ce；Y₂ SiO₅ :Ce；Y₃ Al₅ O₁₂ :Tb；ZnS:Ag,Al；ZnS:Ag；ZnS:Cu,Al或ZnS:Cu,Au,Al；(Zn,Cd)S:Cu,Cl+(Zn,Cd)S:Ag,Cl；Y₂ SiO₅ :Tb；Y₂ OS:Tb；Y₃ (Al,Ga)₅ O₁₂ :Ce；Y₃ (Al,Ga)₅ O₁₂ :Tb；InBO₃ :Tb；InBO₃ :Eu；InBO₃ :Tb+InBO₃ :Eu；InBO₃ :Tb+InBO₃ :Eu+ZnS:Ag；(Ba,Eu)Mg₂ Al₁₆ O₂₇ ；(Ce,Tb)MgAl₁₁ O₁₉ ；BaMgAl₁₀ O₁₇ :Eu,Mn；BaMg₂ Al₁₆ O₂₇ :Eu(II)；BaMgAl₁₀ O₁₇ :Eu,Mn；BaMg₂ Al₁₆ O₂₇ :Eu(II),Mn(II)；Ce_0.67 Tb_0.33 MgAl₁₁ O₁₉ :Ce,Tb；Zn₂ SiO₄ :Mn,Sb₂ O₃ ；CaSiO₃ :Pb,Mn；CaWO₄ (白鎢礦)；CaWO₄ :Pb；MgWO₄ ；(Sr,Eu,Ba,Ca)₅ (PO₄ )₃ Cl；Sr₅ Cl(PO₄ )₃ :Eu(II)；(Ca,Sr,Ba)₃ (PO₄ )₂ Cl₂ :Eu；(Sr,Ca,Ba)₁₀ (PO₄ )₆ Cl₂ :Eu；Sr₂ P₂ O₇ :Sn(II)；Sr₆ P₅ BO₂₀ :Eu；Ca₅ F(PO₄ )₃ :Sb；(Ba,Ti)₂ P₂ O₇ :Ti；3Sr₃ (PO₄ )₂ .SrF₂ :Sb,Mn；Sr₅ F(PO₄ )₃ :Sb,Mn；Sr₅ F(PO₄ )₃ :Sb,Mn；LaPO₄ :Ce,Tb；(La,Ce,Tb)PO₄ ；(La,Ce,Tb)PO₄ :Ce,Tb；Ca₃ (PO₄ )₂ .CaF₂ :Ce,Mn；(Ca,Zn,Mg)₃ (PO₄ )₂ :Sn；(Zn,Sr)₃ (PO₄ )₂ :Mn；(Sr,Mg)₃ (PO₄ )₂ :Sn；(Sr,Mg)₃ (PO₄ )₂ :Sn(II)；Ca₅ F(PO₄ )₃ :Sb,Mn；Ca₅ (F,Cl)(PO₄ )₃ :Sb,Mn；(Y,Eu)₂ O₃ ；Y₂ O₃ :Eu(III)；Mg₄ (F)GeO₆ :Mn；Mg₄ (F)(Ge,Sn)O₆ :Mn；Y(P,V)O₄ :Eu；YVO₄ :Eu；Y₂ O₂ S:Eu；3.5 MgO π 0.5 MgF₂ π GeO₂ :Mn；Mg₅ As₂ O₁₁ :Mn；SrAl₂ O₇ :Pb；LaMgAl₁₁ O₁₉ :Ce；LaPO₄ :Ce；SrAl₁₂ O₁₉ :Ce；BaSi₂ O₅ :Pb；SrFB₂ O₃ :Eu(II)；SrB₄ O₇ :Eu；Sr₂ MgSi₂ O₇ :Pb；MgGa₂ O₄ :Mn(II)；Gd₂ O₂ S:Tb；Gd₂ O₂ S:Eu；Gd₂ O₂ S:Pr；Gd₂ O₂ S:Pr,Ce,F；Y₂ O₂ S:Tb；Y₂ O₂ S:Eu；Y₂ O₂ S:Pr；Zn(0.5)Cd(0.4)S:Ag；Zn(0.4)Cd(0.6)S:Ag；CdWO₄ ；CaWO₄ ；MgWO₄ ；Y₂ SiO₅ :Ce；YAlO₃ :Ce；Y₃ Al₅ O₁₂ :Ce；Y₃ (Al,Ga)₅ O₁₂ :Ce；CdS:In；ZnO:Ga；ZnO:Zn；(Zn,Cd)S:Cu,Al；ZnS:Cu,Al,Au；ZnCdS:Ag,Cu；ZnS:Ag；蒽、EJ-212、Zn₂ SiO₄ :Mn；ZnS:Cu；NaI:Tl；CsI:Tl；LiF/ZnS:Ag；LiF/ZnSCu,Al,Au；及氮化物諸如，LaAl(Si₆ Al₃ )N₇ O₃ :Ce³⁺ ；Ca_0.898 Ce_0.068 Si₉ Al₃ ON₁₅ ；La_4.9 Ce_0.1 Si₃ O₁₂ N；La_0.96 Ce_0.04 SiO₂ N；La_2.82 Ce_0.18 Si₈ O₄ N₁₁ ；(Ca,Sr,Ba)Si₂ O₂ N₂ :Eu²⁺ ；(Sr,Ba)YSi₄ N₇ :Eu²⁺ ；(Ca,Sr,Ba)₂ Si₅ N₈ :Eu²⁺ ；及(Sr,Ca)AlSiN₃ :Eu²⁺ 。Examples of suitable particulate phosphors include at least one of the following: YAG (Y ₃ Al ₅ O ₁₂ ); Ce: YAG; Zn ₂ SiO ₄ : Mn (zinc ore); ZnS: Ag + (Zn, Cd) S: Ag; ZnS: Ag + ZnS: Cu + Y ₂ O ₂ S: Eu; ZnO: Zn; KCl; ZnS: Ag, Cl or ZnS: Zn; (KF, MgF ₂ ): Mn; (Zn, Cd) S: Ag or (Zn, Cd) S: Cu; Y ₂ O ₂ S: Eu + Fe ₂ O ₃ , ZnS: Cu, Al; ZnS: Ag + Co-on-Al ₂ O ₃ ; (KF, MgF ₂ ): Mn; (Zn, Cd) S: Cu, Cl; ZnS: Cu or ZnS: Cu, Ag; MgF ₂ : Mn; (Zn, Mg) F ₂ : Mn; Zn ₂ SiO ₄ : Mn, As; ZnS: Ag + (Zn, Cd) S: Cu; Gd ₂ O ₂ S: Tb; Y ₂ O ₂ S: Tb; Y ₃ Al ₅ O ₁₂ : Ce; Y ₂ SiO ₅ : Ce; Y ₃ Al ₅ O ₁₂ : Tb; ZnS: Ag, Al; ZnS: Ag; ZnS: Cu, Al or ZnS: Cu, Au, Al; (Zn, Cd) S: Cu, Cl + (Zn, Cd) S: Ag, Cl; Y ₂ SiO ₅ : Tb; Y ₂ OS: Tb; Y ₃ (Al, Ga) ₅ O ₁₂ : Ce; Y ₃ (Al, Ga) ₅ O ₁₂ : Tb; InBO ₃ : Tb; InBO ₃ : Eu; InBO ₃ : Tb + InBO ₃ : Eu; InBO ₃ : Tb + InBO ₃ : Eu + ZnS: Ag; (Ba, Eu) Mg ₂ Al ₁₆ O ₂₇ ; (Ce, Tb) MgAl ₁₁ O ₁₉ ; BaMgAl ₁₀ O ₁₇ : Eu, Mn; BaMg ₂ Al ₁₆ O ₂₇ : Eu (II); BaMgAl ₁₀ O ₁₇ : Eu, Mn; BaMg ₂ Al ₁₆ O ₂₇ : Eu (II), Mn (II); Ce _0.67 Tb _0.33 MgAl ₁₁ O ₁₉ : Ce, Tb; Zn ₂ SiO ₄ : Mn, Sb ₂ O ₃ ; CaSiO ₃ : Pb, Mn; CaWO ₄ (schematite); CaWO ₄ : Pb; MgWO ₄ ; (Sr, Eu, Ba, Ca) ₅ (PO ₄ ) ₃ Cl; Sr ₅ Cl (PO ₄ ) ₃ : Eu ( II); (Ca, Sr, Ba) ₃ (PO ₄ ) ₂ Cl ₂ : Eu; (Sr, Ca, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu; Sr ₂ P ₂ O ₇ : Sn (II) ; Sr ₆ P ₅ BO ₂₀ : Eu; Ca ₅ F (PO ₄ ) ₃ : Sb; (Ba, Ti) ₂ P ₂ O ₇ : Ti; 3Sr ₃ (PO ₄ ) ₂ .SrF ₂ : Sb, Mn; Sr ₅ F (PO ₄ ) ₃ : Sb, Mn; Sr ₅ F (PO ₄ ) ₃ : Sb, Mn; LaPO ₄ : Ce, Tb; (La, Ce, Tb) PO ₄ ; (La, Ce, Tb) PO ₄ : Ce, Tb; Ca ₃ (PO ₄ ) _2. CaF ₂ : Ce, Mn; (Ca, Zn, Mg) ₃ (PO ₄ ) ₂ : Sn; (Zn, Sr) ₃ (PO ₄ ) ₂ : Mn ; (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn; (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn (II); Ca ₅ F (PO ₄ ) ₃ : Sb, Mn; Ca ₅ (F, Cl) (PO ₄ ) ₃ : Sb, Mn; (Y, Eu) ₂ O ₃ ; Y ₂ O ₃ : Eu (III); Mg ₄ (F) GeO ₆ : Mn; Mg ₄ (F) (Ge, Sn ) O ₆ : Mn; Y (P, V) O ₄ : Eu; YVO ₄ : Eu; Y ₂ O ₂ S: Eu; 3.5 MgO π 0.5 MgF ₂ π GeO ₂ : Mn; Mg ₅ As ₂ O ₁₁ : Mn ; SrAl ₂ O ₇ : Pb; LaMgAl ₁₁ O ₁₉ : Ce; LaPO ₄ : Ce; SrAl ₁₂ O ₁₉ : Ce; BaSi ₂ O ₅ : Pb; SrFB ₂ O ₃ : Eu (II); SrB ₄ O ₇ : Eu ; Sr ₂ MgSi ₂ O ₇ : Pb; MgGa ₂ O ₄ : Mn (II); Gd ₂ O ₂ S: Tb; Gd ₂ O ₂ S: Eu; Gd ₂ O ₂ S: Pr; Gd ₂ O ₂ S: Pr, Ce, F; Y ₂ O ₂ S: Tb; Y ₂ O ₂ S: Eu; Y ₂ O ₂ S: Pr; Zn (0.5) Cd (0.4) S: Ag; Zn (0.4) Cd (0.6) S: Ag; CdWO ₄ ; CaWO ₄ ; MgWO ₄ ; Y ₂ SiO ₅ : Ce; YAlO ₃ : Ce; Y ₃ Al ₅ O ₁₂ : Ce; Y ₃ (Al, Ga) ₅ O ₁₂ : Ce; CdS: In; ZnO: Ga; ZnO: Zn; (Zn, Cd) S: Cu, Al; ZnS: Cu, Al, Au; ZnCdS: Ag, Cu; ZnS: Ag; anthracene, EJ- 212, Zn ₂ SiO ₄ : Mn; ZnS: Cu; NaI: Tl; CsI: Tl; LiF / ZnS: Ag; LiF / ZnSCu, Al, Au; and nitrides such as LaAl (Si ₆ Al ₃ ) N ₇ O ₃ : Ce ³⁺ ; Ca _0.898 Ce _0.068 Si ₉ Al ₃ ON ₁₅ ; La _4.9 Ce _0.1 Si ₃ O ₁₂ N; La _0.96 Ce _0.04 SiO ₂ N; La _2.82 Ce _0.18 Si ₈ O ₄ N ₁₁ ; (Ca, Sr , Ba) Si ₂ O ₂ N ₂ : Eu ²⁺ ; (Sr, Ba) YSi ₄ N ₇ : Eu ²⁺ ; (Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu ²⁺ ; and (Sr, Ca ) AlSiN ₃ : Eu ²⁺ .

