TWI429608B - The manufacturing method of the layered body - Google Patents
The manufacturing method of the layered body Download PDFInfo
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- TWI429608B TWI429608B TW099138127A TW99138127A TWI429608B TW I429608 B TWI429608 B TW I429608B TW 099138127 A TW099138127 A TW 099138127A TW 99138127 A TW99138127 A TW 99138127A TW I429608 B TWI429608 B TW I429608B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
- B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
- B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
- B29C65/54—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive between pre-assembled parts
- B29C65/542—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive between pre-assembled parts by injection
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/18—Handling of layers or the laminate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/18—Handling of layers or the laminate
- B32B38/1858—Handling of layers or the laminate using vacuum
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
- B32B2315/08—Glass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Laminated Bodies (AREA)
- Sealing Material Composition (AREA)
- Electroluminescent Light Sources (AREA)
- Joining Of Glass To Other Materials (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Description
本發明係關於積層體的製造方法,該積層體具備有一對基板、以及存在於該一對基板間的硬化性樹脂組成物之硬化物層。The present invention relates to a method for producing a laminated body comprising a pair of substrates and a cured layer of a curable resin composition existing between the pair of substrates.
依照本發明方法所製得的積層體,適用為諸如夾層玻璃、影像顯示裝置的前面板,更具體而言,適用於諸如液晶顯示裝置(LCD)、有機EL或無機EL之類的EL(電激發光)顯示裝置、電漿顯示裝置、電子墨水型影像顯示裝置之類的平面顯示器(FPD)之前面板,以及諸如薄層太陽電池裝置、觸控面板的保護板等用途。The laminate produced by the method of the present invention is suitable for use as a front panel such as a laminated glass or image display device, and more particularly, for an EL such as a liquid crystal display device (LCD), an organic EL or an inorganic EL. A light-emitting panel display device, a plasma display device, a front panel of a flat panel display (FPD) such as an electronic ink type image display device, and a protective plate such as a thin-film solar cell device or a touch panel.
經由接著層將一對玻璃基板形成一體化的夾層玻璃,因為遭破損的玻璃破片會附著於薄膜上而不會有飛散情形,因而被使用為汽車的防風玻璃,又,因為較難貫穿且強度優異,因而被使用為建物的窗玻璃(安全玻璃、防盜玻璃)(參照專利文獻1、2)。A pair of glass substrates are formed into an integrated laminated glass via an adhesive layer. Since the damaged glass fragments adhere to the film without scattering, they are used as windshields for automobiles, and because they are difficult to penetrate and have strength. A window glass (safety glass, anti-theft glass) which is excellent in use as a building (refer to Patent Documents 1 and 2).
再者,就從防止液晶面板破損、及防止光反射的觀點,已知有將前面板設置於該液晶面板前面的液晶顯示裝置,該前面板係在透明保護板與偏光板間封入透明中間膜者(參照專利文獻3)。Further, from the viewpoint of preventing damage of the liquid crystal panel and preventing light reflection, a liquid crystal display device in which a front panel is provided on the front surface of the liquid crystal panel is known, and the front panel is sealed with a transparent interlayer film between the transparent protective plate and the polarizing plate. (refer to Patent Document 3).
再者,已知有具太陽電池裝置的太陽電池模組,該太陽電池裝置係在成為受光面的透明表面材與背面材間,利用樹脂等密封材料進行密封者(參照專利文獻4)。In addition, a solar cell module having a solar cell device is known which is sealed between a transparent surface material and a back surface material which are light-receiving surfaces, and is sealed with a sealing material such as resin (see Patent Document 4).
依此,具有一對基板、及存在於該一對基板間的硬化性樹脂組成物之硬化物層的積層體,在各種技術領域中有存在的需求。Accordingly, there is a need in various technical fields for a laminate having a pair of substrates and a cured layer of a curable resin composition existing between the pair of substrates.
此積層體的製造方法有多數提案,專利文獻1、2所記載的方法並未限定所使用基板的種類,挾持於基板間而成為中間層的硬化性樹脂組成物種類自由度大,能有效利用用以形成中間層的資源,就生產性優異、環境負荷小的觀點係屬優異。There are many proposals for the production method of the laminate. The methods described in Patent Documents 1 and 2 do not limit the type of the substrate to be used, and the type of the curable resin composition which is interposed between the substrates and becomes an intermediate layer has a large degree of freedom and can be effectively utilized. The resources for forming the intermediate layer are excellent in terms of excellent productivity and small environmental load.
此方法係在其中一基板上的周邊部形成用以封住硬化性樹脂組成物的密封部,之後再對基板上由密封部所包圍的區域供應硬化性樹脂組成物。接著,在減壓環境下,藉由在其中一基板上重疊另一基板,以在一對基板間挾持硬化性樹脂組成物並加以密封。In this method, a sealing portion for sealing a curable resin composition is formed on a peripheral portion of one of the substrates, and then a curable resin composition is supplied to a region surrounded by the sealing portion on the substrate. Next, the other substrate is superposed on one of the substrates in a reduced pressure environment to sandwich and seal the curable resin composition between the pair of substrates.
接著,將挾持著硬化性樹脂組成物且已密封的一對基板,放置在高於前述減壓環境的壓力環境下(例如大氣壓下)。藉由環境壓力的上升,朝一對透明基板彼此密接的方向按壓,同時因為殘留在密閉空間內的空隙體積會配合環境的差壓而縮減,因而硬化性樹脂組成物會流入由一對基板與密封部所密閉的密閉空間中之減壓空間內,致使密閉空間整體被硬化性樹脂組成物均勻填充。然後,藉由使硬化性樹脂組成物硬化來獲得積層體。Next, the pair of substrates which are held by the curable resin composition and sealed are placed under a pressure environment higher than the above-described reduced pressure environment (for example, at atmospheric pressure). When the environmental pressure rises, the pair of transparent substrates are pressed in the direction in which they are in close contact with each other, and since the void volume remaining in the sealed space is reduced in accordance with the environmental differential pressure, the curable resin composition flows into the pair of substrates and is sealed. In the decompression space in the sealed space in which the portion is sealed, the entire sealed space is uniformly filled with the curable resin composition. Then, the laminate is obtained by hardening the curable resin composition.
專利文獻1:國際公開WO2008/081838號公報Patent Document 1: International Publication WO2008/081838
專利文獻2:國際公開WO2009/016943號公報Patent Document 2: International Publication WO2009/016943
專利文獻3:日本專利特開2009-205065號公報Patent Document 3: Japanese Patent Laid-Open Publication No. 2009-205065
專利文獻4:日本專利特開平11-87743號公報Patent Document 4: Japanese Patent Laid-Open No. Hei 11-87743
如上所述,專利文獻1、2所記載之積層體的製造方法,係在減壓環境下,於一對透明基板間挾持硬化性樹脂組成物,經密封後再藉由放置在高於前述減壓環境的壓力環境下(例如大氣壓下),以呈現密閉空間整體被硬化性樹脂組成物均勻填充的狀態。但是,依照所使用之硬化性樹脂組成物的黏度、存在於密封空間中之硬化性樹脂組成物的層厚,會有較難呈現密閉空間整體被硬化性樹脂組成物均勻填充狀態的情況。As described above, in the method for producing a laminate according to Patent Documents 1 and 2, the curable resin composition is held between a pair of transparent substrates in a reduced pressure environment, and after being sealed, it is placed at a higher level than the above-mentioned reduction. In a pressure environment under a pressurized environment (for example, at atmospheric pressure), the entire sealed space is uniformly filled with the curable resin composition. However, depending on the viscosity of the curable resin composition to be used and the layer thickness of the curable resin composition present in the sealed space, it may be difficult to uniformly exhibit a state in which the entire sealed space is uniformly filled with the curable resin composition.
即,當所使用之硬化性樹脂組成物的黏度較高時(例如硬化性樹脂組成物黏度達0.2Pa‧s以上之情況)、以及存在於密封空間之硬化性樹脂組成物的層厚較大時(例如硬化性樹脂組成物的層厚達30μm以上之情況),將挾持著硬化性樹脂組成物並經密封的一對基板,放置在高於前述減壓環境的壓力環境下(例如大氣壓下),之後為縮減殘留在密閉空間中的空隙,其所需時間會有增加的可能性。因而,為能呈現密閉空間整體被硬化性樹脂組成物均勻填充的狀態,便需要較長時間。In other words, when the viscosity of the curable resin composition to be used is high (for example, the viscosity of the curable resin composition is 0.2 Pa‧s or more), and the layer thickness of the curable resin composition existing in the sealed space is large. When the layer thickness of the curable resin composition is 30 μm or more, the pair of substrates which are held by the curable resin composition and sealed are placed under a pressure environment higher than the above-described reduced pressure environment (for example, at atmospheric pressure). ), and then to reduce the voids remaining in the confined space, the time required may increase. Therefore, it takes a long time to present a state in which the entire sealed space is uniformly filled with the curable resin composition.
本發明係為解決上述習知技術的問題點而完成,其目的在於提供:在使被挾持於一對基板間且經密閉的硬化性樹脂組成物硬化以製造積層體的方法中,能縮短為使密閉空間整體被硬化性樹脂組成物均勻填充的所需時間之新穎方法。The present invention has been made to solve the problems of the above-described conventional techniques, and an object thereof is to provide a method for producing a laminated body by curing a sealed curable resin composition held between a pair of substrates, thereby shortening to A novel method of making the entire space of the sealed space uniformly filled with the curable resin composition.
為達成上述目的,本發明積層體的製造方法係包含有下述步驟:準備2片基板;在其中一基板上的周邊部形成密封部,該密封部係用以封住硬化性樹脂組成物者;對其中一基板上由前述密封部所包圍的區域,供應硬化性樹脂組成物;於減壓環境下,在前述被供應的硬化性樹脂組成物上重疊另一基板,以在一對基板間挾持硬化性樹脂組成物並加以密封;及將挾持著硬化性樹脂組成物的一對基板,放置在高於前述減壓環境的第2壓力環境下,於該第2壓力環境下使硬化性樹脂組成物硬化以製造積層體,該積層體的製造方法之特徵在於:控制供應至基板上之前述硬化性樹脂組成物的塗佈狀態、以及在前述硬化性樹脂組成物上重疊另一基板的時期,以在將前述另一基板重疊於其中一基板上之時,存在於由前述密封部所包圍區域中的硬化性樹脂組成物層可滿足下述(1)~(3);In order to achieve the above object, the method for producing a laminate according to the present invention comprises the steps of: preparing two substrates; forming a sealing portion on a peripheral portion of one of the substrates, the sealing portion for sealing the curable resin composition Supplying a curable resin composition to a region surrounded by the sealing portion on one of the substrates; and superposing another substrate on the supplied curable resin composition under a reduced pressure environment to be between the pair of substrates Holding and curing the curable resin composition; and placing a pair of substrates holding the curable resin composition in a second pressure environment higher than the reduced pressure environment, and curing the resin in the second pressure environment The composition is cured to produce a laminate, and the method for producing the laminate is characterized in that a coating state of the curable resin composition supplied onto the substrate is controlled, and a period in which another substrate is superposed on the curable resin composition When the other substrate is superposed on one of the substrates, the layer of the curable resin composition present in the region surrounded by the sealing portion can satisfy (1) to (3);
(1)存在於前述硬化性樹脂組成物層中之空隙,其投影形狀的等值圓直徑(equivalent circle diameter)Dpore 為10mm以下;(1) a void existing in the curable resin composition layer, the projected circle having an equivalent circle diameter D pore of 10 mm or less;
(2)前述硬化性樹脂組成物層中未存在有空隙之部分,其投影形狀的等值圓直徑Dnon-pore 為40mm以下;(2) a portion where the void is not present in the curable resin composition layer, and the equivalence circle diameter D non-pore of the projected shape is 40 mm or less;
(3)前述硬化性樹脂組成物層和存在於前述硬化性樹脂組成物層中之空隙,交互地與前述密封部呈相接觸之狀態。(3) The curable resin composition layer and the voids present in the curable resin composition layer are in a state of being in contact with the sealing portion.
另外,上述所謂「可滿足(1)~(3)」係指可滿足(1)、(2)及(3)所記載要件中任一項。In addition, the above-mentioned "satisfiable (1) to (3)" means that any one of the requirements described in (1), (2), and (3) can be satisfied.
本發明積層體的製造方法中,較佳係在前述一對基板中至少一片為透明基板。In the method for producing a laminate according to the present invention, it is preferable that at least one of the pair of substrates is a transparent substrate.
本發明積層體的製造方法中,前述硬化性樹脂組成物的黏度係0.2~50Pa‧s。In the method for producing a laminate according to the present invention, the viscosity of the curable resin composition is 0.2 to 50 Pa‧s.
本發明積層體的製造方法中,存在於由前述一對基板與前述密封部所密封的空間內之硬化性樹脂組成物層的厚度,係30~3000μm。In the method for producing a laminate according to the present invention, the thickness of the curable resin composition layer in the space sealed by the pair of substrates and the sealing portion is 30 to 3000 μm.
本發明積層體的製造方法中,前述密封部係使用黏度200~3000Pa‧s的第2硬化性樹脂組成物而形成者。In the method for producing a laminate according to the present invention, the sealing portion is formed using a second curable resin composition having a viscosity of 200 to 3,000 Pa s.
本發明積層體的製造方法中,較佳係前述減壓環境為0.1~1000Pa的壓力環境。In the method for producing a laminate according to the present invention, it is preferred that the pressure-reducing environment is a pressure environment of 0.1 to 1000 Pa.
本發明積層體的製造方法,較佳係前述第2環境的壓力較前述減壓環境的壓力高出50kPa以上。另外,相對於該第2壓力環境,在朝由密封部所包圍區域供應的前述樹脂膜形成用硬化性樹脂組成物上,重疊另一基板並在減壓下進行密封的減壓環境,相當於第1壓力環境。In the method for producing a laminate according to the present invention, it is preferred that the pressure in the second environment is higher than the pressure in the reduced pressure environment by 50 kPa or more. In the second pressure environment, the pressure-reducing environment in which the other substrate is superposed on the curable resin composition for resin film formation supplied to the region surrounded by the sealing portion and sealed under reduced pressure is equivalent to The first pressure environment.
本發明積層體的製造方法中,較佳係對其中一基板上由前述密封部所包圍區域進行硬化性樹脂組成物供應,係指對由前述密封部所包圍區域分散滴下硬化性樹脂組成物。In the method for producing a laminate according to the present invention, it is preferable that the curable resin composition is supplied to a region surrounded by the sealing portion on one of the substrates, and the curable resin composition is dispersed in a region surrounded by the sealing portion.
此情況,較佳係藉由在使前述硬化性樹脂組成物分散滴下之際,藉由使前述其中一基板、與分散滴下時所使用噴嘴進行相對性擺動,而滴下的硬化性樹脂組成物之等值圓直徑強制性擴大,俾使在由前述密封部所包圍區域中存在的硬化性樹脂組成物之等值圓直徑呈均勻。In this case, when the curable resin composition is dispersed and dropped, the curable resin composition which is dropped by relatively oscillating the one of the substrates and the nozzle used for dispersion and dropping is preferably used. The diameter of the equivalence circle is forcibly expanded, so that the equivalence circle diameter of the curable resin composition existing in the region surrounded by the sealing portion is uniform.
本發明積層體的製造方法中,對其中一基板上供應前述硬化性樹脂組成物,以在對其中一基板上由前述密封所包圍區域供應前述硬化性樹脂組成物時,使前述硬化性樹脂組成物呈滿足下述(4)~(9)的振動曲線;In the method for producing a laminate according to the present invention, the curable resin composition is supplied onto one of the substrates to form the curable resin composition when the curable resin composition is supplied to a region surrounded by the seal on one of the substrates. The object exhibits a vibration curve satisfying the following (4) to (9);
(4)相對於振動曲線前進方向,在垂直方向依一定的週期(X)與振幅(Y)重複位移;(4) Repeating the displacement in the vertical direction according to a certain period (X) and amplitude (Y) with respect to the forward direction of the vibration curve;
(5)相鄰接之振動曲線的位移係相互呈反相位;(5) The displacements of adjacent vibration curves are opposite to each other;
(6)將開始供應時的振動曲線粗細度設為m(mm)時,前述週期(X)(mm)、及前述振幅(Y)(mm)係滿足下式:(6) When the thickness of the vibration curve at the time of starting supply is m (mm), the period (X) (mm) and the amplitude (Y) (mm) satisfy the following formula:
2.1×m≦X≦10×m2.1×m≦X≦10×m
(2.1×m)/2≦Y≦(10×m)/2(2.1×m)/2≦Y≦(10×m)/2
(7)將開始供應時的振動曲線粗細度設為m(mm)時,振動曲線與密封部間之最短距離d(s-r) (mm)係滿足下式:(7) When the thickness of the vibration curve at the time of starting supply is m (mm), the shortest distance d (sr) (mm) between the vibration curve and the sealing portion satisfies the following formula:
d(s-r) ≦2.5×md (sr) ≦ 2.5 × m
(8)將開始供應時的振動曲線粗細度設為m(mm)時,相鄰接之振動曲線間的最短距離d(r-r) (mm)係滿足下式:(8) When the thickness of the vibration curve at the start of supply is m (mm), the shortest distance d (rr) (mm) between the adjacent vibration curves satisfies the following formula:
d(r-r) ≦5×md (rr) ≦ 5 × m
(9)當E=2Y-2m時,該E(mm)係滿足下式:(9) When E=2Y-2m, the E(mm) system satisfies the following formula:
(Y+d(r-r) )/10≦E≦Y+d(r-r) (Y+d (rr) )/10≦E≦Y+d (rr)
另外,上述所謂「滿足(4)~(9)」係指可滿足(4)至(9)所記載要件中任一項。In addition, the above-mentioned "satisfying (4) to (9)" means that any one of the requirements described in (4) to (9) can be satisfied.
再者,本發明積層體的製造方法中,對其中一基板上供應前述硬化性樹脂組成物,以在對其中一基板上由前述密封所包圍區域進行供應時,前述硬化性樹脂組成物之可滿足下述(10)~(14)的振動曲線和與該振動曲線朝同一方向前進的直線相鄰接;Further, in the method for producing a laminate according to the present invention, the curable resin composition is supplied to one of the substrates to supply the region surrounded by the seal on one of the substrates, and the curable resin composition may be used. a vibration curve satisfying the following (10) to (14) and a line advancing in the same direction as the vibration curve are adjacent to each other;
(10)相對於振動曲線前進方向,在垂直方向依一定的週期(X)與振幅(Y)重複位移;(10) Repeating the displacement in a vertical direction with respect to a certain period (X) and an amplitude (Y) with respect to the direction in which the vibration curve advances;
(11)將開始供應時的振動曲線粗細度設為m(mm)時,前述週期(X)(mm)、及前述振幅(Y)(mm)係滿足下式:(11) When the thickness of the vibration curve at the time of starting supply is m (mm), the period (X) (mm) and the amplitude (Y) (mm) satisfy the following formula:
2.1×m≦X≦10×m2.1×m≦X≦10×m
(2.1×m)/2≦Y≦(10×m)/2(2.1×m)/2≦Y≦(10×m)/2
(12)當振動曲線位於密封部附近,且將開始供應時的振動曲線粗細度設為m(mm)時,該振動曲線與密封部間之最短距離d(s-r) (mm)係滿足下式:(12) When the vibration curve is located near the seal portion and the thickness of the vibration curve at the time of starting supply is m (mm), the shortest distance d (sr) (mm) between the vibration curve and the seal portion satisfies the following formula :
d(s-r) ≦2.5×md (sr) ≦ 2.5 × m
(13)將開始供應時的振動曲線粗細度設為m(mm)時,相鄰接之振動曲線與直線間之最短距離d(r-r) (mm)係滿足下式:(13) When the thickness of the vibration curve at the start of supply is m (mm), the shortest distance d (rr) (mm) between the adjacent vibration curve and the straight line satisfies the following formula:
d(r-r) ≦2.5×md (rr) ≦ 2.5 × m
(14)當E=2Y-2m時,該E(mm)係滿足下式:(14) When E=2Y-2m, the E(mm) system satisfies the following formula:
(Y+d(r-r) )/20≦E≦(Y+d(r-r) )/2(Y+d (rr) )/20≦E≦(Y+d (rr) )/2
另外,上述所謂「滿足(10)~(14)」係指可滿足(10)至(14)所記載要件中任一項。In addition, the above-mentioned "satisfaction (10) to (14)" means that any one of the requirements described in (10) to (14) can be satisfied.
再者,上述本發明積層體的製造方法中,較佳係從硬化性樹脂組成物完成對其中一基板上由前述密封部所包圍區域的滴下開始,直到積層為止的時間係30~1800秒。Further, in the method for producing a laminate according to the present invention, it is preferable that the time from the start of the dropping of the region surrounded by the sealing portion on one of the substrates from the curable resin composition to the time of lamination is 30 to 1800 seconds.
根據本發明積層體的製造方法,可縮短製造積層體過程中所實施之利用硬化性樹脂組成物均勻填充由一對基板與密封部所密閉的空間整體所需要的時間,並可提高積層體的生產性。According to the method for producing a laminated body of the present invention, it is possible to shorten the time required for uniformly filling the space sealed by the pair of substrates and the sealing portion by the curable resin composition, which is carried out during the production of the laminated body, and to improve the laminated body. Productive.
第1圖係基板的平面圖,在基板上的周邊部形成密封部狀態。Fig. 1 is a plan view showing a state in which a sealing portion is formed in a peripheral portion of the substrate.
第2圖係基板的平面圖,在基板由密封部所包圍的部分中形成硬化性樹脂組成物層的狀態。Fig. 2 is a plan view showing a state in which a curable resin composition layer is formed in a portion of the substrate surrounded by the sealing portion.
第3(a)~(c)圖係對基板由密封部所包圍區域點狀分散滴下之硬化性樹脂組成物的經時變化圖。Figs. 3(a) to 3(c) are diagrams showing temporal changes of the curable resin composition in which the substrate is dispersed in a dot shape in a region surrounded by the sealing portion.
第4(a)~(d)圖係硬化性樹脂組成物在第3(a)圖所示狀態時施行真空積層的情況下,硬化性樹脂組成物在真空積層時及解除減壓環境後的狀態圖。When the vacuum-curable resin composition of the fourth (a) to (d) is subjected to vacuum lamination in the state shown in Fig. 3(a), the curable resin composition is laminated at the time of vacuum lamination and after the decompression environment is released. State diagram.
第5(a)~(d)圖係硬化性樹脂組成物在第3(b)圖所示狀態時施行真空積層的情況下,硬化性樹脂組成物在真空積層時及解除減壓環境後的狀態圖。When the vacuum-curable resin composition of the fifth (a) to (d) is subjected to vacuum lamination in the state shown in Fig. 3(b), the curable resin composition is laminated at the time of vacuum lamination and after the decompression environment is released. State diagram.
第6(a)~(d)圖係硬化性樹脂組成物在第3(c)圖所示狀態時施行真空積層的情況下,硬化性樹脂組成物在真空積層時及解除減壓環境後的狀態圖。In the case where the vacuum-curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3(c), the curable resin composition is subjected to vacuum lamination and after the decompression environment is released. State diagram.
第7(a)~(e)圖係對基板由密封部所包圍區域點狀分散滴下之硬化性樹脂組成物的經時變化圖。The seventh (a) to (e) diagrams are time-dependent changes of the curable resin composition in which the substrate is dispersed in a dot shape in a region surrounded by the sealing portion.
第8圖係使用單點噴嘴,對基板由密封部所包圍區域分散滴下硬化性樹脂組成物的順序圖。Fig. 8 is a sequence diagram in which a hard-pointing resin composition is dispersed and dropped on a substrate surrounded by a sealing portion using a single-point nozzle.