如本文中所使用，顆粒填料意謂除顆粒磷光體外之任何精細分散的有機或無機固體。顆粒之尺寸不需要任何特定尺寸，但較佳地係精細顆粒。「精細顆粒(Fine particulate)」係平均粒徑為0.01 µm（微米）至50 µm之顆粒，其根據操作軟體藉由雷射繞射式粒徑分析儀(Laser Diffraction particle size analyzer)（例如，CILAS920粒徑分析儀或Beckman Coulter LS 13 320 SW）所測量，並且表示為數目平均粒徑。對於小於1 µm者之顆粒，使用掃瞄式電子顯微鏡以視化並測量粒徑。為方便起見，可基於根據8-11 ASTM D4315測量表面積或藉由使用各種篩孔尺寸之篩，並從各粒級(size fraction)的累積重量計算平均值來估算平均粒徑。As used herein, particulate filler means any finely divided organic or inorganic solid other than particulate phosphorescent. The size of the particles does not need any particular size, but is preferably fine particles. "Fine particulates" are particles with an average particle diameter of 0.01 µm (micrometers) to 50 µm. They are laser diffractive particle size analyzers (eg, CILAS920) Particle size analyzer or Beckman Coulter LS 13 320 SW) and expressed as a number average particle size. For particles smaller than 1 µm, use a scanning electron microscope to visualize and measure the particle size. For convenience, the average particle diameter can be estimated based on measuring surface area according to 8-11 ASTM D4315 or by using a sieve of various mesh size and calculating an average value from the cumulative weight of each size fraction.