第9圖係使用多點噴嘴,對基板由密封部所包圍區域分散滴下硬化性樹脂組成物的順序圖。Fig. 9 is a sequence diagram in which a multi-point nozzle is used to disperse and deposit a curable resin composition on a substrate surrounded by a sealing portion.
第10圖係使用多點噴嘴,對基板由密封部所包圍區域分散滴下硬化性樹脂組成物的順序圖。Fig. 10 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.
第11圖係使用多點噴嘴,對基板由密封部所包圍區域分散滴下硬化性樹脂組成物的順序圖。Fig. 11 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.
第12圖係使用多點噴嘴,對基板由密封部所包圍區域分散滴下硬化性樹脂組成物的順序圖。Fig. 12 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.
第13圖係滴下後的經過時間t(sec)與硬化性樹脂組成物的等值圓直徑d(mm)間之關係圖。Fig. 13 is a graph showing the relationship between the elapsed time t (sec) after dropping and the equivalent circle diameter d (mm) of the curable resin composition.
第14圖係滴下後的經過時間t、硬化性樹脂組成物的等值圓直徑d及存在於硬化性樹脂組成物層中之空隙的等值圓直徑Dpore 間之關係圖。Fig. 14 is a graph showing the relationship between the elapsed time t after dropping, the equivalence circle diameter d of the curable resin composition, and the equivalence circle diameter D pore of the voids present in the curable resin composition layer.
第15圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 15 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第16圖相當於第15圖之部分放大圖,係顯示振動曲線30a、30b形狀的經時變化。Fig. 16 corresponds to a partially enlarged view of Fig. 15, showing temporal changes in the shape of the vibration curves 30a, 30b.
第17圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 17 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第18圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 18 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第19圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 19 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第20圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 20 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第21圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 21 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第22圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 22 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第23圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 23 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第24圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 24 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
以下,參照圖式針對本發明積層體的製造方法進行說明。Hereinafter, a method of manufacturing a laminated body of the present invention will be described with reference to the drawings.
本發明積層體的製造方法中,一對基板中,於其中一基板上的周邊部形成密封部,該密封部係用以封住硬化性樹脂組成物者。第1圖係基板的平面圖,顯示在基板10上的周邊部形成密封部20之狀態。In the method for producing a laminate according to the present invention, in the pair of substrates, a sealing portion is formed on a peripheral portion of one of the substrates, and the sealing portion is used to seal the curable resin composition. Fig. 1 is a plan view showing a state in which a sealing portion 20 is formed on a peripheral portion of the substrate 10.
本發明積層體的製造方法中,如後所述,因為密封部形成用硬化性樹脂組成物較佳係使用光硬化性樹脂組成物,因而一對基板中,最好至少有1個係屬於透明基板。此時,一對基板中,可僅係其中一者為透明基板而另一者為不透明基板,亦可二片基板均為透明基板。此處,當其中一者係透明基板而另一者係不透明基板時,可在透明基板的周邊部形成密封部,亦可在不透明基板的周邊部形成密封部。In the method for producing a layered product of the present invention, as described later, since the curable resin composition for forming a sealing portion is preferably a photocurable resin composition, at least one of the pair of substrates is preferably transparent. Substrate. In this case, only one of the pair of substrates may be a transparent substrate and the other may be an opaque substrate, or both of the substrates may be transparent substrates. Here, when one of them is a transparent substrate and the other is an opaque substrate, a sealing portion may be formed at a peripheral portion of the transparent substrate, or a sealing portion may be formed at a peripheral portion of the opaque substrate.
另外,透明基板在屬於透明,即具可見光穿透性之基板的前提下,其餘則無特別的限定。透明基板的具體例可如玻璃基板及透明樹脂基板。該等之中,就從具透明性、耐光性、低雙折射性、高平面精度、耐表面刮傷性、及高機械強度的觀點,較佳為玻璃基板。Further, the transparent substrate is not particularly limited as long as it is transparent, that is, a substrate having visible light transmittance. Specific examples of the transparent substrate may be, for example, a glass substrate and a transparent resin substrate. Among these, a glass substrate is preferred from the viewpoints of transparency, light resistance, low birefringence, high planar precision, surface scratch resistance, and high mechanical strength.
玻璃基板的材料除鈉鈣玻璃之外,尚可例如鐵分更低且偏藍之較小的高穿透玻璃(白板)、硼矽酸玻璃等。The material of the glass substrate may be, for example, a high-permeability glass (white plate) or a borosilicate glass having a lower iron content and a smaller blue color than the soda lime glass.
透明樹脂基板的材料可如透明性較高的樹脂材料(聚碳酸酯、聚甲基丙烯酸甲酯等)。The material of the transparent resin substrate can be, for example, a resin material having high transparency (polycarbonate, polymethyl methacrylate, etc.).
再者,透明基板在至少具有可見光穿透性的前提下,亦可係諸如在使光進行散射或折射之目的下對基板表面施行細微凹凸加工者、或對基板表面施行遮光印刷者。Further, the transparent substrate may be a person who applies fine unevenness to the surface of the substrate for the purpose of scattering or refracting light, or a light-shielding printer for the surface of the substrate, on the premise of at least visible light transmittance.
再者,亦可使用由透明基板複數片貼合而成者、或將貼合有光學薄膜等的透明基板當作一體的透明基板來使用者。Further, it is also possible to use a transparent substrate in which a plurality of transparent substrates are bonded together or a transparent substrate to which an optical film or the like is bonded, as a whole.
再者,含有將透明基板當作構成要件其中一部分的構造體亦可使用為透明基板。此種含有將透明基板當作構成要件其中一部分的構造體具體例可如:液晶顯示裝置(LCD)、有機EL或無機EL之類的EL(電激發光)顯示裝置、電漿顯示裝置、電子墨水型影像顯示裝置之類的平面顯示器(FPD)、薄層太陽電池裝置、觸控面板等。Further, a structure including a transparent substrate as a part of the constituent elements may be used as the transparent substrate. Such a structure including a transparent substrate as a part of a constituent element may be, for example, an EL (Electro-Excise Light) display device such as a liquid crystal display device (LCD), an organic EL or an inorganic EL, a plasma display device, or an electron. A flat panel display (FPD) such as an ink type image display device, a thin-film solar cell device, a touch panel, or the like.
當一對基板中,其中一者為不透明基板時,不透明基板的具體例可如:不銹鋼等金屬材料製基板、陶瓷材料製基板、或藉由使可吸收可見光之填充劑分散於基板中而進行遮光的樹脂基板等。When one of the pair of substrates is an opaque substrate, a specific example of the opaque substrate may be a substrate made of a metal material such as stainless steel, a substrate made of a ceramic material, or a dispersion of a visible light-absorbing filler in the substrate. A light-shielded resin substrate or the like.
另外,當一對基板的雙方均為透明基板時,該一對透明基板可由相同材料形成,亦可由不同材料形成。即,一對透明基板的雙方可均為玻璃基板或透明樹脂基板,亦可一對透明基板中,其中一者為玻璃基板而另一者為透明樹脂基板。Further, when both of the pair of substrates are transparent substrates, the pair of transparent substrates may be formed of the same material or may be formed of different materials. That is, both of the pair of transparent substrates may be a glass substrate or a transparent resin substrate, and one of the pair of transparent substrates may be a glass substrate and the other may be a transparent resin substrate.
基板的厚度並無特別的限定,係透明基板的情況時,就從機械強度、透明性的觀點,玻璃基板時通常較佳為1~6mm。特別係要求厚度較薄之透明積層體的情況,玻璃基板的厚度較佳為0.3~1.5mm、更佳為0.3~1mm。又,透明樹脂板時的厚度通常係0.1~3mm。The thickness of the substrate is not particularly limited, and in the case of a transparent substrate, the glass substrate is usually preferably 1 to 6 mm from the viewpoint of mechanical strength and transparency. In particular, in the case where a transparent laminate having a small thickness is required, the thickness of the glass substrate is preferably from 0.3 to 1.5 mm, more preferably from 0.3 to 1 mm. Further, the thickness of the transparent resin sheet is usually 0.1 to 3 mm.
另一方面,不透明基板的情況,就從機械強度、薄型輕量化的觀點,通常係0.8~4mm。On the other hand, in the case of an opaque substrate, it is usually 0.8 to 4 mm from the viewpoint of mechanical strength and thinness and weight reduction.
另外,一對基板的厚度可相互相同、亦可為不同。Further, the thickness of the pair of substrates may be the same or different.
基板的表面,更具體而言,係在周邊部有形成密封部之側的表面,為提升與該密封部間之界面接著力亦可施行表面處理。此處,表面處理可僅對基板的周緣部實施,亦可對基板的表面全體實施。The surface of the substrate, more specifically, the surface on the side where the sealing portion is formed in the peripheral portion, may be subjected to a surface treatment for enhancing the interface adhesion force with the sealing portion. Here, the surface treatment may be performed only on the peripheral portion of the substrate, or may be performed on the entire surface of the substrate.
表面處理的方法係有將基板的表面利用矽烷偶合劑施行處理的方法等。The surface treatment method is a method in which the surface of the substrate is treated with a decane coupling agent or the like.
因為係在對基板上由該密封部所包圍區域供應的硬化性樹脂組成物予以擋止,之後於減壓環境下將被挾持於一對基板間並密封的硬化性樹脂組成物予以封住之目的下來設置密封部,因而在本發明積層體的製造過程中,要求對該密封部所包圍區域供應的硬化性樹脂組成物具有不會發生漏出程度以上的界面接著力,且要求在本發明積層體的製造過程中要有能維持形狀程度的堅固度。The curable resin composition supplied to the region surrounded by the sealing portion on the substrate is blocked, and then the curable resin composition held between the pair of substrates and sealed in a reduced pressure environment is sealed. In the manufacturing process of the laminated body of the present invention, it is required that the curable resin composition supplied to the region surrounded by the sealing portion has an interface adhesion force which does not occur more than the extent of leakage, and is required to be laminated in the present invention. The manufacturing process of the body should have a firmness that maintains the shape.
滿足此種要求的密封部係在其中一基板的周邊部設置表面具接著劑或黏著劑的密封構件便可形成。A sealing portion that satisfies such a requirement can be formed by providing a sealing member having a surface with an adhesive or an adhesive at a peripheral portion of one of the substrates.
此種密封構件的具體例係有如下述者。Specific examples of such a sealing member are as follows.
‧預先在表面設置黏著劑層或接著劑層的帶狀或棒狀長條體(雙面膠帶等)。‧ A strip or rod-shaped strip (double-sided tape, etc.) in which an adhesive layer or an adhesive layer is provided on the surface in advance.
‧在其中一基板表面的周緣部形成接著劑層或黏著劑層,並於其上貼附長條體者。‧ An adhesive layer or an adhesive layer is formed on the peripheral portion of one of the substrate surfaces, and a long body is attached thereto.
‧使用硬化性樹脂組成物以在其中一基板表面的周緣部,利用印刷或點膠等方式形成壩狀密封前驅體,使硬化性樹脂組成物進行硬化後,再於該表面上形成接著劑層或黏著劑層者。‧ using a curable resin composition to form a dam-shaped sealing precursor on the peripheral portion of one of the substrate surfaces by printing or dispensing, to harden the curable resin composition, and then forming an adhesive layer on the surface Or adhesive layer.
再者,將當作第2硬化性樹脂組成物的高黏度硬化性樹脂組成物,使用分配器或模具塗佈機在其中一基板的周邊部塗佈成既定厚度便可形成滿足上述要求的密封部。以下,本說明書中,為形成密封部而使用的硬化性樹脂組成物亦稱「第2硬化性樹脂組成物」。Further, a high-viscosity curable resin composition which is a second curable resin composition can be formed into a seal satisfying the above requirements by applying a predetermined thickness to a peripheral portion of one of the substrates by using a dispenser or a die coater. unit. In the present specification, the curable resin composition used to form the sealing portion is also referred to as a "second curable resin composition".
此處,第2硬化性樹脂組成物在後述的順序中,可在使被挾持於一對基板間並經密封的硬化性樹脂組成物硬化時,亦同時進行硬化,亦可在使已密封的硬化性樹脂組成物進行硬化前便硬化。另外,本發明積層體的製造方法的構成要件之一,係包括有:「在其中一基板上的周邊部上形成密封部,該密封部係用以封住硬化性樹脂組成物者」,此處的「密封部」包含硬化前的密封前驅體,其係為形成密封部而在其中一基板表面的周緣部,將硬化性樹脂組成物形成壩狀者。Here, in the order of the second curable resin composition described later, when the curable resin composition held between the pair of substrates and sealed is cured, the second curable resin composition may be cured at the same time, or may be sealed. The curable resin composition is hardened before being hardened. Further, one of the constituent elements of the method for producing a laminated body according to the present invention includes: "a sealing portion is formed on a peripheral portion of one of the substrates, and the sealing portion is for sealing a curable resin composition". The "sealing portion" at the position includes a sealing precursor before curing, which is a peripheral portion of the surface of one of the substrates on which the sealing portion is formed, and the curable resin composition is formed into a dam shape.
第2硬化性樹脂組成物係就從在對由密封部所包圍區域供應硬化性樹脂組成物時,具有能封住該樹脂膜形成用硬化性樹脂組成物的強度、當依照後述順序實施真空積層與解除減壓環境時,能配合存在於由一對基板與密封部所密封的空間內之硬化性樹脂組成物層的厚度而使該密封部變形、以及當依照後述順序實施真空積層及解除減壓環境時,密封部具有能承受大氣壓之強度的觀點,黏度較佳為200~3000Pa‧s、更佳為500~2000Pa‧s。When the curable resin composition is supplied to the region surrounded by the sealing portion, the second curable resin composition has a strength capable of sealing the curable resin composition for forming the resin film, and performs vacuum lamination in the order described later. When the pressure-reducing environment is released, the thickness of the curable resin composition layer existing in the space sealed by the pair of substrates and the sealing portion can be deformed to deform the sealing portion, and vacuum lamination and release reduction can be performed in the order described later. When the environment is pressed, the sealing portion has a strength capable of withstanding atmospheric pressure, and the viscosity is preferably 200 to 3,000 Pa s, more preferably 500 to 2,000 Å s.
此處,為能保持一對基板彼此間的間隔,亦可在第2硬化性樹脂組成物中摻入既定粒徑的間隔粒子。Here, in order to maintain the space between the pair of substrates, spacer particles having a predetermined particle diameter may be incorporated into the second curable resin composition.
另外,第2硬化性樹脂組成物係後述的光硬化性樹脂組成物,較佳係使用滿足上述黏度者。In addition, it is preferable that the second curable resin composition is a photocurable resin composition to be described later, and the above-mentioned viscosity is used.
為使對由該密封部所包圍區域供應的硬化性樹脂組成物不會漏出,密封部最好形成較由該密封部所包圍區域供應的硬化性樹脂組成物所構成之層(以下,在本說明書中,有簡稱「硬化性樹脂組成物層」的情況)的既定厚度多出若干厚度之狀態。例如較佳為硬化性樹脂組成物層既定厚度的1.1倍以上且2倍以下。In order to prevent the curable resin composition supplied to the region surrounded by the sealing portion from leaking, the sealing portion preferably forms a layer composed of a curable resin composition supplied from a region surrounded by the sealing portion (hereinafter, In the specification, there is a state in which a predetermined thickness of the "curable resin composition layer" is abbreviated to a certain thickness. For example, the curable resin composition layer is preferably 1.1 times or more and 2 times or less the predetermined thickness.
再者,密封部的寬度係依照硬化性樹脂組成物層的厚度而有所差異,較佳為0.5~5mm、0.5~3mm程度。Further, the width of the sealing portion varies depending on the thickness of the curable resin composition layer, and is preferably about 0.5 to 5 mm and about 0.5 to 3 mm.
當藉由前述黏度的第2硬化性樹脂組成物之塗佈而形成密封部時,因為在密封部形成時所使用的第2硬化性樹脂組成物係屬於高黏度,因而諸如對由密封部所包圍區域供應的硬化性樹脂組成物,在塗佈後其形狀並不會有經時變化。所以,所形成的密封部有發生部分性缺損、或密封部的寬度有部分性變細的細化情況,而該等缺點不會經時消除。因而,當所形成之密封部有發生部分性缺損或細化的情況,在依照後述順序實施真空積層前、或者在實施真空積層時,對由密封部所包圍區域供應的硬化性樹脂組成物會滲出到較該密封部更靠外側處,因而在存在於由一對基板與密封部所密閉的空間內之硬化性樹脂組成物中會有出現較大空隙的可能性。又,對由密封部所包圍區域供應的硬化性樹脂組成物滲出到較該密封部更靠外側處,便會有損及所製造之積層體式樣性的可能性。When the sealing portion is formed by the application of the second curable resin composition having the viscosity described above, since the second curable resin composition used in the formation of the sealing portion is high in viscosity, such as by the sealing portion The curable resin composition supplied in the surrounding area does not change its shape over time after coating. Therefore, the formed seal portion has a partial defect, or the width of the seal portion is partially thinned, and these defects are not eliminated over time. Therefore, when the formed sealing portion is partially defective or refinished, the curable resin composition supplied to the region surrounded by the sealing portion may be applied before the vacuum lamination is performed in the order described later or when the vacuum lamination is performed. Since it oozes to the outside of this sealing part, there exists a possibility that a large gap exists in the hardening resin composition which exists in the space enclosed by a pair of board|substrate and a sealing part. Further, when the curable resin composition supplied from the region surrounded by the sealing portion oozes to the outside of the sealing portion, the laminated body pattern to be produced may be damaged.
再者,當所形成的密封部有發生部分性缺損或細化的情況,在依照後述順序實施減壓環境解除時,氣體會侵入由一對基板與密封部所密閉的空間內,而導致存在於密閉空間內的硬化性樹脂組成物有出現較大空隙的可能性。Further, when the formed sealing portion is partially defective or refining, when the decompression environment is released in the order described later, the gas enters the space sealed by the pair of the substrate and the sealing portion, resulting in the presence of the gas. The curable resin composition in a sealed space has a possibility of occurrence of a large void.
再者,形成密封部之際,在塗佈的始終點部分發生硬化性樹脂組成物重疊的情況不會經時消除,因而當依照後述順序實施真空積層之際,密封部的厚度成為部分性不均勻情形,導致在存在於由一對基板與密封部所密閉空間內的硬化性樹脂組成物有出現較大空隙的可能性。又,因發生重疊部分的密封部寬度會變大,導致會有損及所製造之積層體式樣性的可能性。In addition, when the sealing portion is formed, the case where the curable resin composition overlaps at the point where the coating is applied is not eliminated over time. Therefore, when the vacuum lamination is performed in the order described later, the thickness of the sealing portion becomes partial. In a uniform case, there is a possibility that a large gap occurs in the curable resin composition existing in the sealed space between the pair of substrates and the sealing portion. Further, the width of the sealing portion where the overlapping portion occurs is increased, which may impair the quality of the laminated body to be produced.
所以,藉由塗佈第2硬化性樹脂組成物而形成密封部時,為能不致發生前述的問題,最好在塗佈第2硬化性樹脂組成物後,便檢查有無發生諸如部分性缺損、細化、重疊之類的缺點。但,因為依照缺點的大小,亦有不會發生上述問題的情況,因此最好檢查有無超過預定容許範圍大小的缺點。Therefore, when the sealing portion is formed by applying the second curable resin composition, it is preferable that the second curable resin composition is applied, and then it is preferable to cause partial defects such as partial defects, after the second curable resin composition is applied. Shortcomings such as refinement and overlap. However, since the above problem does not occur depending on the size of the defect, it is preferable to check whether or not there is a disadvantage that the predetermined allowable range is exceeded.
檢查方法有藉由影像處理來確認經塗佈後的硬化性樹脂組成物中所存在之缺點的尺寸之方法。The inspection method is a method of confirming the size of the defects existing in the coated curable resin composition by image processing.
其次,將硬化性樹脂組成物供應給基板上由密封部所包圍的區域。Next, the curable resin composition is supplied to the region on the substrate surrounded by the sealing portion.
硬化性樹脂組成物的供應量預先設定為當依照後述順序在一對基板間挾持硬化性樹脂組成物並加以密封時,由一對基板與密封部所密閉的空間剛好會被硬化性樹脂組成物填充的量。此時,可預先考慮因硬化性樹脂組成物的硬化收縮造成體積減少的情形之後,才決定硬化性樹脂組成物的供應量。When the curable resin composition is held between the pair of substrates in the order described below and sealed, the space sealed by the pair of substrates and the sealing portion is set to be a curable resin composition. The amount of fill. At this time, the supply amount of the curable resin composition can be determined only after the volume reduction due to the hardening shrinkage of the curable resin composition is considered in advance.
本發明積層體的製造方法中,當依照後述順序在一對基板間挾持硬化性樹脂組成物並加以密封時,存在於由一對基板與密封部所密封的空間內之硬化性樹脂組成物層的厚度最好為30~3000μm。理由係為使硬化性樹脂組成物層不僅具有當作一對基板間之接著劑的功能,且具有能對該層賦予機械強度的功能,因而需要厚度,另一方面,一般諸如開口構件或顯示構件要求為薄型輕量化,因而最好不要無端增厚。In the method for producing a laminate according to the present invention, when the curable resin composition is sandwiched between a pair of substrates and sealed in the order described later, the curable resin composition layer exists in a space sealed by the pair of substrates and the sealing portion. The thickness is preferably from 30 to 3000 μm. The reason is that the curable resin composition layer not only functions as an adhesive between a pair of substrates, but also has a function of imparting mechanical strength to the layer, and thus requires a thickness, and on the other hand, generally, such as an opening member or a display The component requirements are thin and lightweight, so it is best not to increase the thickness without any reason.
當依照後述順序在一對基板間挾持硬化性樹脂組成物並加以密封時,在由一對基板與密封部所密封的空間內存在之硬化性樹脂組成物層的厚度更佳係30~800μm、特佳係100~400μm。又,依照情況,會有硬化性樹脂組成物層厚度越薄越佳的情況,此情況,硬化性樹脂組成物層的厚度較佳係30~400μm、更佳係100~200μm、特佳係100~160μm。When the curable resin composition is held between the pair of substrates in the order described below and sealed, the thickness of the curable resin composition layer in the space sealed by the pair of substrates and the sealing portion is preferably 30 to 800 μm. The special system is 100 to 400 μm. In addition, the thickness of the curable resin composition layer may be as small as possible. In this case, the thickness of the curable resin composition layer is preferably 30 to 400 μm, more preferably 100 to 200 μm, and particularly preferably 100. ~160μm.
硬化性樹脂組成物的供應方法如將依照上述順序形成密封部的基板平放,再利用諸如分配器等供應機構呈點狀或線狀滴下而進行供應者。另外,相關硬化性樹脂組成物的具體供應順序容後呈述。The method of supplying the curable resin composition is such that the substrate on which the sealing portion is formed in the above-described order is laid flat, and then supplied by a supply mechanism such as a dispenser in a dot shape or a linear shape. Further, the specific supply sequence of the relevant curable resin composition is described later.
本發明的製造方法,相較於在預先形成的積層體間隙注入硬化性樹脂的習知方法(例如日本專利特開昭57-165411號公報、特開2001-339088號公報所記載的方法,組合於本說明書中),可使用較高黏度的硬化性樹脂組成物。藉此,可使硬化性樹脂組成物硬化時降低硬化收縮、及提升硬化後的樹脂層的機械強度。In the method of the present invention, a method of injecting a curable resin into a gap of a laminate formed in advance (for example, a method described in JP-A-57-165411, JP-A-2001-339088, In the present specification, a curable resin composition having a higher viscosity can be used. Thereby, when the curable resin composition is cured, the hardening shrinkage can be lowered, and the mechanical strength of the resin layer after curing can be improved.
所使用的樹脂膜形成用硬化性樹脂組成物之黏度,就從在工業性製造、移送、塗佈大量硬化性樹脂組成物的步驟中較容易處置之觀點,較佳係0.2~50Pa‧s。The viscosity of the curable resin composition for forming a resin film to be used is preferably from 0.2 to 50 Pa s from the viewpoint of easy handling in the steps of industrial production, transfer, and application of a large amount of the curable resin composition.
另外,此處所謂「樹脂膜形成用硬化性樹脂組成物的黏度」,係指在本發明積層體的製造方法實施時之溫度區域中的黏度,特別係在將硬化性樹脂組成物供應給由密封部所包圍區域中之後,再依照後述順序實施至真空積層的溫度區域中之黏度。例如當依常溫實施該等順序時,即為常溫下的硬化性樹脂組成物黏度。所以,雖依照實施該等順序時的溫度而有所差異,但不管何種情況均在5~80℃溫度範圍內。關於此點,上述密封部形成時所使用的第2硬化性樹脂組成物之黏度亦同。In addition, the term "viscosity of the curable resin composition for forming a resin film" as used herein means the viscosity in the temperature region at the time of carrying out the method for producing the layered product of the present invention, in particular, the supply of the curable resin composition to After the region surrounded by the sealing portion, the viscosity in the temperature region of the vacuum laminate is carried out in the order described later. For example, when the order is carried out at normal temperature, it is the viscosity of the curable resin composition at normal temperature. Therefore, although it differs according to the temperature at the time of performing these order, it is in the temperature range of 5-80 degreeC in any case. In this regard, the viscosity of the second curable resin composition used in the formation of the sealing portion is also the same.
所使用硬化性樹脂組成物的黏度較佳係1~20Pa‧s、更佳係5~20Pa。The viscosity of the curable resin composition to be used is preferably from 1 to 20 Pa s, more preferably from 5 to 20 Pa.
滿足上述黏度的硬化性樹脂組成物,係可使用含有如下述高分子量硬化性化合物(寡聚物等)的硬化性樹脂組成物。A curable resin composition containing a high molecular weight curable compound (oligomer or the like) as described below can be used as the curable resin composition satisfying the above viscosity.
因為高分子量的硬化性化合物可減少硬化性樹脂組成物中化學鍵結的數量,因而使硬化性樹脂組成物硬化時的硬化收縮情形會變小,且會提升硬化後的樹脂層的機械強度。另一方面,高分子量的硬化性化合物大多係屬於高黏性。因而,就從可確保硬化後的樹脂層的機械強度並抑制氣泡殘存的觀點,最好利用在高分子量硬化性化合物中溶解分子量較小的硬化性單體來調整黏度。可是,藉由使用分子量較小的硬化性單體,硬化性樹脂組成物的黏度雖會降低,但卻使硬化性樹脂組成物硬化時的硬化收縮情形變大,且機械強度容易降低。Since the high molecular weight curable compound can reduce the number of chemical bonds in the curable resin composition, the hardening shrinkage when the curable resin composition is cured becomes small, and the mechanical strength of the cured resin layer is enhanced. On the other hand, many high molecular weight curable compounds are highly viscous. Therefore, from the viewpoint of securing the mechanical strength of the resin layer after curing and suppressing the remaining of the bubbles, it is preferable to adjust the viscosity by dissolving the curable monomer having a small molecular weight in the high molecular weight curable compound. However, the viscosity of the curable resin composition is lowered by using a curable monomer having a small molecular weight, but the curing shrinkage at the time of curing the curable resin composition is increased, and the mechanical strength is liable to lower.
所使用的硬化性樹脂組成物最好係光硬化性樹脂組成物。光硬化性樹脂組成物相較於熱硬化性樹脂組成物,可利用較少的熱能並在短時間內硬化。所以,本發明藉由使用光硬化性樹脂組成物,便可降低製造積層體時的環境負荷。又,因為利用數份至數十份程度的光硬化性樹脂組成物便可實質的硬化,因而積層體的生產效率較高。The curable resin composition to be used is preferably a photocurable resin composition. The photocurable resin composition can be hardened in a short time by using less heat energy than the thermosetting resin composition. Therefore, in the present invention, by using the photocurable resin composition, the environmental load at the time of manufacturing the laminated body can be reduced. Further, since the photocurable resin composition can be substantially cured by using several to several tens of parts, the production efficiency of the laminated body is high.
所謂「光硬化性樹脂組成物」係指利用光的作用進行硬化而形成樹脂層的材料。光硬化性樹脂組成物係可舉例如下述物,可在硬化後的樹脂層的硬度不會過高之範圍內使用。The "photocurable resin composition" refers to a material that is cured by the action of light to form a resin layer. The photocurable resin composition is, for example, the following, and can be used in a range in which the hardness of the resin layer after curing is not excessively high.
‧含有加成聚合性不飽和基之化合物與光聚合起始劑的組成物。‧ A composition containing a compound having an addition polymerizable unsaturated group and a photopolymerization initiator.
‧依不飽和基與硫醇基的莫耳數大約相等的比例含有具1~6個不飽和基的聚烯烴化合物(三聚異氰酸三烯丙酯等)與具1~6個硫醇基的聚硫醇化合物(三乙二醇二硫醇),且含光聚合起始劑的組成物。‧ a polyolefin compound having 1 to 6 unsaturated groups (triallyl isocyanurate, etc.) and 1 to 6 thiols in a ratio approximately equal to the molar number of the thiol group A polythiol compound (triethylene glycol dithiol) having a composition of a photopolymerization initiator.
‧含有具2個以上環氧基之環氧化合物與光陽離子產生劑的組成物。‧ A composition containing an epoxy compound having two or more epoxy groups and a photocationic generator.
光硬化性樹脂組成物就從硬化速度較快速、硬化後的樹脂層透明性較高之觀點,更佳係含有具有選自由丙烯醯氧基及甲基丙烯醯氧基所構成群組中之1種以上的基(以下稱「(甲基)丙烯醯氧基」)之化合物的至少1種與光聚合起始劑。The photocurable resin composition preferably has a group selected from the group consisting of acryloxy group and methacryloxy group from the viewpoint that the curing rate is fast and the transparency of the cured resin layer is high. At least one of the above compounds (hereinafter referred to as "(meth)acryloxy)" and a photopolymerization initiator are used.
具(甲基)丙烯醯氧基的化合物(以下亦稱「(甲基)丙烯酸酯系化合物」),較佳係每1分子具有1~6個(甲基)丙烯醯氧基的化合物,就從硬化後的樹脂層不會變為過硬的觀點,更佳為每1分子具有1~3個(甲基)丙烯醯氧基的化合物。A compound having a (meth) acryloxy group (hereinafter also referred to as "(meth) acrylate compound") is preferably a compound having 1 to 6 (meth) acryloxy groups per molecule. From the viewpoint that the resin layer after curing does not become excessively hard, it is more preferably a compound having 1 to 3 (meth) acryloxy groups per molecule.
(甲基)丙烯酸酯系化合物就從硬化後的樹脂層的耐光性而言,最好係盡可能未含芳香環的脂肪族或脂環式化合物。The (meth) acrylate-based compound is preferably an aliphatic or alicyclic compound which does not contain an aromatic ring as much as possible from the light resistance of the resin layer after curing.
再者,(甲基)丙烯酸酯系化合物就從提升在與基板間之界面接著力的觀點,更佳為具羥基的化合物。在(甲基)丙烯酸酯系化合物總量中,具羥基的(甲基)丙烯酸酯系化合物的含量較佳為25質量%以上、更佳為40質量%以上。另一方面,具羥基的化合物容易導致硬化後的樹脂層彈性係數變得過高,特別係使用具羥基的(甲基)丙烯酸酯時,依照積層體的用途會有硬化後的樹脂層變得過硬的可能性。例如使用於平面顯示器(FPD)的前面板時,因為硬化後的樹脂層最好係屬於低彈性係數,因而在(甲基)丙烯酸酯系化合物總量中,具羥基的(甲基)丙烯酸酯含量較佳在40質量%以下、更佳在30質量%以下。Further, the (meth) acrylate-based compound is more preferably a compound having a hydroxyl group from the viewpoint of enhancing the adhesion force at the interface with the substrate. The content of the (meth) acrylate-based compound having a hydroxyl group in the total amount of the (meth) acrylate-based compound is preferably 25% by mass or more, and more preferably 40% by mass or more. On the other hand, a compound having a hydroxyl group tends to cause an excessively high modulus of elasticity of the resin layer after curing, and in particular, when a (meth)acrylate having a hydroxyl group is used, the resin layer after hardening becomes used depending on the use of the laminate. The possibility of being strong. For example, when used in a front panel of a flat panel display (FPD), since the resin layer after hardening is preferably a low modulus of elasticity, a hydroxyl group-containing (meth) acrylate is contained in the total amount of the (meth) acrylate compound. The content is preferably 40% by mass or less, more preferably 30% by mass or less.
再者,譬如玻璃基板與聚碳酸酯等樹脂基板的積層之異種材料製基板彼此間的積層,於不同表面能量的基板表面,為能使樹脂層對任一基板均能顯現出適當密接力,可使用呈低彈性係數之黏著態樣的樹脂層。Further, for example, a laminate of a substrate made of a different material such as a glass substrate and a resin substrate such as polycarbonate may be laminated on the surface of the substrate having different surface energies so that the resin layer can exhibit a proper adhesion to any of the substrates. A resin layer having an adhesive state of a low modulus of elasticity can be used.
另一方面,當將較薄玻璃基板與較厚玻璃基板進行積層時,藉由設置高彈性係數且薄至0.1mm以下的樹脂層,亦可提高積層體的機械強度,且此時亦可將具羥基的(甲基)丙烯酸酯含量設為60質量%以上。On the other hand, when a thin glass substrate and a thick glass substrate are laminated, the mechanical strength of the laminated body can be improved by providing a resin layer having a high modulus of elasticity and being as thin as 0.1 mm or less. The (meth) acrylate content having a hydroxyl group is set to 60% by mass or more.
(甲基)丙烯酸酯系化合物可為較低分子量的化合物(以下稱「丙烯酸酯系單體」),亦可為具重複單元的較高分子量化合物(以下稱「(甲基)丙烯酸酯系寡聚物」)。The (meth) acrylate-based compound may be a compound having a relatively low molecular weight (hereinafter referred to as "acrylate monomer"), or a compound having a higher molecular weight having a repeating unit (hereinafter referred to as "(meth) acrylate-based oligo) Polymer").
(甲基)丙烯酸酯系化合物係可舉例如:由1種以上(甲基)丙烯酸酯系單體構成者、由1種以上(甲基)丙烯酸酯系寡聚物構成者、由1種以上(甲基)丙烯酸酯系單體與1種以上(甲基)丙烯酸酯系寡聚物構成者,較佳為由1種以上丙烯酸酯系寡聚物構成者、或由1種以上丙烯酸酯系寡聚物與1種以上(甲基)丙烯酸酯系單體構成者。在提高與基板間之密接性的目的下,更佳為含有胺甲酸酯系寡聚物(其係由丙烯醯氧基與甲基丙烯醯氧基其中一者或雙方構成的硬化性官能基,在每1分子中平均具有1.8~4個)、與甲基丙烯酸羥烷基酯(其係具有羥基數1個或2個且碳數3~8的羥烷基)的硬化性樹脂組成物。The (meth) acrylate type compound may be one composed of one or more (meth) acrylate monomers, one or more (meth) acrylate oligomers, and one or more. The (meth)acrylate monomer and one or more (meth)acrylate oligomers are preferably composed of one or more acrylate oligomers or one or more acrylates. The oligomer is composed of one or more (meth)acrylate monomers. More preferably, the urethane-based oligomer (which is a curable functional group composed of one or both of an acryloxy group and a methacryloxy group) is contained for the purpose of improving the adhesion to the substrate. A curable resin composition having an average of 1.8 to 4 per molecule and a hydroxyalkyl methacrylate having a hydroxyalkyl group having 1 or 2 hydroxyl groups and 3 to 8 carbon atoms .
再者,當積層體用途係平面顯示器(FPD)的前面板時,為使硬化過程的樹脂收縮等不會對平面顯示器(FPD)的顯示性能造成不良影響,較佳係硬化後的樹脂層屬於更低彈性係數。因而,較佳係含有寡聚物(其每1分子中平均具有1.8~4個由(甲基)丙烯醯氧基構成的硬化性官能基)、羥烷基甲基丙烯酸酯(其具有羥基數1個或2個且碳數3~8的羥烷基)、以及1種以上未含羥基的(甲基)丙烯酸酯系單體之硬化性樹脂組成物。且,未具有羥基的(甲基)丙烯酸酯系單體總含量,較佳係依質量比計多於上述具羥基的(甲基)丙烯酸酯系單體含量。又,亦可取代未具羥基的(甲基)丙烯酸酯系單體,改為使用具有羥基1個且碳數12~22之羥烷基的羥烷基(甲基)丙烯酸酯羥基。Furthermore, when the use of the laminate is a front panel of a flat panel display (FPD), in order to prevent the resin shrinkage during the hardening process from adversely affecting the display performance of the flat panel display (FPD), it is preferred that the cured resin layer belongs to Lower elastic modulus. Therefore, it is preferred to contain an oligomer (having an average of 1.8 to 4 hardening functional groups composed of a (meth) acryloxy group per molecule), and a hydroxyalkyl methacrylate (having a hydroxyl group number) One or two hydroxyalkyl groups having 3 to 8 carbon atoms) and one or more curable resin compositions of a (meth) acrylate monomer having no hydroxyl group. Further, the total content of the (meth) acrylate monomer having no hydroxyl group is preferably more than the above-mentioned hydroxy group-containing (meth) acrylate monomer content. Further, instead of the (meth)acrylate monomer having no hydroxyl group, a hydroxyalkyl (meth)acrylate hydroxyl group having one hydroxyl group and a hydroxyalkyl group having 12 to 22 carbon atoms may be used instead.
(甲基)丙烯酸酯系單體係若考慮光硬化性樹脂組成物會被放置於減壓裝置內的減壓環境下,最好為具有能充分抑制揮發性程度之低蒸氣壓的化合物。當硬化性樹脂組成物含有未具羥基的(甲基)丙烯酸酯系單體時,可使用諸如:碳數8~22的(甲基)丙烯酸烷基酯、較低分子量的聚乙二醇或聚丙二醇等聚醚二醇的單(甲基)丙烯酸酯、或二(甲基)丙烯酸酯等,較佳為碳數8~22的甲基丙烯酸烷基酯。In the case where the (meth)acrylate-based single-system is placed under a reduced pressure in a decompression device, it is preferable to have a low vapor pressure which can sufficiently suppress the degree of volatility. When the curable resin composition contains a (meth) acrylate monomer having no hydroxyl group, for example, an alkyl (meth) acrylate having a carbon number of 8 to 22, a polyethylene glycol having a lower molecular weight or A mono(meth)acrylate or a di(meth)acrylate of a polyether diol such as polypropylene glycol is preferably an alkyl methacrylate having 8 to 22 carbon atoms.
(甲基)丙烯酸酯系寡聚物較佳係具有含2個以上重複單元的鏈(聚胺甲酸酯鏈、聚酯鏈、聚醚鏈、聚碳酸酯鏈等)、與(甲基)丙烯醯氧基之分子構造的(甲基)丙烯酸酯系寡聚物。該(甲基)丙烯酸酯系寡聚物係有如通稱「胺甲酸酯丙烯酸酯寡聚物」之具胺甲酸酯鍵結(通常更進一步包括聚酯鏈、聚醚鏈)、與2個以上(甲基)丙烯醯氧基的(甲基)丙烯酸酯系寡聚物。胺甲酸酯丙烯酸酯寡聚物係因為依照胺甲酸酯鏈的分子設計,可對硬化後的樹脂層的機械性能、及在與基板間之密接性等進行廣範圍調整,因而屬更佳。The (meth) acrylate-based oligomer preferably has a chain (polyurethane chain, polyester chain, polyether chain, polycarbonate chain, etc.) having two or more repeating units, and (meth) A (meth) acrylate-based oligomer having a molecular structure of propylene methoxy group. The (meth) acrylate-based oligomer has a urethane bond (generally further including a polyester chain or a polyether chain) as commonly referred to as a "urethane acrylate oligomer", and two A (meth) acrylate-based oligomer of the above (meth) acryloxy group. The urethane acrylate oligomer is preferable because it can adjust the mechanical properties of the cured resin layer and the adhesion to the substrate in a wide range according to the molecular design of the urethane chain. .
(甲基)丙烯酸酯系寡聚物的數平均分子量較佳係1000~100000、更佳係10000~70000。若數平均分子量小於1000,則會提高硬化後的樹脂層的交聯密度,導致有損及樹脂層柔軟性的可能性。反之,若數平均分子量大於100000,則會有未硬化的硬化性樹脂組成物黏度變得過大的可能性。當(甲基)丙烯酸酯系寡聚物的黏度過高時,最好併用(甲基)丙烯酸酯系單體,俾使整體硬化性樹脂組成物的黏度降低。The number average molecular weight of the (meth) acrylate-based oligomer is preferably from 1,000 to 100,000, more preferably from 10,000 to 70,000. When the number average molecular weight is less than 1,000, the crosslinking density of the resin layer after curing is increased, which may impair the flexibility of the resin layer. On the other hand, if the number average molecular weight is more than 100,000, the viscosity of the uncured curable resin composition may become excessive. When the viscosity of the (meth) acrylate-based oligomer is too high, it is preferable to use a (meth) acrylate-based monomer in combination to reduce the viscosity of the entire curable resin composition.
另一方面,當使用為密封部形成時所使用之第2硬化性樹脂組成物的情況,為能較容易將黏度調整為上述200~3000Pa‧s範圍內,最好含有具硬化性基且數平均分子量30000~100000的硬化性寡聚物的1種以上者、與具硬化性基且(甲基)丙烯酸酯系單體的1種以上者,並在寡聚物與單體的合計(100質量%)中,單體比例為15~50質量%。On the other hand, in the case where the second curable resin composition used for forming the sealing portion is used, it is preferable to adjust the viscosity to the range of 200 to 3000 Pa‧s, preferably containing a hardening group. One or more of the curable oligomers having an average molecular weight of 30,000 to 100,000, and one or more of the curable groups and the (meth)acrylate monomers, and the total of the oligomers and monomers (100) In the mass%), the monomer ratio is 15 to 50% by mass.
(甲基)丙烯酸酯系寡聚物更佳係在硬化中能提高反應性的丙烯酸酯系寡聚物。The (meth) acrylate-based oligomer is more preferably an acrylate-based oligomer capable of improving reactivity during curing.
光聚合起始劑可舉例如:苯乙酮系、酮縮醇系、苯偶姻或苯偶姻醚系、氧化膦系、二苯基酮系、噻噸酮系、醌系等光聚合起始劑,較佳為苯乙酮系或氧化膦系光聚合起始劑。當利用短波長可見光進行硬化時,就從光聚合起始劑的吸收波長帶來看,更佳為氧化膦系光聚合起始劑。藉由併用吸收波長帶不同的2種以上光聚合起始劑,便可縮短硬化時間、密封部形成時所使用之第2硬化性樹脂組成物能提高表面硬化性,因而屬更佳。The photopolymerization initiator may, for example, be an acetophenone-based, ketal-based, benzoin or benzoin ether-based, phosphine oxide-based, diphenylketone-based, thioxanthone-based or fluorene-based photopolymerization system. The initiator is preferably an acetophenone-based or phosphine oxide-based photopolymerization initiator. When hardening is performed by using short-wavelength visible light, it is more preferably a phosphine oxide-based photopolymerization initiator from the viewpoint of the absorption wavelength of the photopolymerization initiator. By using two or more kinds of photopolymerization initiators having different absorption wavelength bands in combination, the curing time can be shortened, and the second curable resin composition used in the formation of the sealing portion can be improved in surface hardenability.
光陽離子產生劑可例如鎓鹽系化合物等。The photocation generator can be, for example, a phosphonium salt compound or the like.
硬化性樹脂組成物係視必要亦可含有諸如:聚合終止劑、光硬化促進劑、鏈轉移劑、光安定劑(紫外線吸收劑、自由基捕獲劑等)、抗氧化劑、難燃化劑、接著性提升劑(矽烷偶合劑等)、顏料、染料等各種添加劑,較佳係含有聚合終止劑、光安定劑。特別係聚合終止劑含有少於聚合起始劑的量,便可改善硬化性樹脂組成物的安定性,亦可調整硬化後的樹脂層的分子量。The curable resin composition may contain, for example, a polymerization terminator, a photohardening accelerator, a chain transfer agent, a light stabilizer (ultraviolet absorber, a radical scavenger, etc.), an antioxidant, a flame retardant, and then Various additives such as a property enhancer (such as a decane coupling agent), a pigment, and a dye preferably contain a polymerization terminator and a light stabilizer. In particular, the polymerization terminator contains less than the amount of the polymerization initiator, and the stability of the curable resin composition can be improved, and the molecular weight of the resin layer after curing can be adjusted.
但,依照積層體的用途,最好避免含有會妨礙硬化後樹脂層之光線穿透可能性的添加劑。若舉一例,當積層體用途係平面顯示器(FPD)的前面板、薄層太陽電池裝置的情況,因為前者係來自形成顯示影像的平面顯示器(FPD)的射出光與反射光、後者係太陽光會穿透硬化後樹脂層,因而最好避免含有會妨礙該等光線穿透可能性的添加劑。例如紫外線吸收劑便會吸收穿透樹脂層的太陽光的紫外線成分,導致入射於薄層太陽電池裝置中的光量降低、或對平面顯示器(FPD)的顯示影像色調造成不良影響之可能性。但是,另一方面,對太陽光可穿透的樹脂層要求耐光性,特別係對紫外線等短波長光的耐久性。所以,含有紫外線吸收劑等的情況,較佳係適當調整其吸收特性、調配量等。However, depending on the use of the laminate, it is preferable to avoid the inclusion of an additive which may hinder the possibility of light penetration of the resin layer after hardening. As an example, when the laminated body is used as a front panel of a flat panel display (FPD) or a thin-film solar battery device, the former is emitted light and reflected light from a flat panel display (FPD) forming a display image, and the latter is sunlight. It will penetrate the hardened resin layer and it is therefore preferable to avoid the inclusion of additives which would impede the possibility of such light penetration. For example, the ultraviolet absorber absorbs the ultraviolet component of sunlight that penetrates the resin layer, resulting in a decrease in the amount of light incident on the thin-film solar cell device or a possibility of adversely affecting the color tone of the display image of a flat panel display (FPD). However, on the other hand, the resin layer which is transparent to sunlight is required to have light resistance, and particularly is durability against short-wavelength light such as ultraviolet rays. Therefore, in the case where an ultraviolet absorber or the like is contained, it is preferred to appropriately adjust the absorption characteristics, the blending amount, and the like.
再者,為提高與基板間之密接性、及調整硬化後樹脂層的彈性係數,較佳係含有鏈轉移劑,更佳係分子內具硫醇基的鏈轉移劑。Further, in order to improve the adhesion to the substrate and adjust the elastic modulus of the resin layer after curing, it is preferred to contain a chain transfer agent, and more preferably a chain transfer agent having a thiol group in the molecule.
聚合終止劑係可舉例如:氫醌系(2,5-二第三丁基氫醌等)、兒茶酚系(對第三丁基兒茶酚等)、蒽醌系、酚噻系、羥甲苯系等聚合終止劑。Examples of the polymerization terminator include hydroquinone (2,5-di-t-butylhydroquinone, etc.), catechol-based (for tert-butylcatechol), lanthanide, and phenolthiophene. A polymerization terminator such as a hydroxytoluene system.
光安定劑係可舉例如:紫外線吸收劑(苯并***系、二苯基酮系、水楊酸酯系等)、自由基捕獲劑(受阻胺系)等。The photosensitizer may, for example, be a UV absorber (such as a benzotriazole-based, diphenylketone-based or salicylate-based) or a radical scavenger (hindered amine-based).