適用於組成物之顆粒填料可係強化填料、傳導性填料（導熱及/或導電）、顏料（非磷光體）、及擴充填料(extending filler)。顆粒填料可係觸變性的。可添加任何顆粒填料至聚矽氧烷組成物，但當填料顆粒具有會導致非潛伏UV鹼催化劑（諸如DBU）之抑制的表面特性時，本發明之聚矽氧烷組成物的優點更加明顯。此類填料在表面會具有活性基團，最典型係氧化物，其將導致鹼催化劑之抑制。亦可看到填料的表面具有酸性性質。不希望受理論的束縛，磷光體/填料對有機鹼催化劑之抑制可能主要係由於兩個原因所引起：(1)引起催化劑抑制之填料在表面上包含許多路易士酸位點（例如，金屬陽離子中心），其可能使有機鹼與其等緊密結合，及(2)填料之大且多孔表面可限制緊密結合的有機鹼，並防止其等即使在加熱時也不會出現活性催化位點。顯示鹼催化劑之抑制的合適顆粒填料之實例包括但不限於SiO₂ 、TiO₂ 、Al₂ O₃ 、ZrO₂ 、BaTiO₃ 、Ta₂ O₅ 、Fe₂ O₃ 、ZnO、及SrTiO₃ 、AlN、Si₃ N₄ 、及BN之至少一者。較佳地，顆粒填料可係發煙二氧化矽或氧化鈦，其已顯示會引起習知鹼催化劑之抑制。Particulate fillers suitable for the composition can be reinforcing fillers, conductive fillers (thermally and / or electrically conductive), pigments (non-phosphor), and extending fillers. The particulate filler may be thixotropic. Any particulate filler may be added to the polysiloxane composition, but the advantages of the polysiloxane composition of the present invention are even more pronounced when the filler particles have surface characteristics that can cause inhibition of non-latent UV base catalysts such as DBU. Such fillers will have active groups on the surface, the most typical type of oxide, which will lead to the inhibition of the base catalyst. It can also be seen that the surface of the filler has acidic properties. Without wishing to be bound by theory, the inhibition of organic base catalysts by phosphors / fillers may be caused by two main reasons: (1) The fillers that cause catalyst inhibition contain many Lewis acid sites on the surface (eg, metal cation (Center), which may cause organic bases to be tightly bound to them, and (2) the large and porous surface of the filler may limit tightly bound organic bases, and prevent them from appearing active catalytic sites even when heated. Examples of suitable particulate fillers that show inhibition of alkali catalysts include, but are not limited to, SiO ₂ , TiO ₂ , Al ₂ O ₃ , ZrO ₂ , BaTiO ₃ , Ta ₂ O ₅ , Fe ₂ O ₃ , ZnO, and SrTiO ₃ , AlN, At least one of Si ₃ N ₄ and BN. Preferably, the particulate filler may be fumed silica or titanium oxide, which has been shown to cause inhibition by conventional alkali catalysts.

較佳地，聚矽氧烷組成物包含至少15 wt%之顆粒，較佳地至少25 wt%、較佳地至少30 wt%、較佳地至少35 wt%、較佳地至少40 wt%、較佳地至少45 wt%、較佳地至少50 wt%；及同時較佳地不大於85 wt%、較佳地不大於80 wt%、較佳地不大於75 wt%、較佳地不大於70 wt%。較佳地，聚矽氧烷包含至少8莫耳%之矽醇基團，較佳地至少10莫耳%；及同時較佳地不大於40莫耳%、較佳地不大於35莫耳%、較佳地不大於30莫耳%、較佳地不大於25莫耳%、較佳地不大於20莫耳%。其他組分Preferably, the polysiloxane composition contains at least 15 wt% particles, preferably at least 25 wt%, preferably at least 30 wt%, preferably at least 35 wt%, preferably at least 40 wt%, Preferably at least 45 wt%, preferably at least 50 wt%; and at the same time preferably not more than 85 wt%, preferably not more than 80 wt%, preferably not more than 75 wt%, preferably not more than 70 wt%. Preferably, the polysiloxane contains at least 8 mole% of silanol groups, preferably at least 10 mole%; and at the same time preferably not more than 40 mole%, preferably not more than 35 mole% , Preferably not more than 30 mole%, preferably not more than 25 mole%, and preferably not more than 20 mole%. Other components

較佳地，可固化聚矽氧烷組成物進一步包含用以調節組成物之黏度的一或多種溶劑。對於特定組成物，容易判定達到所欲黏度之溶劑量，但較佳地（多種）溶劑之存在量以組分(a)、(b)、及(c)之重量和計，係＞ 0至50 wt%，較佳地5至30 wt%。可使用與其他組分化學性相容且能夠降低黏度之任何溶劑，但較佳的溶劑包括烴類、酯類、酮類；較佳地C₆ -C₁₈ 烴、C₃ -C₁₈ 酯、C₄ -C₁₈ 酮；較佳地甲苯、庚烷、丙酸丙酯、乙酸丁酯、甲基異丁基酮。可固化聚矽氧烷組成物之用途Preferably, the curable polysiloxane composition further comprises one or more solvents for adjusting the viscosity of the composition. For a particular composition, it is easy to determine the amount of solvent to achieve the desired viscosity, but preferably the amount of solvent (s) present is based on the weight and sum of components (a), (b), and (c), and is> 0 to 50 wt%, preferably 5 to 30 wt%. Any solvent that is chemically compatible with other components and can reduce viscosity can be used, but preferred solvents include hydrocarbons, esters, ketones; preferably C ₆ -C ₁₈ hydrocarbons, C ₃ -C ₁₈ esters, C ₄ -C ₁₈ ketones; preferably toluene, heptane, propyl propionate, butyl acetate, methyl isobutyl ketone. Uses of curable polysiloxane composition

在本文中所述之可固化聚矽氧烷組成物可用於希望藉由UV固化聚矽氧組成物之任何應用，但在需要基於聚矽氧烷的密封材料及遠端磷光體之光學應用中係特別有用的。可固化聚矽氧烷對於可見光實質上係透明的，並且非常適合用於光學用途。可固化聚矽氧烷組成物可形成膜並施加於適當位置，之後其係完全固化的。因此，本發明之一態樣係含有磷光體之膜，該膜藉由固化可固化聚矽氧烷組成物而形成。此類膜可具有任何厚度諸如10、20、30、50、100、125、或150微米，並且可係厚達200、300、或500微米。可藉由將可固化聚矽氧烷組成物塗佈至基材或離型襯墊上來製造膜。此類膜可用作為發光二極體(LED)封裝材料，或被定位成遠離與LED的直接接觸，作為遠端磷光體。可將LED結合到各種光學裝置中。方法及定義The curable polysiloxane composition described herein can be used in any application where it is desired to cure the polysiloxane composition by UV, but in optical applications requiring a polysiloxane-based sealing material and a remote phosphor Department is particularly useful. Curable polysiloxanes are substantially transparent to visible light and are well suited for optical applications. The curable polysiloxane composition can form a film and be applied in place, after which it is fully cured. Therefore, one aspect of the present invention is a phosphor-containing film, which is formed by curing a curable polysiloxane composition. Such films can have any thickness such as 10, 20, 30, 50, 100, 125, or 150 microns, and can be up to 200, 300, or 500 microns thick. Films can be made by applying a curable polysiloxane composition to a substrate or a release liner. Such films can be used as a light emitting diode (LED) packaging material, or positioned far away from direct contact with the LED as a remote phosphor. LEDs can be incorporated into various optical devices. Methods and definitions

在本文中使用下列用語意圖在賦予其等如下所述之含義。冠詞「一(a)」、「一(an)」、及「該(the)」各自係指一或多者。「組合(Combination)」意指將二或更多個項目以任何方法放在一起。「可(may)」表示一種選擇。重量百分比表示為wt%。莫耳百分比表示為莫耳%。The use of the following terms in this text is intended to give them meanings as described below. The articles "a", "an", and "the" each refer to one or more of them. "Combination" means putting two or more items together in any way. "May" means an option. Weight percentages are expressed as wt%. The Mohr percentage is expressed as Mohr%.

矽氧烷單元及側鏈之莫耳分率係藉由²⁹ Si-NMR及H-NMR來判定。測試材料之NMR樣本係藉由下列來製備：於一小瓶中稱量約4克之無溶劑聚矽氧烷材料（藉由在室溫下隔夜乾燥來製備）、及4克之0.04M Cr(acac)₃ 於CDCl₃ 之溶液，並徹底混合。然後將樣本轉移至無矽NMR管中。使用Varian Mercury 400 MHz NMR取得光譜。Molar fractions of the siloxane units and side chains were determined by ²⁹ Si-NMR and H-NMR. An NMR sample of the test material was prepared by weighing approximately 4 grams of a solvent-free polysiloxane material (prepared by drying overnight at room temperature) in a vial, and 4 grams of 0.04M Cr (acac) ₃ in CDCl ₃ solution and mix thoroughly. The sample was then transferred to a silicon-free NMR tube. Spectra were acquired using Varian Mercury 400 MHz NMR.

樣本之矽醇含量係於29Si NMR光譜中T(Ph,OZ)及T(Ph,OZ2)區域之積分值計算而來。T(烷基)基團視為完全縮合（假設）並從T(Ph,OZ)區域中減去。藉由將來自²⁹ Si NMR的D(Me₂ )之積分值乘以分率（偶合劑之Si莫耳數/合成配方中所用之PDMS的Si莫耳數）來計算T(烷基)含量。The silanol content of the sample was calculated from the integrated values of the T (Ph, OZ) and T (Ph, OZ2) regions in the 29Si NMR spectrum. The T (alkyl) group is considered to be fully condensed (hypothetical) and subtracted from the T (Ph, OZ) region. The T (alkyl) content was calculated by multiplying the integrated value of D (Me ₂ ) from the ²⁹ Si NMR by the fraction (Si mole number of the coupling agent / Si mole number of PDMS used in the synthetic formulation).