抗氧化劑係可舉例如磷系、硫系的化合物。The antioxidant is, for example, a phosphorus-based or sulfur-based compound.
光聚合起始劑及各種添加劑因為硬化性樹脂組成物會被放置於減壓環境下,因此最好係分子量較大、減壓下的蒸氣壓較小之化合物。Since the photopolymerization initiator and various additives are placed under a reduced pressure environment, the curable resin composition is preferably a compound having a large molecular weight and a small vapor pressure under reduced pressure.
其次,在減壓環境下,依照上述順序對基板上由密封部所包圍區域供應的硬化性樹脂組成物上重疊另一基板。為達成此步驟,只要在其中一基板的表面中,依上述順序供應有硬化性樹脂組成物之一側的表面朝向另一基板的狀態下,使一對基板與另一基板重疊便可。藉此在一對基板間挾持硬化性樹脂組成物並加以密封。Next, in the reduced pressure environment, the other substrate is superposed on the curable resin composition supplied from the region surrounded by the sealing portion on the substrate in the above-described order. In order to achieve this step, in a state in which the surface on one side of the curable resin composition is supplied to the other substrate in the above-described order, the pair of substrates may be overlapped with the other substrate. Thereby, the curable resin composition is held between the pair of substrates and sealed.
以下,在本說明書中有將於減壓環境下,在對由密封部所包圍區域供應的硬化性樹脂組成物上重疊另一基板的順序簡稱為「真空積層」之情況。In the present specification, the order in which the other substrate is superposed on the curable resin composition supplied to the region surrounded by the sealing portion in a reduced pressure environment is simply referred to as "vacuum lamination".
本發明積層體的製造方法中,存在於其中一基板之由密封部所包圍區域中的硬化性樹脂組成物層,係在滿足下述(1)~(3)的狀態下施行真空積層。In the method for producing a laminated body of the present invention, the curable resin composition layer in the region surrounded by the sealing portion of one of the substrates is subjected to vacuum lamination in a state satisfying the following (1) to (3).
(1)存在於前述硬化性樹脂組成物層中之空隙,其投影形狀的等值圓直徑Dpore 為10mm以下。(1) The voids present in the curable resin composition layer have a contour circle diameter D pore of a projection shape of 10 mm or less.
(2)硬化性樹脂組成物層中未存在有空隙之部分,其投影形狀的等值圓直徑Dnon-pore 為40mm以下。(2) A portion where no void is present in the curable resin composition layer, and the equivalent circle diameter D non-pore of the projected shape is 40 mm or less.
(3)前述硬化性樹脂組成物層和與存在於前述硬化性樹脂組成物層中之空隙,交互地與前述密封部呈相接觸之狀態。(3) The curable resin composition layer and the void existing in the curable resin composition layer are in a state of being in contact with the sealing portion.
第2圖係基板的平面圖,在該基板10的周邊部形成密封部20,在由該密封部20所包圍的部分中形成硬化性樹脂組成物層30。在該硬化性樹脂組成物層30中均勻存在空隙40。2 is a plan view of a substrate, a sealing portion 20 is formed on a peripheral portion of the substrate 10, and a curable resin composition layer 30 is formed in a portion surrounded by the sealing portion 20. The voids 40 are uniformly present in the curable resin composition layer 30.
本發明製造方法中,存在於密封部所包圍區域中的硬化性樹脂組成物層在滿足上述(1)~(3)的狀態下施行真空積層之理由,說明如下。In the production method of the present invention, the reason why the curable resin composition layer in the region surrounded by the sealing portion is subjected to vacuum lamination in the state satisfying the above (1) to (3) will be described below.
如上述,本發明製造方法中,當對基板之由密封部所包圍區域供應硬化性樹脂組成物時,在已形成密封部的基板呈平放的狀態下,利用分配器等供應機構,將硬化性樹脂組成物呈點狀或線狀供應。當供應機構係使用分配器時,供應硬化性樹脂組成物的噴嘴形態並無特別的限定,可使用例如第8圖所示的單點噴嘴100,如第9~11圖所示的多點噴嘴(分支噴嘴)101、102、103,如第17圖所示的多點噴嘴(分支噴嘴)104中任一者。第17圖中,為形成複數的振動曲線30b,而使用多點噴嘴(分支噴嘴)104,但為形成1條粗細度較大的振動曲線,亦可使用多點噴嘴(分支噴嘴)。又,亦可在如第9~11圖所示的多點噴嘴(分支噴嘴)101、102、103,或如第17圖所示的多點噴嘴(分支噴嘴)104前端安裝狹縫噴嘴。上述所謂「單點噴嘴」係指將硬化性樹脂組成物滴下於基板上的硬化性樹脂組成物供應機構(分配器)的前端噴嘴由一個構成者;所謂「多點噴嘴」係指將硬化性樹脂組成物滴下於基板上的硬化性樹脂組成物供應機構(分配器)的前端噴嘴由複數個構成者;又所謂「分支噴嘴」係指將硬化性樹脂組成物滴下於基板上的硬化性樹脂組成物供應機構(分配器)之前端部分支為複數噴嘴者。As described above, in the manufacturing method of the present invention, when the curable resin composition is supplied to the region surrounded by the sealing portion of the substrate, the substrate having the sealing portion is laid flat, and the substrate is sealed by a supply mechanism such as a dispenser. The resin composition is supplied in a dot or a line. When the dispenser is used in the supply mechanism, the nozzle form to which the curable resin composition is supplied is not particularly limited, and for example, the single-point nozzle 100 shown in Fig. 8 can be used, and the multi-point nozzle shown in Figs. 9 to 11 can be used. (Branch nozzles) 101, 102, 103, any one of the multi-point nozzles (branch nozzles) 104 shown in Fig. 17. In Fig. 17, a multi-point nozzle (branching nozzle) 104 is used to form a plurality of vibration curves 30b, but a multi-point nozzle (branch nozzle) may be used to form one vibration curve having a large thickness. Further, a slit nozzle may be attached to the multi-point nozzles (branch nozzles) 101, 102, and 103 as shown in Figs. 9 to 11 or the tip end of the multi-point nozzle (branching nozzle) 104 as shown in Fig. 17. In the above-mentioned "single-point nozzle", the front end nozzle of the curable resin composition supply means (dispenser) in which the curable resin composition is dropped on the substrate is composed of one; the "multi-point nozzle" means hardenability. The front end nozzle of the curable resin composition supply means (dispenser) on which the resin composition is dropped on the substrate is composed of a plurality of members; the "branch nozzle" is a curable resin which drops the curable resin composition onto the substrate. The front end portion of the composition supply mechanism (dispenser) is branched into a plurality of nozzles.
第3(a)~(c)圖係對基板由密封部所包圍區域點狀分散滴下的硬化性樹脂組成物之經時變化圖。The third (a) to (c) diagrams are time-dependent changes of the curable resin composition in which the substrate is dispersed in a dot shape in a region surrounded by the sealing portion.
第3(a)圖係剛將硬化性樹脂組成物從硬化性樹脂組成物供應機構(分配器)前端的單點噴嘴點狀分散滴下後的狀態圖,在基板10由密封部20所包圍區域中,硬化性樹脂組成物30呈點狀分散。In the third (a), a state in which the curable resin composition is dropped from a single-point nozzle at the tip end of the curable resin composition supply means (dispenser), and the substrate 10 is surrounded by the sealing portion 20 In the middle, the curable resin composition 30 is dispersed in a dot shape.
硬化性樹脂組成物隨時間經過會有其形狀崩壞的情況,藉由呈點狀分散的硬化性樹脂組成物彼此間相接觸,便如第3(b)圖所示,經由在內部形成空隙40的狀態,由密封部20所包圍區域將呈面狀擴展。When the curable resin composition collapses over time, the curable resin composition dispersed in a dot shape is in contact with each other, and as shown in FIG. 3(b), a void is formed inside. In the state of 40, the area surrounded by the sealing portion 20 will expand in a planar shape.
然後,若再經過時間,空隙40便會消滅,而如第3(c)圖所示,在由密封部20所包圍區域中,硬化性樹脂組成物30呈均勻存在狀態。Then, if the elapsed time elapses, the void 40 is destroyed, and as shown in Fig. 3(c), the curable resin composition 30 is uniformly present in the region surrounded by the sealing portion 20.
本案發明者等發現當施行真空積層時,分散滴下在由密封部所包圍區域中的硬化性樹脂組成物,存在於第3(a)~(c)圖中任一狀態中,而此時的硬化性樹脂組成物狀態會對後續硬化性樹脂組成物層的狀態造成影響,更具體而言係將實施真空積層後的積層體(即在一對基板間挾持硬化性樹脂組成物層並加以密封的積層體),放置在高於減壓環境的壓力環境下之狀態時,會對硬化性樹脂組成物層中有無空隙造成影響。本案發明者等發現特別係就該積層體放置在高於減壓環境的壓力環境之狀態下空隙會消失的觀點,相較於第3(c)圖的狀態之下,乍看雖較佳於第3(b)圖,但並非如此,而是如第3(b)圖,最好在有存在某特定尺寸空隙的狀態下實施真空積層之事。The inventors of the present invention found that when the vacuum laminate is applied, the curable resin composition which is dispersed and dropped in the region surrounded by the sealing portion exists in any of the states (3) to (c), and at this time, The state of the curable resin composition affects the state of the subsequent curable resin composition layer, and more specifically, the laminated body after vacuum lamination (that is, the curable resin composition layer is sandwiched between a pair of substrates and sealed When it is placed in a pressure environment higher than a reduced pressure environment, it affects the presence or absence of voids in the curable resin composition layer. The inventors of the present invention have found that the voids disappear in a state in which the laminated body is placed in a pressure environment higher than a reduced pressure environment, and it is preferable to look at the state in the third (c) state. Fig. 3(b), but not the case, but as shown in Fig. 3(b), it is preferable to carry out vacuum lamination in the presence of a certain size of void.
雖後有詳述,經真空積層實施後的積層體被放置於較經實施真空積層過的減壓環境更高之壓力環境下(例如大氣壓下。本說明書中,實施真空積層的減壓環境的下一步驟,即高於前述減壓環境之壓力環境下,與上述減壓環境相比,稱為「第2壓力環境下」)(以下,本說明書中,有將該順序稱「解除減壓環境」的情況)。藉由解除減壓環境而造成的環境壓力上升,朝一對基板彼此間相密接的方向按押,同時殘留在硬化性樹脂組成物層中的空隙體積會配合該環境的差壓而縮減,藉此由一對基板與密封部所密閉的密閉空間整體便利用硬化性樹脂組成物而被均勻填充。另外,前述真空積層實施後的積層體係由2片基體及密封部所密封的樹脂層形成用硬化性樹脂組成物呈尚未硬化狀態者,此便是所謂的「積層體前驅體」,本說明書中,亦有將包括樹脂層形成用硬化性樹脂組成物尚未硬化的積層狀態物、及樹脂層形成用組成物已呈硬化狀態物在內稱為「積層體」。Although detailed later, the laminated body after the vacuum lamination is placed under a higher pressure environment than the vacuum-decompressed pressure-reduced environment (for example, at atmospheric pressure. In the present specification, the vacuum-decomposed environment is implemented. In the next step, that is, in a pressure environment higher than the above-described decompression environment, it is referred to as "in the second pressure environment" as compared with the above-described decompression environment (hereinafter, in the present specification, the order is referred to as "decompression". The situation of the environment). By increasing the environmental pressure caused by the release of the decompression environment, the pair of substrates are pressed in the direction in which they are in close contact with each other, and the void volume remaining in the curable resin composition layer is reduced by the differential pressure of the environment. The entire sealed space sealed by the pair of substrates and the sealing portion is uniformly filled with the curable resin composition. In addition, in the laminated system after the vacuum lamination is performed, the curable resin composition for forming a resin layer sealed by the two substrates and the sealing portion is not yet cured, and this is a so-called "layer precursor". In addition, a layered state material in which the curable resin composition for forming a resin layer is not cured, and a material in which the resin layer forming composition is cured is also referred to as a "layered body".
然而,根據施行真空積層時硬化性樹脂組成物的狀態,並無法充分發揮因解除減壓環境所造成的上述作用,在減壓環境解除後的硬化性樹脂組成物層中會有空隙殘存。關於此點,參照第4~6圖進行說明。However, depending on the state of the curable resin composition at the time of performing the vacuum lamination, the above-described action due to the release of the decompression environment cannot be sufficiently exhibited, and voids remain in the curable resin composition layer after the decompression environment is released. This point will be described with reference to Figs. 4 to 6 .
第4(a)~(d)圖係硬化性樹脂組成物在第3(a)圖所示狀態時施行真空積層的情況下,真空積層時及解除減壓環境後的硬化性樹脂組成物狀態圖,第4(a)圖相當於第3(a)圖。但,省略在基板周邊部形成的密封部。針對此點,在第4(b)~(d)圖及後示的第5,6圖中亦同。第4(b)圖係真空積層實施時的硬化性樹脂組成物狀態圖,第4(c)、(d)圖係減壓環境解除後的硬化性樹脂組成物狀態圖,顯示減壓環境解除後的硬化性樹脂組成物狀態之經時變化。In the case where the vacuum-curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3(a), the state of the curable resin composition after vacuum lamination and after the decompression environment is released is shown in the fourth (a) to (d). Fig. 4(a) corresponds to Fig. 3(a). However, the sealing portion formed at the peripheral portion of the substrate is omitted. This point is also the same in the fourth (b) to (d) and the fifth and sixth figures which will be described later. 4(b) is a state diagram of a curable resin composition when vacuum lamination is performed, and 4(c) and (d) are diagrams showing a state of a curable resin composition after the decompression environment is released, showing that the decompression environment is released. The state of the subsequent curable resin composition changes over time.
如第4(a)圖所示,當硬化性樹脂組成物30在基板10上點狀分散的狀態下實施真空積層時,如第4(b)圖所示,藉由呈點狀分散的硬化性樹脂組成物30彼此間相接觸,該硬化性樹脂組成物便在基板10上呈面狀擴展。但,在面上擴展的硬化性樹脂組成物30之層中,除呈均勻分散的小空隙40之外,尚有無規則存在的大空隙41。As shown in Fig. 4(a), when the curable resin composition 30 is vacuum-laminated in a state where the substrate 10 is dot-dispersed, as shown in Fig. 4(b), it is hardened by a dot-like dispersion. The resin compositions 30 are in contact with each other, and the curable resin composition spreads in a planar shape on the substrate 10. However, in the layer of the curable resin composition 30 which spreads on the surface, in addition to the uniformly dispersed small voids 40, there are irregular voids 41 which are irregularly present.
如第4(c)、(d)圖所示,減壓環境解除後,存在於硬化性樹脂組成物30之層中的空隙40,41會經時地縮小,但無規則存在的大空隙41卻不會消除而係殘存於該層中的狀態。空隙殘存的狀態不僅只有第4~6圖所記載之狀態而已,尚有各種狀態。As shown in the fourth (c) and (d), after the pressure reduction environment is released, the voids 40, 41 existing in the layer of the curable resin composition 30 are reduced over time, but the large gaps 41 are irregularly present. It does not eliminate and remains in the state of the layer. The state in which the void remains is not only the state described in the fourth to sixth figures, but also various states.
第5(a)~(d)圖係當在硬化性樹脂組成物呈第3(b)圖所示狀態下施行真空積層時,真空積層時及減壓環境後的硬化性樹脂組成物狀態圖,第5(a)圖係圖中的硬化性樹脂組成物與空隙間之關係多少有些差異,但相當於第3(b)圖。第5(b)圖係真空積層實施時的硬化性樹脂組成物狀態圖,第5(c)、(d)圖係減壓環境解除後的硬化性樹脂組成物狀態圖,經減壓環境解除後的硬化性樹脂組成物狀態之經時變化。In the fifth (a) to (d), when the vacuum resin composition is subjected to vacuum lamination in the state shown in Fig. 3(b), the state of the curable resin composition after vacuum lamination and after a reduced pressure environment is shown. The relationship between the curable resin composition in the figure (5) and the void is somewhat different, but corresponds to the third (b) diagram. Fig. 5(b) is a state diagram of the curable resin composition at the time of the vacuum lamination, and the fifth (c) and (d) are diagrams showing the state of the curable resin after the decompression environment is released, and are relieved by the reduced pressure environment. The state of the subsequent curable resin composition changes over time.
如第5(a)圖所示,在存在於硬化性樹脂組成物30之層中之空隙40均較小,且空隙40彼此間的間距為較小狀態下,依均勻存在於該層中的狀態實施真空積層時,便如第5(b)圖所示,在真空積層實施前後,硬化性樹脂組成物狀態並未有如何的變化,但如第5(c)圖所示,藉由解除減壓環境,存在於硬化性樹脂組成物30之層中的空隙40會縮小,然後,如第5(d)圖所示,存在於層中的空隙會消除。As shown in Fig. 5(a), the voids 40 present in the layer of the curable resin composition 30 are small, and the gaps 40 are relatively small, and are uniformly present in the layer. When the vacuum lamination is performed in the state, as shown in Fig. 5(b), the state of the curable resin composition does not change before and after the vacuum lamination, but as shown in Fig. 5(c), In the reduced pressure environment, the voids 40 present in the layer of the curable resin composition 30 are reduced, and then, as shown in Fig. 5(d), the voids present in the layer are eliminated.
第6(a)~(d)圖係硬化性樹脂組成物在第3(c)圖所示狀態時施行真空積層的情況下,真空積層時及減壓環境解除後的硬化性樹脂組成物狀態圖,第6(a)圖係相當於第3(c)圖。第6(b)圖係真空積層實施時的硬化性樹脂組成物狀態圖,第6(c)、(d)圖係減壓環境解除後的硬化性樹脂組成物狀態圖,減壓環境解除後的硬化性樹脂組成物狀態之經時變化。In the case where the vacuum-hardened resin composition is subjected to vacuum lamination in the state shown in Fig. 3(c), the state of the curable resin composition after vacuum lamination and after the decompression environment is released is shown in Fig. 6(a) to (d). Fig. 6(a) is equivalent to Fig. 3(c). 6(b) is a state diagram of a curable resin composition when vacuum lamination is performed, and 6th (c) and (d) are diagrams showing a state of a curable resin composition after the decompression environment is released, and after the decompression environment is removed, The state of the curable resin composition changes over time.
如第6(a)圖所示,當基板10上的硬化性樹脂組成物30並未形成空隙而呈均勻存在之狀態下實施真空積層時,便如第6(b)圖所示,藉由實施真空積層而沿硬化性樹脂組成物30之層的外緣形成大空隙41。此種大空隙41係如第6(c)、(d)圖所示,減壓環境解除後雖會經時的縮小,但呈未消除而殘存於該層中的狀態。As shown in Fig. 6(a), when the hardened resin composition 30 on the substrate 10 is formed into a uniform state without forming a void, as shown in Fig. 6(b), The vacuum lamination is performed to form a large void 41 along the outer edge of the layer of the curable resin composition 30. As shown in the sixth (c) and (d), the large gap 41 is in a state in which the reduced pressure environment is reduced over time, but remains in the layer without being eliminated.
本發明的製造方法中,使用黏度為0.2~50Pa‧s的較高黏度樹脂膜形成用硬化性樹脂組成物,且形成在由密封部所包圍區域中的硬化性樹脂組成物層厚度亦達30μm以上之相對來說較厚狀態,因此在減壓環境解除後的硬化性樹脂組成物層中容易有殘存空隙的傾向。所以,針對此現象,在滿足上述(1)~(3)的狀態下實施真空積層,對不致在減壓環境解除後的硬化性樹脂組成物層中殘存空隙來說係屬重要。In the production method of the present invention, a curable resin composition for forming a high-viscosity resin film having a viscosity of 0.2 to 50 Pa‧s is used, and the thickness of the curable resin composition layer formed in the region surrounded by the sealing portion is also 30 μm. Since the above is relatively thick, it tends to have voids remaining in the curable resin composition layer after the pressure reduction environment is released. Therefore, in this state, it is important to carry out vacuum lamination in a state in which the above (1) to (3) are satisfied, and it is important that no void remains in the curable resin composition layer after the decompression environment is released.
若硬化性樹脂組成物層滿足上述(1)~(3),包含與密封部20間之界面的硬化性樹脂組成物30之層全體,在存在於硬化性樹脂組成物30之層中的空隙40均較小,且空隙40彼此間的間距為較小的狀態下,呈均勻存在於該層中的狀態。所以,藉由實施真空積層,然後解除減壓環境,便可使存在於硬化性樹脂組成物30之層中的空隙縮小並消除。When the curable resin composition layer satisfies the above (1) to (3), the entire layer of the curable resin composition 30 including the interface with the sealing portion 20 is present in the voids in the layer of the curable resin composition 30. 40 is small, and in a state where the gaps between the gaps 40 are small, they are uniformly present in the layer. Therefore, by performing vacuum lamination and then releasing the decompression environment, the voids existing in the layer of the curable resin composition 30 can be reduced and eliminated.
上述(1)、(2)中,所謂「存在於硬化性樹脂組成物層中之空隙的投影形狀」及「硬化性樹脂組成物層中未存在有空隙之部分的投影形狀」,係指空隙對硬化性樹脂組成物層表面的投影形狀、及未存在空隙的部分對該層表面的投影形狀。以下,本說明書中,將空隙投影形狀的等值圓直徑,簡稱「空隙的等值圓直徑」,將未存在空隙部分的投影形狀之等值圓直徑,簡稱「未存在空隙部分的等值圓直徑」。In the above (1) and (2), the "projection shape of the voids present in the curable resin composition layer" and the "projection shape of the portion where the voids are not present in the curable resin composition layer" means voids. The projected shape of the surface of the curable resin composition layer and the projected shape of the portion where the void is not present on the surface of the layer. Hereinafter, in the present specification, the equivalence circle diameter of the void projection shape is simply referred to as "the equivalence circle diameter of the void", and the equivalence circle diameter of the projection shape in which the void portion is not present is simply referred to as "the equivalence circle in which the void portion is not present". diameter".
另外,上述(1)係指存在於硬化性樹脂組成物層中的所有空隙,其投影形狀的等值圓直徑Dpore 在10mm以下。又,上述(2)係指存在於硬化性樹脂組成物層中的所有未存在空隙部分,其投影形狀的等值圓直徑Dnon-pore 在40mm以下。Further, the above (1) means all the voids present in the curable resin composition layer, and the projected shape has an equivalence circle diameter D pore of 10 mm or less. Further, the above (2) means all the void-free portions present in the curable resin composition layer, and the equivalence circle diameter D non-pore of the projected shape is 40 mm or less.
第2圖係使用硬化性樹脂組成物供應機構(分配器)的單點噴嘴,將硬化性樹脂組成物呈點狀滴下於基板上之後的硬化性樹脂組成物狀態圖,同圖中,Dnon-pore 係指「未存在空隙部分的等值圓直徑」,Dpore 係指「空隙的等值圓直徑」。2 is a state diagram of a curable resin composition in which a curable resin composition is dropped onto a substrate in a dot shape using a single-point nozzle of a curable resin composition supply means (dispenser), and in the same figure, D non -pore means "equal diameter of the void portion", and D pore means "equal diameter of the void".