當測試方法編號未指明日期時，測試方法係指此文件優先權日之最新測試方法。對測試方法之參照含有對測試群(testing society)及測試方法編號之參照兩者。ASTM意指ASTM International。實例 When the test method number does not specify a date, the test method refers to the latest test method on the priority date of this document. A reference to a test method includes both a reference to a testing society and a test method number. ASTM means ASTM International. Examples

這些實例意圖對所屬技術領域中具有通常知識者說明本發明，並且不應解釋為限制不一定意味著限制申請專利範圍中所闡述之本發明的範疇。方法These examples are intended to illustrate the invention to those having ordinary skill in the art, and should not be construed as limiting to necessarily limit the scope of the invention as set forth in the scope of the patent application. method

UV 照射：藉由使用Fusion UV System Inc.塗佈機（現為Heraeus Noblelight, Hanau, Germany）以1至5 J/cm² 之UV功率照射經塗佈的膜，然後摺疊以用於流變測試。UV塗佈機提供200 nm至450 nm之寬的UV帶。 UV irradiation : The coated film was irradiated with a UV power of 1 to 5 J / cm ² by using a Fusion UV System Inc. coater (now Heraeus Noblelight, Hanau, Germany) and then folded for rheological testing . UV coaters provide UV bands from 200 nm to 450 nm.

流變測試 ：藉由使用ARES-G2流變儀(TA Instruments, New Castle, Delaware, USA)，遵循70℃至125（或150）℃、10℃/min的升溫程式，並且在125（或150）℃下等溫60 min，進行流變測試。聚矽氧烷-1 之製備： Rheological test : By using the ARES-G2 rheometer (TA Instruments, New Castle, Delaware, USA), follow the heating program of 70 ° C to 125 (or 150) ° C, 10 ° C / min, and at 125 (or 150 ) Isothermal for 60 min at ℃ for rheological test. Preparation of polysiloxane-1 :

步驟I：將矽醇封端之聚苯基甲基矽氧烷用甲基三乙醯氧基矽烷/乙基三乙醯氧基矽烷(MTA/ETA)封蓋：將18.49g（0.0813莫耳的Si）經混合之MTA及ETA（1:1之比），在手套箱中於氮氣下添加至880 g之聚苯基甲基矽氧烷（6.456莫耳的Si）溶液，接著在室溫下攪拌1小時以獲得封蓋之矽氧烷溶液。Step I: Cap the silanol-terminated polyphenylmethylsiloxane with methyltriacetoxysilane / ethyltriacetoxysilane (MTA / ETA). Si) mixed with MTA and ETA (1: 1 ratio), added to a solution of 880 g of polyphenylmethylsiloxane (6.456 moles of Si) in a glove box under nitrogen, then at room temperature Stir for 1 hour to obtain a capped silicone solution.

步驟II：製備聚矽氧烷 -1 共聚物：將720 g（5.271莫耳的Si）之苯基-T樹脂（其包含C₆ H₅ SiO_3/2 單元，Mw：約2000，矽醇含量：約65莫耳%）及601 g之丙酸丙酯的混合物，在氮封(nitrogen blanket)下添加至配備有溫度計、機械攪拌、附接有Dean-Stark設備之水冷式冷凝器之5L 4頸圓底燒瓶中。Dean-Stark設備預填充有丙酸丙酯，並使用加熱包加熱。將反應在回流下加熱30分鐘並移除3.82 g的水。然後將來自步驟I之封蓋矽氧烷溶液快速地添加至苯基-T樹脂溶液，接著回流2小時並移除5.58g的水。在115℃下，將約134.1 g之MTA/ETA（1：1之比率，0.589莫耳）添加至反應混合物，然後在回流下加熱2小時並移除約2.72 g的水。最後對反應進行三次水處理。對於各水處理，將反應冷卻至100℃，添加174 g之去離子水，然後在回流下加熱一段時間並藉由共沸蒸餾來移除水。最後，藉由蒸餾移除部分溶劑，以將最終的非揮發性含量(NVC)增加至73.4%，作為用於未來用途之聚矽氧烷 -1 產物溶液。所製備之聚矽氧烷-1含有約15莫耳%之矽醇。比較例AStep II: Preparation of polysiloxane- 1 copolymer: 720 g (5.271 moles of Si) of phenyl-T resin (which contains C ₆ H ₅ SiO _3/2 units, Mw: about 2000, silanol content : About 65 mol%) and 601 g of propyl propionate, added under a nitrogen blanket to a 5L 4 of a water-cooled condenser equipped with a thermometer, mechanical stirring, and a Dean-Stark device attached Neck round bottom flask. Dean-Stark equipment is pre-filled with propyl propionate and heated using a heat pack. The reaction was heated at reflux for 30 minutes and 3.82 g of water was removed. The capped siloxane solution from step I was then quickly added to the phenyl-T resin solution, followed by refluxing for 2 hours and removing 5.58 g of water. At 115 ° C., about 134.1 g of MTA / ETA (1: 1 ratio, 0.589 mole) was added to the reaction mixture, and then heated under reflux for 2 hours and about 2.72 g of water was removed. The reaction was finally subjected to three water treatments. For each water treatment, the reaction was cooled to 100 ° C, 174 g of deionized water was added, and then heated under reflux for a period of time and the water was removed by azeotropic distillation. Finally, some solvents were removed by distillation to increase the final non-volatile content (NVC) to 73.4% as a polysiloxane- 1 product solution for future use. The prepared polysiloxane-1 contained about 15 mol% of silanol. Comparative Example A