再者,第15圖係使用硬化性樹脂組成物供應機構(分配器)的列狀多點噴嘴,一邊使多點噴嘴進行擺動,一邊將硬化性樹脂組成物呈線狀滴下於基板上之後的硬化性樹脂組成物狀態圖,同圖中,Dnon-pore 係指「未存在空隙部分的等值圓直徑」,Dpore 係指「空隙的等值圓直徑」。另外,上述所謂「等值圓」並不僅侷限於圓形狀,廣泛涵蓋其中一部分為圓形、橢圓形、曲面形狀的各種形狀。當非為圓形狀時,該形狀之等值圓直徑係指其長軸、短軸中,長軸與短軸的平均直徑。In addition, the fifteenth figure is a column-shaped multi-point nozzle which uses a curable resin composition supply means (dispenser), and after the multi-point nozzle is swung, the curable resin composition is dropped onto the substrate in a linear form. In the figure of the composition of the curable resin, in the same figure, D non-pore means "equivalent circle diameter in which no void portion exists", and D pore means "equal diameter of void". Further, the above-mentioned "equivalent circle" is not limited to a circular shape, and various shapes including a circular shape, an elliptical shape, and a curved surface shape are widely encompassed. When it is not a circular shape, the equivalent circle diameter of the shape refers to the average diameter of the major axis, the minor axis, and the major axis and the minor axis.
當硬化性樹脂組成物層未滿足上述(1)的情況,因為在硬化性樹脂組成物30之層中存在有較大空隙,因此即便實施真空積層,然後再解除減壓環境,仍無法使存在於硬化性樹脂組成物的層中之空隙消除,而呈在該層中仍殘存空隙的狀態。When the curable resin composition layer does not satisfy the above (1), since a large void exists in the layer of the curable resin composition 30, even if vacuum lamination is performed and then the decompression environment is released, the existence cannot be made. The voids in the layer of the curable resin composition are eliminated, and a state in which voids remain in the layer remains.
本發明製造方法中,存在於硬化性樹脂組成物層中的空隙,其投影形狀的等值圓直徑Dpore 較佳係3mm以下。In the production method of the present invention, the voids present in the curable resin composition layer have a contour circle diameter D pore of a projection shape of preferably 3 mm or less.
當硬化性樹脂組成物層未滿足上述(2)的情況,因為存在於硬化性樹脂組成物30之層中的空隙40彼此間之間距較大,及/或因為空隙40在該層中呈不均勻存在,因而即便實施真空積層,然後再解除減壓環境,仍無法使在硬化性樹脂組成物層中存在的空隙消除,而呈在該層中仍殘存空隙的狀態。When the curable resin composition layer does not satisfy the above condition (2), since the voids 40 present in the layer of the curable resin composition 30 are large from each other, and/or because the void 40 does not exist in the layer Since it is evenly distributed, even if the vacuum layer is applied and the pressure-reduced environment is released, the voids existing in the curable resin composition layer cannot be eliminated, and the voids remain in the layer.
本發明製造方法中,硬化性樹脂組成物層中未存在有空隙之部分,其投影形狀的等值圓直徑Dnon-pore 較佳係15mm以下。In the production method of the present invention, the portion of the curable resin composition layer where no void is present, and the equivalence circle diameter D non-pore of the projected shape is preferably 15 mm or less.
當硬化性樹脂組成物層未滿足上述(3)的情況時,硬化性樹脂組成物層經常與密封部呈接觸狀態、或空隙經常與密封部呈接觸狀態。前者的情況,如使用第6(a)~(d)圖進行說明,藉由實施真空積層,沿硬化性樹脂組成物30之層的外緣形成大空隙41。此種大空隙並無法利用減壓環境的解除而消除,呈現在該層中仍殘存空隙的狀態。後者的情況,在實施真空積層時,沿硬化性樹脂組成物層之外緣存在有大空隙,因此即便實施真空積層,然後再解除減壓環境,仍無法使存在於硬化性樹脂組成物層中的空隙消除,而呈現在該層中仍殘存空隙的狀態。When the curable resin composition layer does not satisfy the above (3), the curable resin composition layer is often in contact with the sealing portion, or the void is often in contact with the sealing portion. In the former case, as described with reference to FIGS. 6(a) to 6(d), a large gap 41 is formed along the outer edge of the layer of the curable resin composition 30 by performing vacuum lamination. Such a large gap cannot be eliminated by the release of the reduced pressure environment, and a state in which a void remains in the layer is exhibited. In the latter case, when the vacuum laminate is applied, a large gap exists along the outer edge of the curable resin composition layer. Therefore, even if vacuum deposition is performed and then the pressure reduction environment is released, the presence of the curable resin composition layer cannot be caused. The voids are eliminated, and a state in which voids remain in the layer is present.
本發明製造方法中,為在滿足上述(1)~(3)的狀態下實施真空積層,只要依以下順序實施如使用分配器將硬化性樹脂組成物分散滴下的順序便可。In the production method of the present invention, in order to carry out the vacuum lamination in a state in which the above (1) to (3) are satisfied, the order in which the curable resin composition is dispersed and dropped by using a dispenser may be carried out in the following order.
在基板由密封部所包圍區域中呈點狀分散滴下的硬化性樹脂組成物,係從分散滴下後經過時間t,其狀態便如第7(a)~(e)圖所示進行變化。此處,第7(a)圖係剛將硬化性樹脂組成物30分散滴下於基板10由密封部20所包圍區域後(即t=0)的狀態圖,而在由該密封部20所包圍區域中,硬化性樹脂組成物30呈點狀分散。然後,藉由呈點狀分散的硬化性樹脂組成物30彼此間相接觸,便如第7(b)圖所示,硬化性樹脂組成物30在由密封部20所包圍區域中擴展為面狀,在從分散滴下起經過時間t1 的時點於硬化性樹脂組成物30層中形成空隙40。然後,空隙40係經時的變小,在從分散滴下起經過時間t2 的時點,如第7(c)圖所示,該空隙40的等值圓直徑D1 呈滿足上述(1)的狀態,即成為Dpore =10mm。然後,空隙40再更進一步經時的變小,在從分散滴下起經過時間t3 的時點,如第7(d),(e)圖所示,空隙40將消除。時間t2 係依照基板的大小而有所差異,但較佳為30~1800秒、50~1000秒程度。The curable resin composition in which the substrate is dispersed in a dot shape in a region surrounded by the sealing portion is changed from the time t after the dispersion and the time t, and the state is changed as shown in the seventh (a) to (e). Here, the seventh (a) is a state in which the curable resin composition 30 is dispersed and dropped on the region surrounded by the sealing portion 20 (that is, t=0), and is surrounded by the sealing portion 20. In the region, the curable resin composition 30 is dispersed in a dot shape. Then, the curable resin composition 30 which is dispersed in a dot shape is in contact with each other, and as shown in Fig. 7(b), the curable resin composition 30 is expanded into a planar shape in a region surrounded by the sealing portion 20. in dropping from the time point t 1 dispersed in curable resin layer 40 to form voids 30 in the elapsed time. Then, the void 40 becomes smaller as time passes, and as the time t 2 elapses from the dispersion dripping, as shown in Fig. 7(c), the equivalence circle diameter D 1 of the void 40 satisfies the above (1). State, that is, D pore = 10mm. Then, the gap 40 becomes smaller again by a further, in dropping point elapsed from the time t 3 the dispersion, such as section 7 (d), (e) shown in FIG, 40 will eliminate the void. The time t 2 varies depending on the size of the substrate, but is preferably about 30 to 1800 seconds and 50 to 1000 seconds.
當使用具有配合硬化性樹脂組成物滴下部位數量之噴嘴的分配器,將硬化性樹脂組成物對既定區域統括滴下時,只要在依下式所示之時間t範圍內實施減壓積層便可。When a dispenser having a nozzle having a number of dropping portions of the curable resin composition is used, when the curable resin composition is dropped onto a predetermined region, the pressure-reducing layer may be applied in the range of time t shown by the following formula.
t2 ≦t≦t3 t 2 ≦t≦t 3
但,依照基板的尺寸,並無法實現統括滴下硬化性樹脂組成物,如第8圖所示,一邊使噴嘴100在基板10由密封部20所包圍區域上進行移動,一邊滴下硬化性樹脂組成物30。此情況,從滴下開始起至滴下結束為止發生時間差的結果,依照施行滴下的時期,硬化性樹脂組成物的形狀會變為不同狀態,結果會有存在於硬化性樹脂組成物30之層中的空隙40,其等值圓直徑Dpore 變為不均勻的問題。However, according to the size of the substrate, it is not possible to realize the dripping curable resin composition, and as shown in Fig. 8, the nozzle 100 is dropped while the substrate 10 is moved by the region surrounded by the sealing portion 20, and the curable resin composition is dropped. 30. In this case, as a result of the time difference from the start of the dropping to the end of the dropping, the shape of the curable resin composition is changed depending on the period of the dropping, and as a result, it may be present in the layer of the curable resin composition 30. The void 40 has a problem that the equivalence circle diameter D pore becomes uneven.
當取代第8圖所示單點噴嘴100,改為使用如第9、10圖所示之多點噴嘴(分支噴嘴)101、102時,因為從滴下開始起至滴下結束所需時間會縮短,因而可緩和上述問題,但並無法完全解決問題。When the single-point nozzle 100 shown in Fig. 8 is used instead of the multi-point nozzles (branch nozzles) 101 and 102 as shown in Figs. 9, 10, the time required from the start of the dropping to the end of the dropping is shortened. Therefore, the above problems can be alleviated, but the problem cannot be completely solved.
所以,如第8~10圖所示,當在基板10由密封部20所包圍區域上,一邊使噴嘴100、101、102進行移動,一邊滴下硬化性樹脂組成物30時,在由密封部20所包圍的全區域中,必需注意要滿足上述(1)~(3)。具體而言,必需在從最初滴下起t3 以內且從最後滴下起t2 以上的時間內實施真空積層。為此便必需將滴下條件設定成從滴下開始起至滴下結束的所需時間ts為滿足下式:Therefore, as shown in FIGS. 8 to 10, when the curable resin composition 30 is dropped while the nozzles 100, 101, and 102 are moved while the substrate 10 is surrounded by the sealing portion 20, the sealing portion 20 is formed by the sealing portion 20. In the entire area enclosed, it is necessary to pay attention to satisfying the above (1) to (3). Specifically, it is necessary to carry out vacuum lamination in a time period from the initial dropping to t 3 and from the last dropping to t 2 or more. For this purpose, it is necessary to set the dropping condition so that the required time ts from the start of the dropping to the end of the dropping is satisfied by the following formula:
ts <(t3 -t2 )t s <(t 3 -t 2 )
當在基板由密封部所包圍區域上,一邊使噴嘴進行移動,一邊滴下硬化性樹脂組成物時所發生的上述問題,藉由配合滴下時期,強制性改變所滴下的硬化性樹脂組成物的形狀,更具體而言,強制性擴展硬化性樹脂組成物的投影形狀的等值圓直徑(以下在本說明書簡稱「硬化性樹脂組成物的等值圓直徑」),便可解決上述問題。In the above-mentioned problem that occurs when the curable resin composition is dropped while the nozzle is moved by the nozzle, the shape of the curable resin composition to be dropped is forcibly changed by the dripping period. More specifically, the above-mentioned problem can be solved by the equivalent circle diameter of the projected shape of the mandatory expansion-curable resin composition (hereinafter referred to as "the equivalent circle diameter of the curable resin composition" in the present specification).
如第11圖所示,當在基板10由密封部20所包圍區域上,一邊使多點噴嘴(分支噴嘴)103進行移動,一邊滴下硬化性樹脂組成物30時,依照進行滴下的時期,硬化性樹脂組成物的形狀可呈不同的狀態。當著眼於硬化性樹脂組成物的等值圓直徑時,在較早階段滴下的硬化性樹脂組成物,相較於在較晚階段滴下的硬化性樹脂組成物,等值圓直徑會變大。因為基板10係具有各種大小,因此就準備能滴下於基板整面的噴嘴而言,在成本面上較為困難,因而多數情況係使用多點噴嘴。As shown in Fig. 11, when the multi-point nozzle (branch nozzle) 103 is moved while the multi-point nozzle (branch nozzle) 103 is moved, the hard resin composition 30 is dropped, and the hardening is performed in accordance with the period of dropping. The shape of the resin composition may be in a different state. When focusing on the equivalence circle diameter of the curable resin composition, the curable resin composition dropped at an earlier stage becomes larger in diameter than the curable resin composition dropped at a later stage. Since the substrate 10 has various sizes, it is difficult to prepare a nozzle that can be dropped on the entire surface of the substrate on the cost side, and therefore, a multi-point nozzle is often used.
相對於此,藉由強制性擴展在較晚階段滴下的硬化性樹脂組成物之等值圓直徑,便可縮小因滴下時期所造成的硬化性樹脂組成物之等值圓直徑的差,更甚者亦可使已滴下的硬化性樹脂組成物的等值圓直徑呈均勻。第12圖中,藉由強制性擴展在較晚階段滴下的硬化性樹脂組成物之等值圓直徑,便可使存在於基板10由密封部20所包圍區域中的硬化性樹脂組成物30之等值圓直徑均勻。On the other hand, by forcibly expanding the equivalence circle diameter of the curable resin composition dropped at a later stage, the difference in the equivalence circle diameter of the curable resin composition due to the dropping period can be reduced, and even more It is also possible to make the equivalence circle diameter of the dripped curable resin composition uniform. In Fig. 12, the curable resin composition 30 existing in the region surrounded by the sealing portion 20 of the substrate 10 can be made by forcibly expanding the equivalence circle diameter of the curable resin composition dropped at a later stage. The contour circle has a uniform diameter.
強制性擴展已滴下的硬化性樹脂組成物之等值圓直徑的方法,如第12圖中箭頭所示,藉由使基板10與多點噴嘴(分支噴嘴)103進行相對性擺動,而強制性擴展硬化性樹脂組成物的等值圓直徑之方法。此情況,亦可使基板10進行擺動,亦可使多點噴嘴(分支噴嘴)103進行擺動。又,藉由使滴下後的硬化性樹脂組成物接觸到諸如攪拌子等任何突起物,亦可強制性擴展硬化性樹脂組成物的等值圓直徑。The method of forcibly expanding the equivalence circle diameter of the hardened resin composition that has been dropped, as shown by the arrow in Fig. 12, is mandatory by causing the substrate 10 to be relatively oscillated with the multi-point nozzle (branching nozzle) 103. A method of expanding the equivalent circle diameter of a curable resin composition. In this case, the substrate 10 may be oscillated, or the multi-point nozzle (branch nozzle) 103 may be oscillated. Further, by bringing the curable resin composition after the dropping into contact with any projection such as a stirrer, it is possible to forcibly expand the equivalence circle diameter of the curable resin composition.
已滴下的硬化性樹脂組成物之等值圓直徑要擴展為何種程度,只要依循以下的想法後再實施便可。The extent to which the equivalence circle diameter of the hardened resin composition that has been dropped is expanded can be carried out by following the following ideas.
第13圖係當滴下某硬化性樹脂組成物時,在所滴下的時點(即t=0)硬化性樹脂組成物之等值圓直徑為d0 時,滴下後的經過時間t(sec)與該硬化性樹脂組成物的等值圓直徑d(mm)間之關係圖。如該圖所示,在從開始滴下起經過時間ta 、tb 、tn 時所滴下之硬化性樹脂組成物,藉由分別將該硬化性樹脂組成物的等值圓直徑擴展為da 、db 、dn ,便可使滴下完成時的硬化性樹脂組成物之等值圓直徑呈均勻。Fig. 13 is a graph showing the elapsed time t (sec) after dropping, when a certain curable resin composition is dropped, at the time point (i.e., t = 0), the equivalence circle diameter of the curable resin composition is d 0 . A graph showing the relationship between the equivalence circle diameter d (mm) of the curable resin composition. As shown in the figure, the curable resin composition which has been dropped when the time t a , t b , and t n have elapsed from the start of the dripping, is expanded by the equivalence circle diameter of the curable resin composition to d a Further, d b and d n can make the equivalent circle diameter of the curable resin composition at the time of completion of the dropping uniform.
本案發明者等經實驗性確認到滴下後的經過時間t與該硬化性樹脂組成物的等值圓直徑d的增量(d-d0)之間,成立下式關係:The inventors of the present invention experimentally confirmed that the elapsed time t after the dropping and the increment (d-d0) of the equivalence circle diameter d of the curable resin composition establish the following relationship:
d-d0 =α×t1/2 Dd 0 =α×t 1/2
式中,α係依照硬化性樹脂組成物的黏性、基板表面對硬化性樹脂組成物的濕潤性、已滴下的各個硬化性樹脂組成物的體積而決定之係數。In the formula, α is a coefficient determined by the viscosity of the curable resin composition, the wettability of the substrate surface to the curable resin composition, and the volume of each of the curable resin compositions that have been dropped.
根據該式,藉由將所滴下的硬化性樹脂組成物之等值圓直徑設為何種程度擴展,便可使滴下完成時的硬化性樹脂組成物之等值圓直徑呈均勻。另外,藉由使基板10與噴嘴103進行相對性擺動,當擴展已滴下的硬化性樹脂組成物之等值圓直徑時,只要將擺動的振幅S設為依上式所求得之等值圓直徑d的增量(d-d0 )便可。According to this formula, by expanding the diameter of the equivalence circle of the hardened resin composition to be dropped, the equivalence circle diameter of the curable resin composition at the time of completion of the dropping can be made uniform. Further, when the substrate 10 and the nozzle 103 are relatively oscillated, when the equi-circular diameter of the deposited curable resin composition is expanded, the amplitude S of the wobble is set to the equivalent circle obtained by the above formula. The increment of diameter d (dd 0 ) can be.
滴下後的經過時間t、硬化性樹脂組成物的等值圓直徑d、及存在於硬化性樹脂組成物層中之空隙的等值圓直徑Dpore 間之關係將進一步敘述。The relationship between the elapsed time t after the dropping, the equivalence circle diameter d of the curable resin composition, and the equivalence circle diameter D pore of the voids present in the curable resin composition layer will be further described.
第14圖係滴下後的經過時間t、硬化性樹脂組成物的等值圓直徑d、及存在於硬化性樹脂組成物層中之空隙的等值圓直徑Dpore 間之關係圖。由圖中得知,隨著滴下後的經過時間t之增加,硬化性樹脂組成物的等值圓直徑d亦會增加,而空隙的等值圓直徑Dpore 則會減少。圖形中的t1 、t2 及t3 係與第7圖同義。即,在從分散滴下起經過時間t1 時,在硬化性樹脂組成物30的層中形成空隙40,在經過時間t2 時,該空隙40的等值圓直徑Dpore =10mm,在經過時間t3 時,空隙40會消除。Fig. 14 is a graph showing the relationship between the elapsed time t after dropping, the equivalence circle diameter d of the curable resin composition, and the equivalence circle diameter D pore of the voids present in the curable resin composition layer. As is apparent from the figure, as the elapsed time t after the dropping increases, the equivalence circle diameter d of the curable resin composition also increases, and the equivalence circle diameter D pore of the voids decreases. The t 1 , t 2 and t 3 in the graph are synonymous with the seventh graph. That is, the elapsed time t 1, a gap 40 is formed in the layer of curable resin composition 30 is dropped from the dispersion since, when the elapsed time t 2, the equivalent circular diameter of the void of D pore 40 = 10mm, the elapsed time At t 3 , the gap 40 will be eliminated.
依如上述,當統括滴下硬化性樹脂組成物時,只要在依下式所示之時間t內實施減壓積層便可。As described above, when the curable resin composition is dripped, the pressure-reducing layer may be applied in the time t shown by the following formula.
t2 ≦t≦t3 t 2 ≦t≦t 3
根據第14圖的圖形,實施減壓積層時,若硬化性樹脂組成物的等值圓直徑d、及空隙的等值圓直徑Dpore 分別在以下範圍內便可。According to the pattern of Fig. 14, when the pressure reduction laminate is applied, the equivalence circle diameter d of the curable resin composition and the equivalence circle diameter D pore of the voids may be within the following ranges.
d2 ≦d≦d3 d 2 ≦d≦d 3
D3 ≦Dpore ≦D2 D 3 ≦D pore ≦D 2
當在基板由密封部所包圍區域上,一邊使噴嘴進行移動,一邊滴下硬化性樹脂組成物時,藉由使基板與噴嘴進行相對性擺動,且將已滴下的硬化性樹脂組成物的等值圓直徑,配合其滴下的時期進行適當擴展,便可使滴下結束時的硬化性樹脂組成物之等值圓直徑呈均勻。此處,將第1次滴下與第X次滴下間之時間差設為Tx-1 、第1次滴下的硬化性樹脂組成物因經過時間Tx-1 而造成的等值圓直徑擴展設為Δdx-1 、第X次的擺動振幅設為Sx 時,若將第X次的擺動振幅Sx 設為Sx =Δdx-1 的話,在滴下結束時便可使硬化性樹脂組成物的等值圓直徑呈均勻。When the curable resin composition is dropped while moving the nozzle while the substrate is moved by the sealing portion, the substrate and the nozzle are relatively oscillated, and the equivalent of the curable resin composition that has been dropped is obtained. The diameter of the circle is appropriately expanded in accordance with the period of the dropping, so that the equivalence circle diameter of the curable resin composition at the end of the dropping can be made uniform. Here, the time difference between the first drop and the Xth drop is set to T x-1 , and the hardened resin composition dropped for the first time has an equivalence circle diameter expansion due to the elapse of time T x-1 . When Δd x-1 and the X-th swing amplitude are S x , when the X-th swing amplitude S x is S x =Δd x-1 , the curable resin composition can be obtained at the end of the dropping. The equivalent circle diameter is uniform.
此處,就縮短從開始滴下起至實施真空積層的時間之觀點,最好在剛要實施真空積層前便使所有硬化性樹脂組成物的等值圓直徑成為d2 。為能達成此情形,當最後滴下的硬化性樹脂組成物之等值圓直徑設為df 時,最好將d2 與df 的差分(d2 -df )當作振幅從第1次滴下開始進行擺動。此時,第n次的擺動振幅Sn 為Sn =Δdx-1 +(d2 -df )。Here, from the viewpoint of shortening the time from the start of the dripping to the time of performing the vacuum lamination, it is preferable to make the equivalence circle diameter of all the curable resin compositions d 2 immediately before the vacuum lamination is performed. In order to achieve this, when the equivalence circle diameter of the last dripped curable resin composition is set to d f , it is preferable to use the difference (d 2 -d f ) between d 2 and d f as the amplitude from the first time. The drip starts to swing. At this time, the n-th swing amplitude S n is S n =Δd x-1 +(d 2 -d f ).
使用分配器將硬化性樹脂組成物呈線狀塗佈的情況,亦是當實施真空積層之際,存在於基板由密封部所包圍區域中的硬化性樹脂組成物層必需滿足上述(1)~(3)。In the case where the curable resin composition is applied in a linear form by using a dispenser, the layer of the curable resin which is present in the region surrounded by the sealing portion of the substrate must satisfy the above (1) to the case of performing vacuum lamination. (3).
本發明的製造方法中,為能在滿足上述(1)~(3)的狀態下實施真空積層,只要依以下順序實施如將硬化性樹脂組成物呈線狀塗佈的順序便可。In the production method of the present invention, in order to carry out the vacuum lamination in a state in which the above (1) to (3) are satisfied, the order in which the curable resin composition is applied in a line may be carried out in the following order.
第15圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 15 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第15圖中,硬化性樹脂組成物的塗佈圖案形成振動曲線30a,30b,該振動曲線30a,30b係相對於硬化性樹脂組成物供應機構(分配器)的列狀多點噴嘴進行方向(第15圖的情況,為基板10的長邊方向),在垂直方向(第15圖的情況,為基板10的短邊方向)依一定的週期X及振幅Y進行重複位移者。該振動曲線係具有藉由使基板與噴嘴進行相對性擺動而將硬化性樹脂組成物施行塗佈而在基板上獲得之硬化性樹脂組成物的帶狀既定週期與振幅之圖案塗膜。藉由將硬化性樹脂組成物施行塗佈成為振動曲線30a、30b,便可使基板10由密封部20所包圍區域中的較小空隙40呈均勻分散的狀態。此處應注意之處,如使用第16圖進行的後述,振動曲線30a,30b的形成時期、與空隙40的形成時期通常並未一致,藉由振動曲線30a、30b的形狀進行經時性變化,便會形成空隙40。此處,當硬化性樹脂組成物呈線狀塗佈時,塗佈的方法最好係僅從基板的長邊或短邊中任一方向進行塗佈。從基板的長邊與短邊二方向進行塗佈,因為會發生已塗佈的硬化性樹脂組成物重疊、樹脂厚度出現較厚部分與較薄部分的情況,因而最好避免。又,在重疊部分中會有捲入氣泡的可能性,結果容易導致最終製品中發生氣泡殘留情形,因而最好避免。In Fig. 15, the application pattern of the curable resin composition forms vibration curves 30a, 30b which are oriented with respect to the columnar multi-nozzle of the curable resin composition supply means (dispenser) ( In the case of Fig. 15, the longitudinal direction of the substrate 10 is repeated in the vertical direction (the short-side direction of the substrate 10 in the case of Fig. 15) by a constant period X and an amplitude Y. This vibration curve is a pattern coating film having a predetermined cycle period and amplitude of a curable resin composition obtained by applying a curable resin composition to the substrate by relatively swinging the substrate and the nozzle. By applying the curable resin composition to the vibration curves 30a and 30b, the substrate 10 can be uniformly dispersed in a small gap 40 in the region surrounded by the sealing portion 20. Here, it should be noted that, as will be described later using Fig. 16, the formation period of the vibration curves 30a, 30b and the formation period of the gap 40 are generally not coincident, and the shape of the vibration curves 30a, 30b is changed with time. A gap 40 is formed. Here, when the curable resin composition is applied in a line shape, the coating method is preferably applied only from one of the long side or the short side of the substrate. It is preferable to apply the coating from the long side and the short side of the substrate in such a manner that the applied curable resin composition overlaps and the resin thickness is thicker and thinner. Further, there is a possibility that bubbles are caught in the overlapping portion, and as a result, air bubbles are likely to occur in the final product, and thus it is preferable to avoid them.
另外,為使由密封部20所包圍區域中的較小空隙40呈均勻分散狀態,由第15圖中得知,相互鄰接振動曲線30a、30b的位移必需相互成為反相位。Further, in order to uniformly disperse the small gaps 40 in the region surrounded by the sealing portion 20, it is understood from Fig. 15 that the displacements of the mutually adjacent vibration curves 30a, 30b must be opposite to each other.
此處,就從基板10由密封部20所包圍區域中的較小空隙40呈均勻分散狀態的觀點,當將開始供應時的振動曲線30a之粗細度設為m(mm)時,週期X(mm)與振幅Y(mm)最好分別滿足下式:Here, from the viewpoint that the small gap 40 in the region surrounded by the sealing portion 20 of the substrate 10 is in a uniformly dispersed state, when the thickness of the vibration curve 30a at the time of starting supply is set to m (mm), the period X ( Mm) and the amplitude Y (mm) preferably satisfy the following formula:
2.1×m≦X≦10×m2.1×m≦X≦10×m
(2.1×m)/2≦Y≦(10×m)/2(2.1×m)/2≦Y≦(10×m)/2
更佳係週期X及振幅Y滿足下式:Better system cycle X and amplitude Y satisfy the following formula:
3×m≦X≦6×m3×m≦X≦6×m
(3×m)/2≦Y≦(6×m)/2(3×m)/2≦Y≦(6×m)/2
另外,上述說明中,利用與振動曲線30a的粗細度間之關係,對週期X及振幅Y的較佳範圍進行說明,與振動曲線30b的粗細度間之關係亦同。針對此點,下述d(s-r) 、d(r-r) 的較佳範圍亦同。Further, in the above description, the preferred range of the period X and the amplitude Y is described by the relationship with the thickness of the vibration curve 30a, and the relationship between the thickness and the thickness of the vibration curve 30b is also the same. For this point, the preferred ranges of d (sr) and d (rr) described below are also the same.
再者,當實施真空積層之際,因為必需滿足上述(2),即硬化性樹脂組成物層中未存在空隙之部分,其投影形狀的等值圓直徑Dnon-pore 必需在40mm以下,因而週期X最好在40mm以下、更佳在15mm以下。又,振幅Y較佳在20mm以下、更佳在7.5mm以下。In addition, when vacuum lamination is carried out, since it is necessary to satisfy the above (2), that is, a portion where no void exists in the curable resin composition layer, the equivalence circle diameter D non-pore of the projected shape must be 40 mm or less. The period X is preferably 40 mm or less, more preferably 15 mm or less. Further, the amplitude Y is preferably 20 mm or less, more preferably 7.5 mm or less.
再者,就沿密封部20不致產生較大空隙的觀點,振動曲線30a與密封部20間之最短距離d(s-r) 最好滿足下式:Further, from the viewpoint that the sealing portion 20 does not cause a large gap, the shortest distance d (sr) between the vibration curve 30a and the sealing portion 20 preferably satisfies the following formula:
d(s-r) ≦2.5×md (sr) ≦ 2.5 × m
此時,就與密封部20的各部位間之關係,要求振動曲線30a與密封部20間之最短距離d(s-r) 滿足上式。即圖中上側的密封部20與振動曲線30a間之最短距離、圖中下側的密封部20與振動曲線30b間之最短距離,要求圖中左側或圖中右側的密封部20、與振動曲線30a或振動曲線30b間之最短距離全部滿足上式。At this time, the shortest distance d (sr) between the vibration curve 30a and the sealing portion 20 is required to satisfy the above equation in relation to the respective portions of the sealing portion 20. That is, the shortest distance between the upper sealing portion 20 and the vibration curve 30a in the figure, and the shortest distance between the sealing portion 20 and the vibration curve 30b on the lower side in the drawing, the sealing portion 20 on the left side or the right side in the drawing, and the vibration curve are required. The shortest distance between 30a or the vibration curve 30b all satisfies the above formula.
振動曲線30a與密封部20間之最短距離d(s-r) ,更佳係滿足下式:The shortest distance d (sr) between the vibration curve 30a and the sealing portion 20 preferably satisfies the following formula:
d(s-r) ≦0.5×md (sr) ≦0.5×m
振動曲線30a與密封部20間之最短距離d(s-r) 的下限值並無特別的限定,振動曲線30a與密封部20相接亦可。但,若振動曲線30a與密封部20重疊,因為僅有該部分的硬化性樹脂組成物層厚度會變大,因而最好振動曲線30a與密封部20不要重疊。The lower limit of the shortest distance d (sr) between the vibration curve 30a and the sealing portion 20 is not particularly limited, and the vibration curve 30a may be in contact with the sealing portion 20. However, if the vibration curve 30a overlaps with the sealing portion 20, since only the thickness of the portion of the curable resin composition layer becomes large, it is preferable that the vibration curve 30a and the sealing portion 20 do not overlap.
再者,就使振動曲線30a、30b間不會產生較大空隙的觀點,最好相鄰接的振動曲線30a、30b的最短距離d(r-r) 滿足下式:Further, from the viewpoint of not causing a large gap between the vibration curves 30a and 30b, it is preferable that the shortest distance d (rr) of the adjacent vibration curves 30a and 30b satisfies the following formula:
d(r-r) ≦5×md (rr) ≦ 5 × m
此情況,振動曲線30a、30b中,與開始供應時的粗細度m間之關係最好能滿足上式。In this case, the relationship between the vibration curves 30a and 30b and the thickness m at the time of starting supply preferably satisfies the above formula.
相鄰接的振動曲線30a、30b的最短距離d(r-r) 更佳係滿足下式:The shortest distance d (rr) of the adjacent vibration curves 30a, 30b preferably satisfies the following formula:
d(r-r) ≦md (rr) ≦m
相鄰接的振動曲線30a、30b的最短距離d(r-r) 下限值並無特別的限定,相鄰接的振動曲線30a、30b相接亦可。但,若振動曲線30a、30b重疊,因為僅有該部分的硬化性樹脂組成物層厚度會變大,因而最好振動曲線30a、30b不要重疊。The shortest distance d (rr) lower limit value of the adjacent vibration curves 30a and 30b is not particularly limited, and the adjacent vibration curves 30a and 30b may be in contact with each other. However, if the vibration curves 30a and 30b are overlapped, since only the thickness of the portion of the curable resin composition layer becomes large, it is preferable that the vibration curves 30a and 30b do not overlap.
第16圖係相當於第15圖之部分放大圖的圖示。其中,為能圖示振動曲線30a、30b形狀的經時變化,便以擴大相鄰接振動曲線30a、30b之間隔的狀態表示。第16圖振動曲線30a、30b係如虛線所示,其粗細度會經時的擴大,導致相鄰接的振動曲線30a、30b相接而形成空隙40。Fig. 16 is a view corresponding to a partially enlarged view of Fig. 15. Here, in order to show the temporal change of the shape of the vibration curves 30a and 30b, the state in which the interval between the adjacent vibration curves 30a and 30b is widened is shown. The vibration curves 30a and 30b of Fig. 16 are indicated by broken lines, and the thickness thereof is enlarged over time, so that the adjacent vibration curves 30a and 30b are in contact with each other to form the gap 40.
另外,在形成相鄰接之振動曲線30a、30b時,振動曲線30a、30b相接的情況下,便會在形成振動曲線30a、30b的時點形成空隙40。Further, when the adjacent vibration curves 30a and 30b are formed, when the vibration curves 30a and 30b are in contact with each other, the gap 40 is formed at the time when the vibration curves 30a and 30b are formed.
此處,所形成之空隙40的直徑E(mm),更具體而言,係在振動曲線30a、30b的振幅Y方向上之空隙40的直徑E(即等值圓直徑),其依下式所示:Here, the diameter E (mm) of the formed void 40, more specifically, the diameter E (ie, the equivalence circle diameter) of the void 40 in the amplitude Y direction of the vibration curves 30a, 30b, is as follows Shown as follows:
E=2Y-2mE=2Y-2m
在實施真空積層時,最好空隙40的直徑E滿足下式,即呈滿足上述(1)~(3)的狀態,更具體係滿足上述(1)及(2)的狀態。When the vacuum lamination is carried out, it is preferable that the diameter E of the void 40 satisfies the following formula, that is, the state satisfying the above (1) to (3), and the system satisfies the above (1) and (2).
(Y+d(r-r) )/10≦E≦Y+d(r-r) (Y+d (rr) )/10≦E≦Y+d (rr)
另外,上述係以振動曲線30a、30b的振幅Y及粗細度m呈相等之情況為前提來記載。當振動曲線30a、30b的振幅Ya 、Yb 及粗細度ma 、mb 係不同時,空隙40的直徑E便依下式所示:In addition, the above description is based on the assumption that the amplitude Y and the thickness m of the vibration curves 30a and 30b are equal. When the amplitudes Y a , Y b and the thicknesses m a and m b of the vibration curves 30a and 30b are different, the diameter E of the gap 40 is expressed by the following formula:
E=Ya +Yb -(ma +mb )E=Y a +Y b -(m a +m b )
(Ya +Yb +2d(r-r) )/20≦E≦(Ya +Yb +2d(r-r) )/2(Y a +Y b +2d (rr) )/20≦E≦(Y a +Y b +2d (rr) )/2
再者,就從較容易工業性高速且曲線狀塗佈、以及由使密封部所包圍區域中的硬化性樹脂組成物與空隙間之比率為適當的觀點,開始供應時的振動曲線粗細度m較佳係1~40mm、更佳係3~15mm。In addition, from the viewpoint of being easy to industrially high-speed and curved coating, and the ratio between the curable resin composition and the void in the region surrounded by the sealing portion is appropriate, the vibration curve thickness m at the start of supply is started. It is preferably 1 to 40 mm, more preferably 3 to 15 mm.
為能將硬化性樹脂組成物塗佈呈既定振動曲線30a、30b,便如第17圖所示,使用在圖中x軸、y軸任一方向上均可進行移動的噴嘴(多點噴嘴(包括分支噴嘴))104塗佈硬化性樹脂組成物塗佈。In order to apply the curable resin composition to the predetermined vibration curves 30a and 30b, as shown in Fig. 17, a nozzle that can move in either of the x-axis and the y-axis in the drawing (multi-point nozzle (including The branch nozzle)) 104 is coated with a curable resin composition.
如在將硬化性樹脂組成物呈點狀分散滴下的情況所說明,滴下後的硬化性樹脂組成物會經時性擴展,導致其等值圓直徑變大。當將硬化性樹脂組成物呈線狀塗佈時亦會引發同樣的現象,振動曲線30a、30b的粗細度會經時性變粗。As described in the case where the curable resin composition is dispersed in a dot shape, the curable resin composition after the dropping is extended with time, and the diameter of the equivalent circle is increased. The same phenomenon is caused when the curable resin composition is applied in a line shape, and the thickness of the vibration curves 30a and 30b becomes thicker with time.
因而,最好如第18,19圖所示,將形成振動曲線30a時的塗佈方向(第18圖中箭頭所示)、及形成與該振動曲線30a相鄰接之振動曲線30b時的塗佈方向(第19圖中箭頭所示)設為相反方向,理由係如第20圖所示,可使存在於由密封部20所包圍區域中的空隙40大小呈均勻化。Therefore, as shown in Figs. 18 and 19, it is preferable to apply the coating direction (the arrow shown in Fig. 18) when the vibration curve 30a is formed, and the coating curve 30b adjacent to the vibration curve 30a. The cloth direction (indicated by the arrow in Fig. 19) is set to the opposite direction, and the reason is that the size of the gap 40 existing in the region surrounded by the sealing portion 20 can be made uniform as shown in Fig. 20.
再者,第15~20圖係振動曲線30a與30b的振幅Y為相同之例子,但亦可如第21圖所示,振動曲線30a’與振動曲線30b’的振幅Y為不同。Further, although the amplitudes Y of the vibration curves 30a and 30b are the same in the fifteenth to twenty-fifthth embodiments, the vibration curve 30a' and the amplitude Y of the vibration curve 30b' may be different as shown in Fig. 21.
再者,第15~21圖中,相鄰接之硬化性樹脂組成物層的圖案均形成振動曲線,但亦可如第22圖所示,相鄰接之硬化性樹脂組成物層的圖案中,僅有其中一者為振動曲線30a”,而另一者則為直線30c。Further, in the figures 15 to 21, the patterns of the adjacent curable resin composition layers each form a vibration curve, but as shown in Fig. 22, the pattern of the adjacent curable resin composition layer may be Only one of them is the vibration curve 30a", and the other is the straight line 30c.
但,此情況下,最靠近密封部20必需非直線30c而必需是振動曲線30a”。However, in this case, the closest to the sealing portion 20 must be a non-linear line 30c and must be a vibration curve 30a".
再者,振動曲線30a”的週期X及振幅Y,依照與開始供應時的振動曲線粗細度m間之關係,最好滿足上述條件。Further, it is preferable that the period X and the amplitude Y of the vibration curve 30a" satisfy the above conditions in accordance with the relationship between the thickness m of the vibration curve at the time of starting supply.
再者,振動曲線30a”與密封部20間之最短距離d(s-r) ,依照與開始供應時的振動曲線粗細度m間之關係,最好滿足上述條件。Further, the shortest distance d (sr) between the vibration curve 30a" and the sealing portion 20 preferably satisfies the above condition in accordance with the relationship between the thickness m of the vibration curve at the time of starting supply.
再者,相鄰接之振動曲線30a”與直線30c間之最短距離d(r-r) ,依照與開始供應時的振動曲線粗細度m間之關係,最好滿足有關相鄰接之振動曲線間之最短距離d(r-r) 所記載的條件。Furthermore, the shortest distance d (rr) between the adjacent vibration curve 30a" and the straight line 30c is preferably between the adjacent vibration curves according to the relationship between the thickness m of the vibration curve at the start of supply. The condition described in the shortest distance d (rr) .
再者,利用相鄰接之振動曲線30a”與直線30c的相接而形成之空隙E(mm),更具體而言,係在振動曲線30a”的振幅Y方向上之空隙的直徑E(即等值圓直徑),其最好滿足下式:(Y+d(r-r) )/20≦E≦(Y+d(r-r) )/2再者,第15~22圖中,在基板10的長邊方向上形成硬化性樹脂組成物之層的圖案,但亦可如第23圖所示,在基板10的短邊方向上形成硬化性樹脂組成物之層的圖案(30e、30f)。Further, the gap E (mm) formed by the contact of the adjacent vibration curve 30a" with the straight line 30c, more specifically, the diameter E of the gap in the amplitude Y direction of the vibration curve 30a" (ie, Equivalent circle diameter), which preferably satisfies the following formula: (Y+d (rr) ) / 20 ≦ E ≦ (Y + d (rr) ) / 2, in Figures 15 to 22, on the substrate 10 A pattern of a layer of the curable resin composition is formed in the longitudinal direction. However, as shown in FIG. 23, a pattern (30e, 30f) of a layer of the curable resin composition may be formed in the short-side direction of the substrate 10.
再者,第15~23圖中,硬化性樹脂組成物層的圖案係形成振動曲線,但亦可如第24圖所示,係在一定週期X設有寬幅部位31的直線30f、30g。此情況亦適用將硬化性樹脂組成物塗佈呈振動曲線30a、30b時所記載的條件。但,寬幅部位31的最大寬度係滿足關於振動曲線所記載的振幅Y之條件。Further, in the fifteenth to twenty-fifthth drawings, the pattern of the curable resin composition layer forms a vibration curve, but as shown in Fig. 24, the straight lines 30f and 30g of the wide portion 31 may be provided in a predetermined period X. Also in this case, the conditions described when the curable resin composition is applied to the vibration curves 30a and 30b are also applicable. However, the maximum width of the wide portion 31 satisfies the condition of the amplitude Y described in the vibration curve.
本發明積層體的製造方法中,真空積層可依照以下順序實施。以下,本說明書中,一對基板中,將表面上有形成密封部及硬化性樹脂組成物層之側的基板稱為「其中一基板」,將表面上並無形成該等之側的基板稱為「另一基板」。In the method for producing a laminate of the present invention, the vacuum laminate can be carried out in the following order. In the present invention, the substrate on the surface on which the sealing portion and the curable resin composition layer are formed is referred to as "one of the substrates", and the substrate on the surface is not formed. It is "another substrate."
將其中一基板放入減壓裝置中,在減壓裝置內的固定支撐盤上將該基板平放成硬化性樹脂組成物層之面朝上狀態。One of the substrates was placed in a decompression device, and the substrate was placed flat on the fixed support disk in the decompression device to face up in a state in which the curable resin composition layer was placed.
在減壓裝置內的上部設有可朝上下方向移動的移動支撐機構,在移動支撐機構安裝有另一基板。此處,當在另一基板表面上形成薄膜系太陽電池裝置時,便將形成有薄膜系太陽電池裝置之側的表面朝下。又,當積層體的用途係平面顯示器(FPD)時,便將顯示影像之側的表面朝下。又,當在另一基板的表面設有抗反射層時,便將沒有形成抗反射層之側的表面朝下。A moving support mechanism that can move in the vertical direction is provided in an upper portion of the pressure reducing device, and another substrate is attached to the moving support mechanism. Here, when a thin film system solar cell device is formed on the surface of another substrate, the surface on the side on which the thin film system solar cell device is formed faces downward. Further, when the use of the laminated body is a flat panel display (FPD), the surface on the side where the image is displayed faces downward. Further, when the antireflection layer is provided on the surface of the other substrate, the surface on the side where the antireflection layer is not formed faces downward.
另一基板放置於其中一基板上方且係未接觸到硬化性樹脂組成物層的位置處。即,不使其中一基板上的硬化性樹脂組成物層與另一基板相接觸而是呈相對向。The other substrate is placed over one of the substrates and is not in contact with the layer of the curable resin composition. That is, the curable resin composition layer on one of the substrates is not brought into contact with the other substrate but is opposed to each other.
另外,亦可將能朝上下方向移動的移動支撐機構設置於減壓裝置內的下部,並在移動支撐機構的上方放置其中一基板。此時,另一基板係安裝於減壓裝置內的上部所設置的固定支撐盤上,並使其中一基板與另一基板相對向。Alternatively, a moving support mechanism movable in the up and down direction may be provided in a lower portion of the decompression device, and one of the substrates may be placed above the moving support mechanism. At this time, the other substrate is mounted on the fixed support disk provided on the upper portion of the pressure reducing device, and one of the substrates is opposed to the other substrate.
再者,亦可使其中一基板與另一基板二者,由設置在減壓裝置內的上下的移動支撐機構來支撐。Furthermore, one of the substrates and the other of the substrates may be supported by upper and lower moving support mechanisms provided in the decompression device.
將其中一基板及另一基板配置於既定位置後,便將減壓裝置的內部予以減壓而形成既定的減壓環境。若可能的話,亦可在減壓操作中或形成既定減壓環境後,在減壓裝置內使其中一基板及另一基板位於既定位置處。After one of the substrates and the other substrate are placed at a predetermined position, the inside of the pressure reducing device is depressurized to form a predetermined reduced pressure environment. If possible, one of the substrates and the other substrate may be placed at a predetermined position in the decompression device after the decompression operation or the formation of the predetermined decompression environment.
在減壓裝置的內部形成既定減壓環境後,將由移動支撐機構所支撐的另一基板朝下方移動,並使另一基板重疊於其中一基板上的硬化性樹脂組成物層上方。After a predetermined decompression environment is formed inside the decompression device, the other substrate supported by the moving support mechanism is moved downward, and the other substrate is superposed on the hard resin composition layer on one of the substrates.
藉由重疊,在其中一基板的表面、另一基板的下面、以及由密封部所包圍的空間內密封著硬化性樹脂組成物。By overlapping, the curable resin composition is sealed in the surface of one of the substrates, the lower surface of the other substrate, and the space surrounded by the sealing portion.
當重疊之際,利用另一基板的本身重量、來自移動支撐機構的按壓等,硬化性樹脂組成物會被擠壓擴散,俾使上述空間內充滿硬化性樹脂組成物,然後藉由解除減壓環境,便形成無空隙的硬化性樹脂組成物層。When overlapping, the curable resin composition is squeezed and diffused by the weight of the other substrate itself, the pressing from the moving support mechanism, etc., so that the space is filled with the curable resin composition, and then the decompression is released. In the environment, a void-free curable resin composition layer is formed.
重疊時的減壓環境係1000Pa以下、較佳為0.1Pa以上。若減壓環境過度低壓,便會有對硬化性樹脂組成物中所含的各成分(硬化性化合物、光聚合起始劑、聚合終止劑、光安定劑等)造成不良影響之可能性。例如若減壓環境過度低壓,各成分便會有氣化的可能性,且為提供減壓環境而頗耗費時間。減壓環境的壓力更佳係1~100Pa。特佳係3~30Pa。The reduced pressure environment at the time of superposition is 1000 Pa or less, preferably 0.1 Pa or more. When the pressure-reduced environment is excessively low, the components (hardening compound, photopolymerization initiator, polymerization terminator, light stabilizer, etc.) contained in the curable resin composition may be adversely affected. For example, if the decompression environment is excessively low, the components may be vaporized, and it takes time to provide a reduced pressure environment. The pressure in the reduced pressure environment is preferably 1 to 100 Pa. Very good 3 to 30Pa.