將5g含有矽醇之聚矽氧烷 -1 （含有15莫耳%之矽醇）與DBU (200 ppm)於SpeedMixer™ (Flack Tek Inc., Landrum, South Carolina, USA)中混合以獲得均勻的糊劑。使用刮塗棒(drawdown bar)在矽化聚對苯二甲酸乙二酯(PET)膜上塗佈125 µm厚度之糊劑。將經塗佈的膜在70℃下預烘烤30分鐘以移除所有溶劑。將經塗佈的膜折疊並熱壓到1毫米厚的盤(puck)中，然後衝壓至1吋(2.54 cm)直徑，用於流變測試。流變儀的溫度曲線係70℃至125℃、10℃/分鐘，然後停留60分鐘。在測試條件下，膜在0.1 min內固化。比較例B5 g of silanol- 1 containing silanol (containing 15 mol% of silanol) and DBU (200 ppm) were mixed in SpeedMixer ™ (Flack Tek Inc., Landrum, South Carolina, USA) to obtain a uniform Paste. Use a drawdown bar to apply a 125 µm thick paste to the siliconized polyethylene terephthalate (PET) film. The coated film was pre-baked at 70 ° C for 30 minutes to remove all solvents. The coated film was folded and hot pressed into a 1 mm thick puck and then stamped to a diameter of 1 inch (2.54 cm) for rheological testing. The temperature curve of the rheometer is 70 ° C to 125 ° C, 10 ° C / min, and then it stays for 60 minutes. Under the test conditions, the film was cured within 0.1 min. Comparative Example B

將5g之聚矽氧烷 -1 與DBU (200 ppm)及10g之磷光體（來自MATERION, Mayfield Heights, Ohio, USA之市售YAG型磷光體）於SpeedMixer中混合以獲得均勻的糊劑。使用刮塗棒在矽化PET膜上塗佈125 µm厚度之糊劑。將經塗佈的膜在70℃下預烘烤30分鐘以移除所有溶劑。將經塗佈的膜折疊並熱壓到1毫米厚的盤(puck)中，然後衝壓至1吋(2.54 cm)直徑，用於流變測試。流變溫度曲線係70℃至125℃、10℃/分鐘，然後停留60分鐘。在測試條件下，膜並未固化。實例15 g of polysiloxane- 1 and DBU (200 ppm) and 10 g of phosphor (commercially available YAG phosphor from MATERION, Mayfield Heights, Ohio, USA) were mixed in SpeedMixer to obtain a uniform paste. Apply a 125 µm thick paste to the siliconized PET film using a doctor blade. The coated film was pre-baked at 70 ° C for 30 minutes to remove all solvents. The coated film was folded and hot pressed into a 1 mm thick puck and then stamped to a diameter of 1 inch (2.54 cm) for rheological testing. The rheological temperature curve is 70 ° C to 125 ° C, 10 ° C / min, and then stays for 60 minutes. The film did not cure under the test conditions. Example 1

將5g之聚矽氧烷 -1 與NB-DBU（2-硝苄基-DBU，由發明人合成）(800 ppm)及10g之磷光體(YAG)於SpeedMixer中混合以獲得均勻的糊劑。使用刮塗棒在矽化PET膜上塗佈125 µm厚度之糊劑。將經塗佈的膜在70℃下預烘烤30分鐘以移除所有溶劑。無紫外光(UV)照射下，將經塗佈的膜折疊並熱壓到1毫米厚的盤中，然後衝壓至1吋直徑，用於流變測試。流變儀的溫度曲線係70℃至125℃、10℃/分鐘，然後停留60分鐘。在測試條件下，膜並未固化。實例25 g of polysiloxane- 1 and NB-DBU (2-nitrobenzyl-DBU, synthesized by the inventor) (800 ppm) and 10 g of phosphor (YAG) were mixed in SpeedMixer to obtain a uniform paste. Apply a 125 µm thick paste to the siliconized PET film using a doctor blade. The coated film was pre-baked at 70 ° C for 30 minutes to remove all solvents. Without ultraviolet (UV) radiation, the coated film was folded and hot pressed into a 1 mm thick disk, and then stamped to a 1 inch diameter for rheological testing. The temperature curve of the rheometer is 70 ° C to 125 ° C, 10 ° C / min, and then it stays for 60 minutes. The film did not cure under the test conditions. Example 2

將5g之聚矽氧烷 -1 與NB-DBU (800 ppm)及10g之磷光體(YAG)於SpeedMixer中混合以獲得均勻的糊劑。使用刮塗棒在矽化PET膜上塗佈125 µm厚度之糊劑。將經塗佈的膜在70℃下預烘烤30分鐘以移除所有溶劑。首先用365 nm UV光(3J/cm² )照射經塗佈的膜，然後將其折疊並熱壓到1毫米厚的盤(puck)中，然後衝壓至1吋(2.54 cm)直徑，用於流變測試。流變儀的溫度曲線係70℃至125℃、10℃/分鐘，然後停留60分鐘。膜在3分鐘內固化。實例35g of polysiloxane- 1 was mixed with NB-DBU (800 ppm) and 10g of phosphor (YAG) in SpeedMixer to obtain a uniform paste. Apply a 125 µm thick paste to the siliconized PET film using a doctor blade. The coated film was pre-baked at 70 ° C for 30 minutes to remove all solvents. The coated film was first irradiated with 365 nm UV light (3J / cm ² ), then folded and hot pressed into a 1 mm thick puck, and then stamped to a 1 inch (2.54 cm) diameter for Rheological test. The temperature curve of the rheometer is 70 ° C to 125 ° C, 10 ° C / min, and then it stays for 60 minutes. The film was cured in 3 minutes. Example 3