從使其中一基板與另一基板相重疊的時點起至解除減壓環境為止的時間,並無特別的限定,可在硬化性樹脂組成物密封後,便馬上解除減壓環境,亦可在硬化性樹脂組成物密封後,仍將減壓狀態維持在既定時間。藉由將減壓狀態維持在既定時間,硬化性樹脂組成物便會在密閉空間內進行流動,俾使其中一基板與另一基板間的間隔能均勻,即便藉由解除減壓環境,而被放置於較實施真空積層時的減壓環境更高之第2壓力環境下,仍可輕易地維持密封狀態。維持減壓狀態的時間係可為數小時以上的長時間,但就從生產效率的觀點,較佳在1小時以內、更佳在10分鐘以內。The time from when the one substrate overlaps the other substrate to when the pressure-reducing environment is released is not particularly limited, and the pressure-reducing environment can be immediately released after the curable resin composition is sealed, or hardened. After the resin composition is sealed, the reduced pressure state is maintained for a predetermined period of time. By maintaining the reduced pressure state for a predetermined period of time, the curable resin composition flows in the sealed space, so that the interval between one of the substrates and the other substrate can be made uniform even by releasing the decompression environment. The sealing state can be easily maintained even in a second pressure environment which is higher than the pressure reducing environment at the time of performing vacuum lamination. The time for maintaining the reduced pressure state may be a long time of several hours or more, but from the viewpoint of production efficiency, it is preferably within 1 hour, more preferably within 10 minutes.
接著,若藉由解除減壓環境,而將挾持著硬化性樹脂組成物的一對基板放置於較減壓環境更高的第2壓力環境下,則藉由環境壓力的上升,其中一基板與另一基板便會朝相密接的方向按壓,因而硬化性樹脂組成物會在密閉空間內進行流動,俾使密閉空間整體被硬化性樹脂組成物均勻地填充,形成沒有空隙的硬化性樹脂組成物層。Then, by releasing the decompression environment and placing the pair of substrates holding the curable resin composition in a second pressure environment higher than the reduced pressure environment, one of the substrates is increased by the increase in the environmental pressure. When the other substrate is pressed in the direction in which it is in contact with each other, the curable resin composition flows in the sealed space, and the entire sealed space is uniformly filled with the curable resin composition to form a curable resin composition having no voids. Floor.
此處,第2壓力環境的壓力最好較實施真空積層的減壓環境高出50kPa以上。第2壓力環境的壓力通常最好為80k~120kPa。第2壓力環境可為大氣壓環境、亦可為較此更高的壓力。就從硬化性樹脂組成物的硬化等操作能在不需要特別設備的情況下便可實施之觀點,最佳為大氣壓環境。Here, the pressure in the second pressure environment is preferably 50 kPa or more higher than the pressure reduction environment in which the vacuum layer is laminated. The pressure in the second pressure environment is usually preferably from 80 k to 120 kPa. The second pressure environment may be an atmospheric pressure environment or a higher pressure. From the viewpoint of the operation such as hardening of the curable resin composition, it is possible to carry out the operation without requiring special equipment, and it is preferably an atmospheric pressure environment.
在上述第2壓力環境下,利用其中一基板與另一基板的按壓而進行之密接積層步驟,係可在執行上述真空積層的減壓裝置中,解除減壓裝置之減壓室的減壓,將該減壓室調整為80k~120kPa的壓力(例如大氣壓),再於該壓力環境下施行使前述樹脂層形成用硬化性樹脂組成物進行硬化的處理,或者亦可從施行真空積層的減壓裝置移往其他的化處理裝置,並將該硬化處理裝置內調整為80k~120kPa的壓力,再於該壓力環境下施行使前述樹脂層形成用硬化性樹脂組成物進行硬化的處理。In the second pressure environment, the pressure-separating step by pressing one of the substrates and the other substrate can release the decompression of the decompression chamber of the decompression device in the decompression device that performs the vacuum lamination. The pressure-reduction chamber is adjusted to a pressure of 80 k to 120 kPa (for example, atmospheric pressure), and the curable resin composition for forming a resin layer is cured in the pressure environment, or may be decompressed from the vacuum lamination. The apparatus is moved to another chemical processing apparatus, and the inside of the hardening processing apparatus is adjusted to a pressure of 80 k to 120 kPa, and the curable resin composition for forming a resin layer is cured in the pressure environment.
將挾持著硬化性樹脂組成物的一對基板保持在較減壓環境更高的第2壓力環境下之時間並無特別的限定。將挾持著硬化性樹脂組成物的一對基板,從減壓裝置中取出並移動至硬化處理裝置中且截至開始進行硬化的製程均在大氣壓環境下執行時,該製程所需要的時間便成為保持於第2壓力環境下的時間。所以,當放置於大氣壓環境下時,密閉空間內的硬化性樹脂組成物層中已不存在空隙的情況、或者在該製程期間硬化性樹脂組成物層中的空隙便已消失的情況,可馬上使硬化性樹脂組成物硬化。當截至空隙消失為止尚需要時間時,截至空隙消失為止前將挾持著硬化性樹脂組成物的一對基板保持於第2壓力環境下。又,因為即便拉長在第2壓力環境下保持的時間,通常仍不會造成阻礙,因而就從製程上的其他必要性,亦可拉長在第2壓力環境下的保持時間。The time during which the pair of substrates holding the curable resin composition is maintained in the second pressure environment higher than the reduced pressure environment is not particularly limited. When a pair of substrates holding the curable resin composition are taken out from the decompression device and moved to the hardening treatment device, and the processes until the start of hardening are performed in an atmospheric pressure environment, the time required for the process is maintained. Time in the second pressure environment. Therefore, when it is placed in an atmospheric pressure environment, there is no gap in the curable resin composition layer in the sealed space, or the void in the curable resin composition layer disappears during the process. The curable resin composition is cured. When it takes time until the void disappears, the pair of substrates holding the curable resin composition are held in the second pressure environment until the void disappears. Further, even if the time elapsed in the second pressure environment is elongated, it is usually not hindered, and the holding time in the second pressure environment can be lengthened from other necessity in the process.
在第2壓力環境下的保持時間可為1日以上的長時間,但就從生產效率的觀點,較佳在6小時以內、更佳在1小時以內,就從更加提高生產效率的觀點,特佳在10分鐘以內。The holding time in the second pressure environment may be a long time of one day or longer, but from the viewpoint of production efficiency, preferably within 6 hours, more preferably within 1 hour, from the viewpoint of further improving production efficiency, Good within 10 minutes.
接著,藉由使密閉空間內的硬化性樹脂組成物進行硬化,便製得具有一對基板、與存在於該一對基板間的硬化性樹脂組成物之硬化物層的積層體。Then, by curing the curable resin composition in the sealed space, a laminate having a pair of substrates and a cured layer of a curable resin composition existing between the pair of substrates is obtained.
使硬化性樹脂組成物硬化的手段,係配合熱硬化性樹脂組成物的種類而任意使用熱硬化或光硬化。但,如上述,所使用的硬化性樹脂組成物較佳係光硬化性樹脂組成物。The means for curing the curable resin composition is arbitrarily used for thermal curing or photocuring in accordance with the type of the thermosetting resin composition. However, as described above, the curable resin composition to be used is preferably a photocurable resin composition.
光硬化性樹脂組成物的情況,例如從光源(紫外線燈、高壓水銀燈等)照射紫外線或短波長可見光,藉由使密閉空間內的硬化性樹脂組成物進行硬化,便製得具有一對基板、與存在於該一對基板間的硬化性樹脂組成物之硬化物層的積層體。In the case of the photocurable resin composition, for example, a light source (ultraviolet lamp, high pressure mercury lamp, or the like) is irradiated with ultraviolet light or short-wavelength visible light, and the curable resin composition in the sealed space is cured to obtain a pair of substrates. A laminate of a cured layer of a curable resin composition existing between the pair of substrates.
光從一對基板中的透明基板側進行照射。當雙方均為透明基板的情況,亦可從二側進行照射。Light is irradiated from the side of the transparent substrate in the pair of substrates. When both of them are transparent substrates, they can be irradiated from both sides.
當所製造的積層體係平面顯示器(FPD)的情況、以及當該平面顯示器係使用穿透型顯示裝置的情況,雖藉由使該裝置產生動作便可獲得透光性,但因為大多屬於在未產生動作的狀態下便不具透光性者,因而便從成為保護板的透明基板照射會使硬化性樹脂組成物硬化的光。另一方面,當該平面顯示器係使用非動作時便呈透明狀態的穿透-散射型顯示裝置時,亦可利用來自顯示裝置側的光。In the case of a laminated system flat panel display (FPD) manufactured and a case where the flat display device uses a transmissive display device, light transmittance can be obtained by causing the device to generate an action, but most of them belong to In the state in which the operation is performed, the light-transmissive property is not obtained. Therefore, the transparent substrate serving as the protective sheet is irradiated with light that hardens the curable resin composition. On the other hand, when the flat-panel display uses a penetration-scattering type display device which is in a transparent state when it is not in operation, light from the display device side can also be utilized.
光較佳係紫外線或450nm以下的可見光。特別係在透明基板上設有抗反射層,而抗反射層或形成抗反射層時所使用的樹脂薄膜係紫外線不會穿透的情況,便必需利用可見光進行硬化。The light is preferably ultraviolet light or visible light of 450 nm or less. In particular, an antireflection layer is provided on the transparent substrate, and the antireflection layer or the resin film used in forming the antireflection layer does not penetrate the ultraviolet rays, and it is necessary to be hardened by visible light.
依照本發明製造方法所獲得的積層體,頗適用於薄層太陽電池裝置或影像顯示裝置等。薄層太陽電池裝置的具體例,係可舉例如:薄膜矽太陽電池裝置、黃銅礦系或CdTe系等化合物半導體太陽電池裝置等等。另一方面,影像顯示裝置的具體例係可舉例如:液晶顯示裝置(LCD)、有機EL與無機EL之類的EL(電激發光)顯示裝置、電漿顯示裝置、以及電子墨水型影像顯示裝置之類的平面顯示器(FPD)。The laminate obtained by the production method of the present invention is suitable for use in a thin-film solar cell device or an image display device. Specific examples of the thin-film solar battery device include, for example, a thin film germanium solar cell device, a compound semiconductor solar cell device such as a chalcopyrite system or a CdTe system, and the like. On the other hand, specific examples of the video display device include, for example, a liquid crystal display device (LCD), an EL (Electrically Excited Light) display device such as an organic EL and an inorganic EL, a plasma display device, and an electronic ink type image display. A flat panel display (FPD) such as a device.
薄層太陽電池裝置的情況係構成積層體的一對基板中,可僅在其中一基板上形成薄層太陽電池裝置,亦可在雙方基板上均有形成薄層太陽電池裝置。In the case of a thin-film solar cell device, a thin-film solar cell device can be formed only on one of the substrates, and a thin-film solar cell device can be formed on both of the substrates.
以下,根據實施例針對本發明進行更具體的說明。但,本發明並不僅侷限於此。另外,例1、例7、例8、例10、例15係屬於實施例,其他的例子則屬於比較例。Hereinafter, the present invention will be more specifically described based on examples. However, the present invention is not limited to this. Further, Examples 1, 7, 7, 8, 10, and 15 are examples, and other examples are comparative examples.
將分子末端經環氧乙烷改質過的雙官能基的聚丙二醇(依羥值計算出的數平均分子量:4000)、與六亞甲二異氰酸酯,依6比7的莫耳比進行混合,接著利用甲基丙烯酸異莰酯(大阪有機化學工業公司製、IBXA)進行稀釋後,於在錫化合物的觸媒存在下進行反應而獲得之預聚物中,依約1比2的莫耳比添加丙烯酸-2-羥乙酯並使其反應,藉此獲得經30質量%甲基丙烯酸異莰酯稀釋過的胺甲酸酯丙烯酸酯寡聚物(以下稱「UC-1」)溶液。UC-1的硬化性基數係2,數平均分子量約55000。UC-1溶液在60℃下的黏度約580Pa‧s。a difunctional polypropylene glycol having a molecular end modified with ethylene oxide (number average molecular weight calculated from a hydroxyl value: 4000), and hexamethylene diisocyanate mixed at a molar ratio of 6 to 7. Then, it is diluted with isodecyl methacrylate (IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and then subjected to a reaction in the presence of a catalyst of a tin compound to obtain a molar ratio of about 1 to 2. A 2-hydroxyethyl acrylate was added and reacted, whereby a solution of a urethane acrylate oligomer (hereinafter referred to as "UC-1") diluted with 30% by mass of isodecyl methacrylate was obtained. The hardening base of UC-1 is 2, and the number average molecular weight is about 55,000. The viscosity of the UC-1 solution at 60 ° C is about 580 Pa‧s.
將90質量份的UC-1溶液、及10質量份的甲基丙烯酸-2-羥丁酯(共榮社化學公司製、LIGHT ESTER HOB)均勻混合而獲得混合物。將100質量份的該混合物、1質量份的1-羥基-環己基-苯基-酮(光聚合起始劑,Ciba Specialty Chemicals公司製、IRGACURE 184)、0.1質量份的雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(光聚合起始劑,Ciba Specialty Chemicals公司製、IRGACURE 819)、0.04質量份的2,5-二第三丁基氫醌(聚合終止劑)、及0.3質量份的紫外線吸收劑(Ciba Specialty Chemicals公司製、TINUVIN 109)均勻混合,便獲得密封部形成用光硬化性樹脂組成物X。90 parts by mass of the UC-1 solution and 10 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER HOB) were uniformly mixed to obtain a mixture. 100 parts by mass of the mixture, 1 part by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 184), 0.1 part by mass of bis(2,4, 6-trimethylbenzimidyl)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 819), 0.04 parts by mass of 2,5-di-t-butylhydroquinone (polymerization termination) The agent () and 0.3 parts by mass of a UV absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 109) were uniformly mixed to obtain a photocurable resin composition X for forming a sealing portion.
在將密封部形成用光硬化性樹脂組成物X放入容器且呈開放狀態下設置於減壓裝置內,將減壓裝置內減壓至約20Pa並保持10分鐘,藉此施行脫泡處理。經測定密封部形成用光硬化性樹脂組成物X(即第2硬化性樹脂組成物)在25℃下的黏度,結果約1400Pa‧s。The photocurable resin composition X for sealing portion formation was placed in a container and opened in a decompression device, and the inside of the decompression device was depressurized to about 20 Pa for 10 minutes to perform a defoaming treatment. The viscosity of the photocurable resin composition X (that is, the second curable resin composition) for forming the seal portion at 25 ° C was measured, and it was about 1400 Pa s.
沿長1100mm、寬900mm、厚2mm的鈉鈣玻璃製基板(以下稱「基板A」。相當於本發明的其中一基板)距外周部靠內側5mm位置,塗佈上述密封部形成用光硬化性樹脂組成物X,便形成厚度1mm的密封部。A substrate made of soda lime glass having a length of 1100 mm, a width of 900 mm, and a thickness of 2 mm (hereinafter referred to as "substrate A", which corresponds to one of the substrates of the present invention) is disposed at a position of 5 mm from the outer peripheral portion, and the photocuring property for forming the sealing portion is applied. The resin composition X forms a sealing portion having a thickness of 1 mm.
將1莫耳的雙官能基的聚丙二醇(依羥值計算出的數平均分子量:2000)、1莫耳的分子末端經環氧乙烷改質過的雙官能基的聚丙二醇(依羥值計算出的數量平均分子量:4000)、及1莫耳的乙二醇均勻混合,獲得多元醇混合物。將該多元醇混合物、與異佛爾酮二異氰酸酯依5比6的莫耳比進行混合,以在錫化合物觸媒存在下進行而獲得預聚物,在該預聚物中依約1比2的莫耳比添加丙烯酸-2-羥乙酯並使其反應,便獲得胺甲酸酯丙烯酸酯寡聚物(以下稱「UA-2」)。UA-2的硬化性基數係2,數平均分子量約19000,25℃下的黏度約1300Pa‧s。1 mole of difunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 2000), 1 mole of diethylene glycol modified with ethylene oxide at the end of the molecule (based on hydroxyl value) The calculated number average molecular weight: 4000), and 1 mole of ethylene glycol were uniformly mixed to obtain a polyol mixture. The polyol mixture is mixed with isophorone diisocyanate at a molar ratio of 5 to 6 to obtain a prepolymer in the presence of a tin compound catalyst, and about 1 to 2 in the prepolymer. The molar ratio of 2-hydroxyethyl acrylate was added to the molar ratio to obtain a urethane acrylate oligomer (hereinafter referred to as "UA-2"). The hardening base of UA-2 is 2, the number average molecular weight is about 19,000, and the viscosity at 25 ° C is about 1300 Pa‧s.
將60質量份的UA-2、及40質量份的甲基丙烯酸-2-羥丁酯(共榮社化學公司製、LIGHT ESTER HOB)均勻混合,並在100質量份的該混合物中,均勻溶解0.2質量份的雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(光聚合起始劑,Ciba Specialty Chemicals公司製、IRGACURE 819)、0.04質量份的2,5-二第三丁基氫醌(聚合終止劑)、以及0.3質量份的紫外線吸收劑(Ciba Specialty Chemicals公司製、TINUVIN 109),便獲得樹脂層形成用光硬化性樹脂組成物Y。60 parts by mass of UA-2 and 40 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER HOB) were uniformly mixed, and uniformly dissolved in 100 parts by mass of the mixture. 0.2 parts by mass of bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 819), 0.04 parts by mass of 2,5- The photo-curable resin composition Y for forming a resin layer was obtained by using a di-tert-butylhydroquinone (polymerization terminator) and 0.3 parts by mass of a UV absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 109).
在將上述樹脂層形成用光硬化性樹脂組成物Y放入容器且呈開放狀態下設置於減壓裝置內,將減壓裝置內減壓至約20Pa並保持10分鐘,藉此施行脫泡處理。經測定樹脂層形成用光硬化性樹脂組成物Y在25℃下的黏度,結果約14Pa‧s。The resin layer-forming photocurable resin composition Y is placed in a container and placed in a decompression device in an open state, and the inside of the decompression device is decompressed to about 20 Pa for 10 minutes, thereby performing defoaming treatment. . The viscosity of the photocurable resin composition Y for forming a resin layer at 25 ° C was measured, and it was about 14 Pa ‧ .
其次,使用如下述的多點噴嘴式分配器,在由密封部所包圍的區域中,將上述樹脂層形成用光硬化性樹脂組成物Y依以下條件分散滴下。Then, the resin layer-forming photocurable resin composition Y was dispersed and dropped in the region surrounded by the sealing portion in the region surrounded by the sealing portion by using a multi-point nozzle type dispenser as described below.
‧滴下的間距:15mm。‧ Dropping pitch: 15mm.
‧硬化性樹脂組成物層的厚度:0.8mm(滴下量:0.18cc/點)。‧ Thickness of the curable resin composition layer: 0.8 mm (drop amount: 0.18 cc/dot).
‧滴下頭:在長邊方向上排列3台使用8×8=64點的多點噴嘴(分支噴嘴)者。‧ Drop head: Three sets of multi-nozzles (branch nozzles) using 8 × 8 = 64 points are arranged in the longitudinal direction.
‧滴下時間:滴下節拍3.3sec×24點=79.2sec。‧ Drop time: Drop the beat 3.3 sec × 24 points = 79.2 sec.
將硬化性樹脂組成物呈點狀分散滴下後的基板A,載置於減壓裝置的真空處理室內升降裝置下側的下平板之上面。將與基板A所使用者為相同形狀且相同厚度的鈉鈣玻璃板(稱「基板B」。相當於本發明的另一基板),靜電吸附於升降裝置上側的上平板之下面。The substrate A in which the curable resin composition was dispersed in a dot shape was placed on the lower surface of the lower plate on the lower side of the vacuum processing chamber of the decompression device. A soda lime glass plate (referred to as "substrate B", which corresponds to another substrate of the present invention) having the same shape and the same thickness as the user of the substrate A is electrostatically adsorbed on the lower surface of the upper plate on the upper side of the lifting device.
接著,將真空處理室形成密封狀態,並施行排氣直到處理室內成為15Pa為止。然後,利用真空處理室內的升降裝置使上下的平板相靠近,便使基板A與基板B積層。在此,從硬化性樹脂組成物完成滴下起至積層為止的時間係120sec。然後,將真空處理室內返回於大氣壓。Next, the vacuum processing chamber was sealed, and evacuation was performed until the treatment chamber became 15 Pa. Then, the upper and lower flat plates are brought closer to each other by the lifting device in the vacuum processing chamber, and the substrate A and the substrate B are laminated. Here, the time from the completion of the dropping of the curable resin composition to the lamination is 120 sec. The vacuum processing chamber is then returned to atmospheric pressure.
其次,利用升降裝置使上下的平板相遠離,並吸附於上側的上平板之吸附墊上,再使由基板A與基板B構成的積層體(稱「積層體C」)從上側的上平板剝離。Next, the upper and lower flat plates are separated from each other by the lifting device, and are adsorbed on the upper suction pad of the upper plate, and the laminated body (referred to as "layered body C") composed of the substrate A and the substrate B is peeled off from the upper upper plate.
然後,將積層體C保持水平並靜置約10分鐘後,再從基板B表面側依目視確認硬化性樹脂組成物層中有無空隙。結果如下表所示。Then, the layered body C was kept horizontal and left to stand for about 10 minutes, and then the presence or absence of voids in the curable resin composition layer was visually observed from the surface side of the substrate B. The results are shown in the table below.
另外,表中的符號意義分別如下:In addition, the meanings of the symbols in the table are as follows:
○:在由密封部所包圍區域中並無存在直徑100μm以上的空隙。○: There is no void having a diameter of 100 μm or more in the region surrounded by the sealing portion.
△:在由密封部所包圍區域中存在直徑100μm以上的空隙個數係1~30個/m2 。△: The number of voids having a diameter of 100 μm or more is 1 to 30/m 2 in a region surrounded by the sealing portion.
×:在由密封部所包圍區域中存在直徑100μm以上的空隙個數係31個/m2 以上。x: The number of voids having a diameter of 100 μm or more is 31/m 2 or more in a region surrounded by the sealing portion.
其次,從積層體C的面方向均勻地由高壓水銀燈照射紫外線,而使硬化性樹脂組成物硬化,藉此獲得夾層玻璃狀的積層體(稱「積層體D」)。Then, ultraviolet rays are uniformly irradiated from the high-pressure mercury lamp from the surface direction of the laminated body C, and the curable resin composition is cured to obtain a laminated glass-like laminated body (referred to as "layered body D").
除使用25℃下的黏度為4Pa‧s之樹脂層形成用光硬化性樹脂組成物以外,其餘均實施與例1同樣的順序。The same procedure as in Example 1 was carried out, except that a photocurable resin composition for forming a resin layer having a viscosity of 4 Pa ‧ at 25 ° C was used.
除使用25℃下的黏度為1Pa‧s之樹脂層形成用光硬化性樹脂組成物以外,其餘均實施與例1同樣的順序。The same procedure as in Example 1 was carried out except that a photocurable resin composition for forming a resin layer having a viscosity of 1 Pa ‧ at 25 ° C was used.
除將滴下間距設為30mm之以外,其餘均實施與例3同樣的順序。The same procedure as in Example 3 was carried out except that the dropping pitch was set to 30 mm.
將基板尺寸設為長1300mm、寬1100mm、厚2mm,並將滴下點數設為40點,且將滴下時間設為132sec(滴下節拍3.3sec×40點)以外,其餘均實施與例1同樣的順序。The same dimensions as in Example 1 were carried out except that the substrate size was 1300 mm in length, 1100 mm in width, and 2 mm in thickness, and the number of dropping points was 40 points, and the dropping time was 132 sec (3.3 sec × 40 points in dropping beat). order.
除將從完成滴下起至積層為止的時間設為70sec以外,其餘均實施與例5同樣的順序。The same procedure as in Example 5 was carried out except that the time from the completion of the dropping to the lamination was 70 sec.
除藉由將在樹脂層形成用光硬化性樹脂組成物滴下時,使滴下頭(噴嘴)依下示條件進行擺動而滴下的該硬化性樹脂組成物之等值圓直徑進行強制性擴展,而使存在於由密封部所包圍區域中的該硬化性樹脂組成物之等值圓直徑呈均勻以外,其餘均實施與例6同樣的順序。When the resin layer-forming photocurable resin composition is dropped, the isocratic diameter of the curable resin composition which is dropped by the dropping head (nozzle) under the following conditions is forcibly expanded. The same procedure as in Example 6 was carried out except that the equivalence circle diameter of the curable resin composition present in the region surrounded by the sealing portion was uniform.
‧第1~24點:無擺動‧1st to 24th points: no swing
‧第25~27點:擺動振幅0.5mm‧25th to 27th: swing amplitude 0.5mm
‧第28~32點:擺動振幅1.0mm‧28th to 32nd point: swing amplitude 1.0mm
‧第33~40點:擺動振幅1.5mm‧33~40 points: swing amplitude 1.5mm
[表1][Table 1]
例1中,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,並無存在Dnon-pore 達100μm以上的空隙。由此結果得知,當實施真空積層之際,存在於基板A由密封部所包圍區域中的硬化性樹脂組成物層呈滿足上述(1)~(3)的狀態。In Example 1, in the curable resin composition layer of the laminate after standing for 10 minutes, there was no void in which D non-pore was 100 μm or more. As a result, when the vacuum layer is formed, the curable resin composition layer in the region surrounded by the sealing portion of the substrate A satisfies the above conditions (1) to (3).
另一方面,使用硬化性樹脂組成物黏度低於例1的例2,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,空隙個數係1~30個/m2 。結果,因為經分散滴下後的硬化性樹脂組成物會更快速擴展,因而判斷當實施真空積層之際,部分會如第7(e)圖所示,形成空隙已消除狀態。On the other hand, the viscosity of the curable resin composition was lower than that of the example 2 of Example 1, and the number of voids in the layer of the curable resin composition of the laminate after standing for 10 minutes was 1 to 30/m 2 . As a result, since the curable resin composition after dispersion and dropping is more rapidly expanded, it is judged that when the vacuum lamination is performed, the portion is formed as shown in Fig. 7(e).
使用硬化性樹脂組成物黏度低於例2的例3,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,空隙個數係31個/m2 。由此結果得知,因為經分散滴下後的硬化性樹脂組成物會更快速擴展,因而呈第7(e)圖所示狀態的部分會更增加。The viscosity of the curable resin composition was lower than that of the example 3 of Example 2, and the number of voids was 31/m 2 in the layer of the curable resin composition of the laminate after standing for 10 minutes. As a result, it has been found that since the curable resin composition after dispersion and dropping is more rapidly expanded, the portion in the state shown in Fig. 7(e) is more increased.
使用與例3相同的硬化性樹脂組成物,但擴大滴下間距的例4,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,空隙個數係1~30個/m2 。由此結果得知,藉由所分散滴下的硬化性樹脂組成物彼此間之間隔擴大,相較於例3之下,呈第7(e)圖所示狀態的部分會減少。In the case of using the same curable resin composition as in Example 3, the number of voids was 1 to 30/m 2 in the layer of the curable resin composition of the laminate after standing for 10 minutes. . As a result, it was found that the interval between the curable resin compositions dispersed and dispersed was increased, and the portion shown in the seventh (e) diagram was reduced as compared with the case of Example 3.
基板尺寸大於例1的例5,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,空隙個數係31個/m2 以上。由此結果得知,滴下點數增加的結果,因為滴下時間(即開始滴下起至滴下完成為止所需要的時間)增加,因而當實施真空積層時,有部分會呈第7(e)圖所示空隙已消除狀態。The substrate size was larger than that of the example 5 of Example 1, and the number of voids was 31/m 2 or more in the layer of the curable resin composition of the laminate after standing for 10 minutes. From this result, it is found that as a result of the increase in the number of dropping points, since the dropping time (that is, the time required from the start of the dropping to the completion of the dropping) is increased, when the vacuum lamination is performed, part of it is shown in Fig. 7(e). The gap has been eliminated.
相對於例5,縮短從滴下完成起至積層為止之時間的例6,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,空隙個數係1~30個/m2 。由此結果得知,雖未生成有第7(e)圖所示狀態的部分,但卻有生成如第7(b)圖所示Dpore 大於10mm的部分。In the example 6 which shortens the time from the completion of the dropping to the lamination, the number of the voids is 1 to 30/m 2 in the curable resin composition layer of the laminated body after standing for 10 minutes. As a result, it was found that although the portion shown in the state shown in Fig. 7(e) was not formed, a portion in which D pore was larger than 10 mm as shown in Fig. 7(b) was generated.
相對於例6,在硬化性樹脂組成物滴下時使滴下頭擺動的例7,經靜置10分鐘後的積層體之硬化性樹脂組成物層中,並無存在直徑達100μm以上的空隙。由此結果得知,藉由滴下頭的擺動而分散滴下的硬化性樹脂組成物之等值圓直徑會擴大,在滴下完成時的硬化性樹脂組成物之等值圓直徑呈均勻。由此結果得知,實施真空積層之際,存在於基板A由密封部所包圍區域中的硬化性樹脂組成物層,呈滿足上述(1)~(3)的狀態。In the example 7 in which the dripping head was swayed when the curable resin composition was dropped, the voids having a diameter of 100 μm or more were not present in the curable resin composition layer of the laminate after standing for 10 minutes. As a result, it is found that the equivalence circle diameter of the curable resin composition dispersed and dropped by the swing of the dropping head is enlarged, and the equivalence circle diameter of the curable resin composition at the time of completion of the dropping is uniform. As a result, when the vacuum layer is formed, the curable resin composition layer in the region surrounded by the sealing portion of the substrate A satisfies the above (1) to (3).
依照與例1同樣的順序,在基板A上形成厚度1mm的密封部。但,基板A係使用長1110mm、寬970mm、厚2mm的鈉鈣玻璃製基板,沿該基板外周部距內側4mm的位置形成密封部。另外,在密封部形成時,使用與例1相同的密封部形成用光硬化性樹脂組成物X。In the same procedure as in Example 1, a sealing portion having a thickness of 1 mm was formed on the substrate A. However, the substrate A was made of a soda lime glass substrate having a length of 1110 mm, a width of 970 mm, and a thickness of 2 mm, and a sealing portion was formed at a position 4 mm from the inner side of the outer peripheral portion of the substrate. In addition, when the sealing portion was formed, the photocurable resin composition X for forming a sealing portion similar to that of Example 1 was used.
其次,在密封部所包圍區域中,將硬化性樹脂組成物塗佈成如第15圖所示的振動曲線30a、30b。硬化性樹脂組成物係使用與例1的樹脂層形成用光硬化性樹脂組成物Y相同者。但,使用25℃下的黏度為2Pa‧s之硬化性樹脂組成物。塗佈條件係如下。Next, the curable resin composition is applied to the vibration curves 30a and 30b as shown in Fig. 15 in the region surrounded by the sealing portion. The curable resin composition is the same as the photocurable resin composition Y for forming a resin layer of Example 1. However, a curable resin composition having a viscosity of 2 Pa ‧ at 25 ° C was used. The coating conditions are as follows.
(塗佈條件)(coating conditions)
‧振動曲線:正弦曲線‧Vibration curve: sinusoid
‧週期X:20mm‧Period X: 20mm
‧振幅Y:10mm‧Amplitude Y: 10mm
‧剛塗佈後的振動曲線粗細度m:6mm‧The thickness of the vibration curve just after coating is m: 6mm
振動曲線的厚度係設定成在真空積層時,硬化性樹脂組成物層的厚度與例1的厚度相同之狀態。就此點,例9~例15亦同。The thickness of the vibration curve is set to a state in which the thickness of the curable resin composition layer is the same as the thickness of Example 1 at the time of vacuum lamination. In this regard, the same applies to Examples 9 to 15.
‧振動曲線與密封部間之最短距離d(s-r) :0mm‧The shortest distance between the vibration curve and the seal d (sr) : 0mm
‧相鄰接之振動曲線彼此間的最短距離d(r-r) :0mm‧The shortest distance d (rr) between adjacent vibration curves: 0mm
‧塗佈裝置:具定量泵16分支頭的塗佈裝置、使用3台‧Coating device: Coating device with a branching head of the dosing pump 16, using 3 sets
(依20×16×3=960mm寬度施行塗佈)(Applicable according to 20×16×3=960mm width)
由下式所求得在振動曲線的振幅Y方向上的空隙直徑E係8mm。The void diameter E in the amplitude Y direction of the vibration curve was obtained by the following equation and was 8 mm.
E=2Y-2mE=2Y-2m
經硬化性樹脂組成物塗佈後,便實施與例1同樣的順序。但,從滴下完成起至積層為止的時間係設為50sec。After the curable resin composition was applied, the same procedure as in Example 1 was carried out. However, the time from the completion of the dropping to the lamination is 50 sec.
除將滴下完成起至積層為止的時間設為25sec之外,其餘均實施與例8同樣的順序。The same procedure as in Example 8 was carried out except that the time from the completion of the dropping to the lamination was 25 sec.
除將振動曲線與密封部間之最短距離d(s-r) 設為1.5mm,並將相鄰接之振動曲線彼此間的最短距離d(r-r )設為3mm之外,其餘均實施與例8同樣的順序。The same procedure as in Example 8 was carried out except that the shortest distance d (sr) between the vibration curve and the sealing portion was set to 1.5 mm, and the shortest distance d (rr ) between the adjacent vibration curves was set to 3 mm. order of.
振動曲線的振幅Y方向上的空隙直徑E係2mm。The gap diameter E in the amplitude Y direction of the vibration curve is 2 mm.
除將剛塗佈後的振動曲線粗細度m設為3mm之外,其餘均實施與例10同樣的順序。此處,振動曲線的振幅Y方向上的空隙直徑E係8mm。The same procedure as in Example 10 was carried out except that the thickness m of the vibration curve immediately after application was set to 3 mm. Here, the gap diameter E in the amplitude Y direction of the vibration curve is 8 mm.
除將剛塗佈後的振動曲線粗細度m設為9mm之外,其餘均實施與例10同樣的順序。The same procedure as in Example 10 was carried out except that the thickness m of the vibration curve immediately after application was set to 9 mm.
振動曲線的振幅Y方向上的空隙直徑E係-4mm。此處,空隙直徑E成為負值乙事,係表示在形成空隙時,相鄰接之振動曲線彼此間有發生重疊情形。The gap diameter E in the amplitude Y direction of the vibration curve is -4 mm. Here, the void diameter E is a negative value, and it means that when the void is formed, the adjacent vibration curves overlap each other.
除將振動曲線的週期X設為15mm,並將振幅Y設為7.5mm之外,其餘均實施與例10同樣的順序。The same procedure as in Example 10 was carried out except that the period X of the vibration curve was set to 15 mm and the amplitude Y was set to 7.5 mm.
振動曲線的振幅Y方向上的空隙直徑E係-3mm。The gap diameter E in the amplitude Y direction of the vibration curve is -3 mm.
除將振動曲線的週期X設為25mm,並將振幅Y設為12.5mm之外,其餘均實施與例10同樣的順序。The same procedure as in Example 10 was carried out except that the period X of the vibration curve was set to 25 mm and the amplitude Y was set to 12.5 mm.
振動曲線的振幅Y方向上的空隙直徑E係7mm。The gap diameter E in the amplitude Y direction of the vibration curve is 7 mm.
除將滴下完成起至積層為止的時間設為50sec之外,其餘均實施與例14同樣的順序。The same procedure as in Example 14 was carried out except that the time from the completion of the dropping to the lamination was 50 sec.
例8中,在靜置10分鐘後的積層體之硬化性樹脂組成物層中,並無存在直徑達100μm以上的空隙。由此結果得知,當實施真空積層之際,存在於基板A由密封部所包圍區域中的硬化性樹脂組成物層,呈滿足上述(1)~(3)的狀態。In Example 8, in the curable resin composition layer of the laminate after standing for 10 minutes, voids having a diameter of 100 μm or more were not present. As a result, when the vacuum layer is formed, the curable resin composition layer in the region surrounded by the sealing portion of the substrate A satisfies the above (1) to (3).
另一方面,從滴下完成起至積層為止的時間較例8短的例9,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,空隙個數係1~30個/m2 。由此結果得知,如第7(b)圖所示有生成Dpore 大於10mm的部分。On the other hand, in the case of the example 9 which is shorter than the example 8 after the completion of the dropping, the number of the voids is 1 to 30/m in the layer of the curable resin composition of the laminate after standing for 10 minutes. 2 . From this result, it is found that as shown in Fig. 7(b), a portion in which D pore is larger than 10 mm is generated.
例10中,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,並無存在直徑達100μm以上的空隙。由此結果得知,當實施真空積層之際,存在於基板A由密封部所包圍區域中的硬化性樹脂組成物層,呈滿足上述(1)~(3)的狀態。In Example 10, voids having a diameter of 100 μm or more were not present in the layer of the curable resin composition of the laminate after standing for 10 minutes. As a result, when the vacuum layer is formed, the curable resin composition layer in the region surrounded by the sealing portion of the substrate A satisfies the above (1) to (3).
相對於例10,將剛塗佈後的振動曲線粗細度m設為較細的例11,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,空隙個數係1~30個/m2 。由此結果得知,當實施真空積層之際,如第7(b)圖所示有生成Dpore 大於10mm的部分。With respect to Example 10, the thickness of the vibration curve immediately after application was set to be finer in Example 11, and in the layer of the curable resin composition of the laminate after standing for 10 minutes, the number of voids was 1 to 30. /m 2 . From this result, it is found that when vacuum lamination is performed, as shown in Fig. 7(b), a portion having a D pore of more than 10 mm is formed.
相對於例10,將剛塗佈後的振動曲線粗細度m設為較粗的例12,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,空隙個數達31個/m2 以上。例12中,因為振動曲線的振幅(Y)方向上的空隙直徑E係-4mm,因而判斷在形成空隙時,相鄰接之振動曲線彼此間有發生重疊的情形。由此結果得知,當實施真空積層之際,有部分如第7(e)圖所示的空隙已為消除狀態。With respect to Example 10, the thickness m of the vibration curve immediately after application was set to be thicker, and in the case of the curable resin composition layer of the laminate after standing for 10 minutes, the number of voids was 31/ m 2 or more. In Example 12, since the gap diameter E in the amplitude (Y) direction of the vibration curve is -4 mm, it is judged that the adjacent vibration curves overlap each other when the void is formed. As a result, it was found that when the vacuum lamination was carried out, the void as shown in Fig. 7(e) was partially eliminated.
相對於例10,縮小振動曲線之週期X與振幅Y的例13,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,空隙個數達31個/m2 以上。例13中,因為振動曲線的振幅Y方向上的空隙直徑E係-3mm,因而判斷在形成空隙時,相鄰接之振動曲線彼此間有發生重疊的情形。由此結果得知,當實施真空積層之際,有部分如第7(e)圖所示的空隙已為消除狀態。With respect to Example 10, in the example 13 in which the period X and the amplitude Y of the vibration curve were reduced, the number of voids in the layer of the curable resin composition of the laminate after standing for 10 minutes was 31/m 2 or more. In Example 13, since the gap diameter E in the amplitude Y direction of the vibration curve is -3 mm, it is judged that the adjacent vibration curves overlap with each other when the void is formed. As a result, it was found that when the vacuum lamination was carried out, the void as shown in Fig. 7(e) was partially eliminated.
相對於例10,放大振動曲線之週期X與振幅Y的例14,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,空隙個數係1~30個/m2 。由此結果得知,當實施真空積層之際,如第7(b)圖所示有生成Dpore 大於10mm的部分。With respect to Example 10, in Example 14 in which the period X and the amplitude Y of the vibration curve were enlarged, the number of voids in the layer of the curable resin composition of the laminate after standing for 10 minutes was 1 to 30/m 2 . From this result, it is found that when vacuum lamination is performed, as shown in Fig. 7(b), a portion having a D pore of more than 10 mm is formed.
相對於例14,拉長從滴下完成起至積層為止的時間之例15,在經靜置10分鐘後的積層體之硬化性樹脂組成物層中,並無存在直徑達100μm以上的空隙。由此結果得知,藉由更縮小Dpore ,當實施真空積層之際,存在於基板A由密封部所包圍區域中的硬化性樹脂組成物層,呈滿足上述(1)~(3)的狀態。In the case of the example 15 in which the time from the completion of the dropping to the lamination was carried out, the voids having a diameter of 100 μm or more were not present in the curable resin composition layer of the laminate after standing for 10 minutes. From this result that, by a more narrow D pore, when a vacuum laminate occasion, the substrate is present in the A layer surrounded by a sealing portion region curable resin, form satisfies the above (1) to (3) status.
根據本發明積層體的製造方法,可縮短在製造積層體的過程中所實施之將由一對基板與密封部所密閉的空間整體,利用硬化性樹脂組成物均勻填充的所需時間,俾可提升積層體的生產性。According to the method for producing a laminated body of the present invention, it is possible to shorten the time required for the entire space sealed by the pair of substrates and the sealing portion to be uniformly filled by the curable resin composition, which can be improved in the process of manufacturing the laminated body. The productivity of the laminate.
另外,2009年11月5日所提出申請的日本專利申請案2009-253984號的說明書、申請專利範圍、圖式及摘要之全部內容均爰引於本案中,並融入為本發明的揭示。In addition, the entire contents of the specification, the scope of the application, the drawings and the abstract of the Japanese Patent Application No. 2009-253984, filed on November 5, 2009, are hereby incorporated by reference.
10...基板10. . . Substrate
20...密封部20. . . Sealing part
30...硬化性樹脂組成物30. . . Curable resin composition
30...硬化性樹脂組成物層30. . . Curable resin composition layer
30a、30a’、30a”、30b、30b’、30d、30e...振動曲線30a, 30a', 30a", 30b, 30b', 30d, 30e... vibration curve
30c、30f、30g...直線30c, 30f, 30g. . . straight line
31...寬幅部位31. . . Wide area
40、41...空隙40, 41. . . Void
100、101、102、103、104...噴嘴100, 101, 102, 103, 104. . . nozzle
101、102、103、104...多點噴嘴(分支噴嘴)101, 102, 103, 104. . . Multi-nozzle (branch nozzle)
Dpore ...存在於前述硬化性樹脂組成物層中之空隙,其投影形狀的等值圓直徑D pore . . . The voids present in the layer of the curable resin composition, the equivalent circle diameter of the projected shape
Dnon-pore ...硬化性樹脂組成物之層中未存在有空隙之部分,其投影形狀的等值圓直徑D non-pore . . . a portion of the layer of the curable resin composition where no void exists, and the equivalent circular diameter of the projected shape
E...空隙的直徑E. . . Diameter of the gap
m、ma、mb...粗細度m, ma, mb. . . Thickness
X...週期X. . . cycle
Y、Ya、Yb...振幅Y, Ya, Yb. . . amplitude
第1圖係基板的平面圖,在基板上的周邊部形成密封部狀態。Fig. 1 is a plan view showing a state in which a sealing portion is formed in a peripheral portion of the substrate.
第2圖係基板的平面圖,在基板由密封部所包圍的部分中形成硬化性樹脂組成物層的狀態。Fig. 2 is a plan view showing a state in which a curable resin composition layer is formed in a portion of the substrate surrounded by the sealing portion.
第3(a)~(c)圖係對基板之由密封部所包圍區域點狀分散滴下之硬化性樹脂組成物的經時變化圖。Figs. 3(a) to 3(c) are diagrams showing temporal changes of the curable resin composition which is dotted and dispersed in a region surrounded by the sealing portion of the substrate.
第4(a)~(d)圖係硬化性樹脂組成物在第3(a)圖所示狀態時施行真空積層的情況下,硬化性樹脂組成物在真空積層時及解除減壓環境後的狀態圖。When the vacuum-curable resin composition of the fourth (a) to (d) is subjected to vacuum lamination in the state shown in Fig. 3(a), the curable resin composition is laminated at the time of vacuum lamination and after the decompression environment is released. State diagram.
第5(a)~(d)圖係硬化性樹脂組成物在第3(b)圖所示狀態時施行真空積層的情況下,硬化性樹脂組成物在真空積層時及解除減壓環境後的狀態圖。When the vacuum-curable resin composition of the fifth (a) to (d) is subjected to vacuum lamination in the state shown in Fig. 3(b), the curable resin composition is laminated at the time of vacuum lamination and after the decompression environment is released. State diagram.
第6(a)~(d)圖係硬化性樹脂組成物在第3(c)圖所示狀態時施行真空積層的情況下,硬化性樹脂組成物在真空積層時及解除減壓環境後的狀態圖。In the case where the vacuum-curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3(c), the curable resin composition is subjected to vacuum lamination and after the decompression environment is released. State diagram.
第7(a)~(e)圖係對基板之由密封部所包圍區域點狀分散滴下之硬化性樹脂組成物的經時變化圖。The seventh (a) to (e) drawings are time-dependent changes of the curable resin composition which is dotted and dispersed in a region surrounded by the sealing portion of the substrate.
第8圖係使用單點噴嘴,對基板由密封部所包圍區域分散滴下硬化性樹脂組成物的順序圖。Fig. 8 is a sequence diagram in which a hard-pointing resin composition is dispersed and dropped on a substrate surrounded by a sealing portion using a single-point nozzle.
第9圖係使用多點噴嘴,對基板由密封部所包圍區域分散滴下硬化性樹脂組成物的順序圖。Fig. 9 is a sequence diagram in which a multi-point nozzle is used to disperse and deposit a curable resin composition on a substrate surrounded by a sealing portion.
第10圖係使用多點噴嘴,對基板由密封部所包圍區域分散滴下硬化性樹脂組成物的順序圖。Fig. 10 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.
第11圖係使用多點噴嘴,對基板由密封部所包圍區域分散滴下硬化性樹脂組成物的順序圖。Fig. 11 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.
第12圖係使用多點噴嘴,對基板由密封部所包圍區域分散滴下硬化性樹脂組成物的順序圖。Fig. 12 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.
第13圖係滴下後的經過時間t(sec)、與硬化性樹脂組成物的等值圓直徑d(mm)間之關係圖。Fig. 13 is a graph showing the relationship between the elapsed time t (sec) after dropping and the equivalent circle diameter d (mm) of the curable resin composition.
第14圖係滴下後的經過時間t、硬化性樹脂組成物的等值圓直徑d、及所存在硬化性樹脂組成物層中之空隙的等值圓直徑Dpore 間之關係圖。Fig. 14 is a graph showing the relationship between the elapsed time t after dropping, the equivalence circle diameter d of the curable resin composition, and the equivalence circle diameter D pore of the voids in the curable resin composition layer.
第15圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 15 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第16圖係相當於第15圖之部分放大圖,顯示振動曲線30a、30b形狀的經時變化。Fig. 16 is a partial enlarged view corresponding to Fig. 15, showing temporal changes in the shape of the vibration curves 30a, 30b.
第17圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 17 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第18圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 18 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第19圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 19 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第20圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 20 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第21圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 21 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第22圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 22 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第23圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 23 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
第24圖係將硬化性樹脂組成物呈線狀塗佈時的較佳塗佈形態圖。Fig. 24 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.
10...基板10. . . Substrate
20...密封部20. . . Sealing part
30...硬化性樹脂組成物層30. . . Curable resin composition layer
40...空隙40. . . Void
Dpore ...存在於前述硬化性樹脂組成物層中之空隙,其投影形狀的等值圓直徑D pore . . . The voids present in the layer of the curable resin composition, the equivalent circle diameter of the projected shape
Dnon-pore ...硬化性樹脂組成物之層中未存在有空隙之部分,其投影形狀的等值圓直徑D non-pore . . . a portion of the layer of the curable resin composition where no void exists, and the equivalent circular diameter of the projected shape
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JP2003222909A (en) * | 2001-11-26 | 2003-08-08 | Three M Innovative Properties Co | Method for manufacturing laminated article with cured resin layer |
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JP5445589B2 (en) | 2014-03-19 |
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