將5g之聚矽氧烷 -1 與NB-DBU (800 ppm)於SpeedMixer中混合以獲得均勻的糊劑。使用刮塗棒在矽化PET膜上塗佈125 µm厚度之糊劑。將經塗佈的膜在70℃下預烘烤30分鐘以移除所有溶劑。用365 nm UV光(3J/cm² )照射經塗佈的膜，然後將其折疊並熱壓到1毫米厚的盤(puck)中，然後衝壓至1吋(2.54 cm)直徑，用於流變測試。流變儀的溫度曲線係70℃至125℃、10℃/分鐘，然後停留60分鐘。膜在半分鐘內固化。5 g of polysiloxane- 1 and NB-DBU (800 ppm) were mixed in SpeedMixer to obtain a homogeneous paste. Apply a 125 µm thick paste to the siliconized PET film using a doctor blade. The coated film was pre-baked at 70 ° C for 30 minutes to remove all solvents. The coated film was irradiated with 365 nm UV light (3J / cm ² ), then folded and hot pressed into a 1 mm thick puck, and then punched to a 1 inch (2.54 cm) diameter for flow Change test. The temperature curve of the rheometer is 70 ° C to 125 ° C, 10 ° C / min, and then it stays for 60 minutes. The film cured in half a minute.

表1顯示實例1至實例3及比較例A至比較例B的流變測試之關鍵數據。在UV照射時，800 ppm之NB-DBU理論上可釋放200 ppm之DBU。Tanδ=1之時間表示固化速度。時間愈短，固化速度愈快。表1 Table 1 shows the key data of the rheological tests of Examples 1 to 3 and Comparative Examples A to B. Under UV irradiation, 800 ppm of NB-DBU can theoretically release 200 ppm of DBU. The time when Tanδ = 1 indicates the curing speed. The shorter the time, the faster the curing speed. Table 1

來自比較例A及B之數據顯示，添加磷光體YAG-D（約67 wt%）幾乎完全抑制了DBU催化劑之催化活性。然而，用UV潛伏DBU催化劑（例如NB-DBU）置換DBU，克服了DBU之磷光體抑制問題。實例1至實例3的流變結果清楚地表明，將67 wt% YAG磷光體添加至含有NB-DBU催化劑的配方中（實例2），相較於不含磷光體的配方（實例3），用UV照射以釋放DBU催化劑不會大大降低固化速度。含有NB-DBU及磷光體YAG之實例1的配方顯示在無UV照射下並未固化以釋放DBU催化劑。The data from Comparative Examples A and B show that the addition of phosphor YAG-D (about 67 wt%) almost completely inhibited the catalytic activity of the DBU catalyst. However, replacing the DBU with a UV latent DBU catalyst (such as NB-DBU) overcomes the phosphor suppression problem of the DBU. The rheological results of Examples 1 to 3 clearly show that when 67 wt% YAG phosphor is added to the formulation containing the NB-DBU catalyst (Example 2), compared with the phosphor-free formulation (Example 3), UV irradiation to release the DBU catalyst does not significantly reduce the curing speed. The formulation of Example 1 containing NB-DBU and phosphor YAG showed no curing to release the DBU catalyst without UV irradiation.

來自實例4至實例7之固化測試進一步證實，UV潛伏鹼催化劑可大大地降低在先前的組成物中已看到的DBU之磷光體抑制問題。實例4：無UV活化之本發明配方之膜的固化：The curing tests from Examples 4 to 7 further confirm that the UV latent base catalyst can greatly reduce the phosphor suppression problem of DBUs that have been seen in previous compositions. Example 4: Curing of a film of the invention formulation without UV activation:

聚矽氧烷-1 用作為基底矽氧烷。將IRGACURE 369溶解於甲苯中以製備10 wt%之催化劑儲備溶液。將0.5 wt%之IRGACURE 369添加至聚矽氧烷 -1 中以得到可固化有機矽氧烷配方。將配方塗佈至膜，並且以與比較例A相同的方式測試流變性，不同的是從70℃升溫至150℃，並且在150℃下等溫60 min。在測試時段期間膜並未固化，但推斷數據表明預計配方在130分鐘內固化。實例5：UV活化之本發明配方之膜的固化： Polysiloxane-1 was used as the base silicone. IRGACURE 369 was dissolved in toluene to prepare a 10 wt% catalyst stock solution. 0.5 wt% of IRGACURE 369 was added to polysiloxane- 1 to obtain a curable organosiloxane formulation. The formulation was applied to a film and tested for rheology in the same manner as in Comparative Example A, except that the temperature was raised from 70 ° C to 150 ° C, and isothermally heated at 150 ° C for 60 min. The film did not cure during the test period, but extrapolated data indicates that the formulation is expected to cure in 130 minutes. Example 5: Curing of a UV-activated film of the present invention:

將實例4中的膜暴露於248 nm、1000mJ/cm² 的UV照射。然後以與比較例A相同的方式測試經暴露的膜之流變性，不同的是從70℃升溫至150℃，並且在150℃下等溫60 min。膜在1分鐘內固化。實例6：無UV活化之本發明配方之磷光體膜的固化：The film in Example 4 was exposed to UV radiation at 248 nm, 1000 mJ / cm ² . The rheology of the exposed film was then tested in the same manner as in Comparative Example A, except that the temperature was raised from 70 ° C to 150 ° C, and isothermal at 150 ° C for 60 min. The film was cured in 1 minute. Example 6: Curing the phosphor film of the present invention without UV activation:

將實例5中5克之本發明配方與11g之磷光體（NYAG4355+NYAG4136+RR6536以5：5：1重量比，所有磷光體來自Intematix, Inc., Freemont, California, USA）在SpeedMixer上混合以獲得均勻的糊劑。然後將漿料塗佈至膜，並且以與比較例A相同的方式測試流變性，不同的是從70℃升溫至150℃，並且在150℃下等溫60 min。磷光體膜在測試條件下並未固化。實例7：UV活化之本發明配方之磷光體膜的固化：5 g of the formulation of the present invention in Example 5 and 11 g of phosphor (NYAG4355 + NYAG4136 + RR6536 in a 5: 5: 1 weight ratio, all phosphors from Intematix, Inc., Freemont, California, USA) were mixed on a SpeedMixer to obtain Even paste. The slurry was then applied to a film and tested for rheology in the same manner as in Comparative Example A, except that the temperature was raised from 70 ° C to 150 ° C, and isothermally heated at 150 ° C for 60 min. The phosphor film was not cured under the test conditions. Example 7: Curing of a UV-activated phosphor film of the present invention:

將實例6中的膜暴露於248 nm、2000mJ/cm² 的UV照射。然後以與比較例A相同的方式測試經暴露的磷光體膜之流變性，不同的是從70℃升溫至150℃，並且在150℃下等溫60 min。經暴露的磷光體膜在5分鐘內固化。產業利用性 The film in Example 6 was exposed to 248 nm, 2000 mJ / cm ² UV irradiation. The rheological properties of the exposed phosphor film were then tested in the same manner as in Comparative Example A, except that the temperature was raised from 70 ° C to 150 ° C, and isothermal at 150 ° C for 60 min. The exposed phosphor film was cured in 5 minutes. Industrial availability

在本文中所述之可固化聚矽氧烷組成物可用於希望藉由UV固化聚矽氧組成物之任何應用。可固化聚矽氧烷組成物在光學應用及包括太陽能光伏設備在內之光伏應用中係特別有用的，其中需要快速地將基於聚矽氧烷的封裝材料及遠端磷光體固化。The curable polysiloxane composition described herein can be used in any application where it is desired to cure the polysiloxane composition by UV. Curable polysiloxane compositions are particularly useful in optical applications and photovoltaic applications including solar photovoltaic devices, where polysiloxane-based packaging materials and remote phosphors need to be quickly cured.

Claims

一種可固化聚矽氧烷組成物，其包含： (a) 10至95 wt%之矽醇官能性聚矽氧烷，其包含矽氧烷單元(R¹ R² SiO_2/2 )_a (R³ SiO_3/2 )_b ， (b) 5至5000 ppm之UV潛伏鹼催化劑，及 (c) 5至90 wt%之顆粒磷光體、填料、或其組合；其中a係0.1至0.9，b係0.1至0.9，a+b係至少0.95且不大於1；R¹ 、R² 、及R³ 獨立地表示羥基或C₁ -C₂₀ 有機取代基；及矽醇官能性聚矽氧烷，其包含5至50莫耳%之矽醇基團。A curable polysiloxane composition comprising: (a) 10 to 95 wt% of a silanol-functional polysiloxane comprising a siloxane unit (R ¹ R ² SiO _2/2 ) _a (R ³ SiO _3/2 ) _b , (b) 5 to 5000 ppm UV latent alkali catalyst, and (c) 5 to 90 wt% particulate phosphor, filler, or a combination thereof; wherein a is 0.1 to 0.9, and b is 0.1 to 0.9, a + b is at least 0.95 and not more than 1; R ¹ , R ² , and R ³ independently represent a hydroxyl group or a C ₁ -C ₂₀ organic substituent; and a silanol-functional polysiloxane including 5 to 50 mol% of silanol groups.

如請求項1之組成物，其中R¹ 、R² 、及R³ 獨立地表示羥基、烷基、烯基、或芳基。The composition of claim 1, wherein R ¹ , R ² , and R ³ independently represent a hydroxyl group, an alkyl group, an alkenyl group, or an aryl group.

如請求項2之組成物，其中R¹ 、R² 、及R³ 獨立地表示羥基、C₁ -C₁₀ 芳基、或C₁ -C₄ 烷基。The composition of claim 2, wherein R ¹ , R ² , and R ³ independently represent a hydroxyl group, a C ₁ -C ₁₀ aryl group, or a C ₁ -C ₄ alkyl group.

如請求項1至3中任一項之組成物，其中該聚矽氧烷係嵌段共聚物，其包含包含(R¹ R² SiO_2/2 )單元之線型部分、及包含(R³ SiO_3/2 )單元之樹脂狀部分。The composition according to any one of claims 1 to 3, wherein the polysiloxane block copolymer comprises a linear portion including (R ¹ R ² SiO _2/2 ) units, and (R ³ SiO _3/2 ) the resinous part of the unit.

如請求項1至4中任一項之組成物，以組分(a)、(b)、及(c)之總重量計，其進一步包含總量至多50 wt%之一或多種溶劑。If the composition of any one of claims 1 to 4, based on the total weight of components (a), (b), and (c), it further comprises one or more solvents in a total amount of up to 50 wt%.

如請求項1至5中任一項之組成物，其中該UV潛伏鹼催化劑係式(I)至(IV)中之一者：其中NB1代表環狀或非環狀三級胺，NB2代表一級或二級胺，該相對離子係形成鹽之任何陰離子，該鹽在該聚矽氧烷組成物中係穩定的，且Ar代表經取代或未經取代的芳基。The composition of any one of claims 1 to 5, wherein the UV latent base catalyst is one of the formulae (I) to (IV): Where NB1 represents a cyclic or acyclic tertiary amine, NB2 represents a primary or secondary amine, the opposite ion system forms any anion of a salt, the salt is stable in the polysiloxane composition, and Ar represents Substituted or unsubstituted aryl.

如請求項6之組成物，其中該UV潛伏鹼催化劑係NB-DBU。The composition of claim 6, wherein the UV latent base catalyst is NB-DBU.

如請求項1至7中任一項之組成物，其中組分(c)含YAG磷光體。The composition according to any one of claims 1 to 7, wherein component (c) contains a YAG phosphor.

一種膜，其包含如請求項1至8中任一項之組成物的固化產物。A film comprising a cured product of the composition according to any one of claims 1 to 8.

一種形成膜產物之方法，其包含下列步驟：用如請求項1至8中任一項之組成物塗覆基材或襯墊、用UV光照射、及將該膜加熱到至少攝氏70度。A method of forming a film product comprising the steps of: coating a substrate or a pad with a composition according to any one of claims 1 to 8, irradiating with UV light, and heating the film to at least 70 degrees Celsius.