TWI591089B - Permeability resin composition, cured product and use thereof - Google Patents

Permeability resin composition, cured product and use thereof Download PDF

Info

Publication number
TWI591089B
TWI591089B TW100128662A TW100128662A TWI591089B TW I591089 B TWI591089 B TW I591089B TW 100128662 A TW100128662 A TW 100128662A TW 100128662 A TW100128662 A TW 100128662A TW I591089 B TWI591089 B TW I591089B
Authority
TW
Taiwan
Prior art keywords
compound
resin composition
ether
electronic device
group
Prior art date
Application number
TW100128662A
Other languages
Chinese (zh)
Other versions
TW201211094A (en
Inventor
板谷亮
Original Assignee
戴西爾化學工業股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 戴西爾化學工業股份有限公司 filed Critical 戴西爾化學工業股份有限公司
Publication of TW201211094A publication Critical patent/TW201211094A/en
Application granted granted Critical
Publication of TWI591089B publication Critical patent/TWI591089B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/36—Epoxy compounds containing three or more epoxy groups together with mono-epoxy compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12044—OLED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/842—Containers
    • H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • Electroluminescent Light Sources (AREA)
  • Epoxy Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

樹脂組成物、其硬化物及其用途 Resin composition, cured product thereof and use thereof

本發明係關於一種有機電致發光元件、電子紙、太陽能電池等被要求有低透濕性的電子裝置用之低透濕性樹脂組成物及其硬化物、用以形成低透濕性封閉材之封閉劑、用以形成低透濕性密封材之密封劑、及使用此等之有機電致發光元件、電子紙及太陽能電池。The present invention relates to a low moisture permeability resin composition for an electronic device which is required to have low moisture permeability, such as an organic electroluminescence element, an electronic paper, a solar cell, and the like, and a cured product thereof for forming a low moisture permeability sealing material. A sealant, a sealant for forming a low moisture permeability sealant, an organic electroluminescence device using the same, an electronic paper, and a solar cell.

本發明係尋求一種能夠用於有機電致發光元件、電子紙、太陽能電池等之被要求有低透濕性的電子裝置用之低透濕性封閉材及密封材等賦予低透濕性之硬化物的樹脂組成物。有人提案一種樹脂組成物，其含有20至80重量份之具有脂肪族環狀骨架的環氧化合物、及80至20重量份之具有芳香族環的環氧化合物與光陽離子聚合起始劑作為有機電致發光元件用封閉劑(參閱專利文獻1)。具體而言，具有脂肪族環狀骨架之環氧化合物、具有芳香族環之環氧化合物係記載在兩末端具有環氧基之化合物。然而，在85℃ 85%RH條件下，其硬化物之透濕度係55g/m2‧24h以上，尚未能夠符合。The present invention is directed to a low moisture permeability sealing material and a sealing material which can be used for an electronic device which is required to have low moisture permeability, such as an organic electroluminescence element, an electronic paper, a solar battery, etc., and a hardening property which imparts low moisture permeability. Resin composition of the substance. There has been proposed a resin composition containing 20 to 80 parts by weight of an epoxy compound having an aliphatic cyclic skeleton, and 80 to 20 parts by weight of an epoxy compound having an aromatic ring and a photocationic polymerization initiator as A blocking agent for electroluminescent elements (see Patent Document 1). Specifically, an epoxy compound having an aliphatic cyclic skeleton and an epoxy compound having an aromatic ring are described as compounds having an epoxy group at both terminals. However, at 85 ° C and 85% RH, the moisture permeability of the cured product was 55 g/m 2 ‧24 h or more, which was not able to be met.

另外，有人提案一種組成物，其含有：(A)1分子中具有至少2個以上環氧丙基、分子量為200至7000之環氧樹脂；(B)1分子中具有至少1個以上環氧丙基、分子量為20000至100000之環氧樹脂；(C)藉能量線照射而活化、產生酸的之潛在性光酸觸媒；及(D)分子中含有環氧丙基之矽烷偶合劑；一種有機EL元件密封用光硬化性樹脂組成物，其含有：相對於100重量份之該(A)成分，含有30至150重量份之該(B)成分，還有，並且相對於100重量份之該(A)成分及(B)成分的合計，含有0.1至10重量份之該(C)成分、含有0.1至10重量份之該(D)成分(參閱專利文獻2)。然而，針對其硬化物的透濕度則未被探討。Further, a composition has been proposed which comprises: (A) an epoxy resin having at least two or more epoxy propyl groups in a molecule of 200 to 7,000; (B) having at least one epoxy in one molecule; a propyl group, an epoxy resin having a molecular weight of 20,000 to 100,000; (C) a latent photoacid catalyst activated by an energy ray to generate an acid; and (D) a decane coupling agent containing a glycidyl group in the molecule; A photocurable resin composition for sealing an organic EL element, comprising: 30 to 150 parts by weight of the component (B) with respect to 100 parts by weight of the component (A), and further, and relative to 100 parts by weight The total of the components (A) and (B) is 0.1 to 10 parts by weight of the component (C) and 0.1 to 10 parts by weight of the component (D) (see Patent Document 2). However, the moisture permeability of the hardened material has not been investigated.

另外，也有人提案一種樹脂組成物，其含有(A)環氧化合物、(B)酚醛清漆樹脂、(C)光陽離子聚合起始劑、及(D)填料作為有機EL等元件封裝用接著劑(參閱專利文獻3)。然而，為了獲得低透濕性，必須要有填料，在不含填料之情形下，於60℃90%RH條件下，其硬化物之透濕度為60 g/m2‧24h，並不充分。Further, a resin composition containing (A) an epoxy compound, (B) a novolac resin, (C) a photocationic polymerization initiator, and (D) a filler as an adhesive for encapsulating an element such as an organic EL has also been proposed. (See Patent Document 3). However, in order to obtain low moisture permeability, it is necessary to have a filler, and in the absence of a filler, the moisture permeability of the cured product at 60 ° C and 90% RH is 60 g / m 2 ‧ 24 h, which is not sufficient.

先前技術文獻Prior technical literature 專利文獻Patent literature

專利文獻1　日本特開2007-46035號公報Patent Document 1 Japanese Patent Laid-Open Publication No. 2007-46035

專利文獻2　日本特開2010-126699號公報Patent Document 2 Japanese Patent Laid-Open Publication No. 2010-126699

專利文獻3　日本專利第2010-24364號公報Patent Document 3 Japanese Patent No. 2010-24364

本發明之目的係在於提供一種樹脂組成物，其能夠作為有機電致發光元件、電子紙、太陽能電池等之被要求有低透濕性之電子裝置用低透濕性封閉材及密封材等使用之賦予具優越之低透濕性的硬化物。An object of the present invention is to provide a resin composition which can be used as a low moisture permeability sealing material and a sealing material for an electronic device requiring low moisture permeability, such as an organic electroluminescence device, an electronic paper, or a solar battery. It imparts a cured product with superior low moisture permeability.

另外，本發明之其他目的係於提供一種低透濕性硬化物，其係使上述低透濕性樹脂組成物硬化所獲得。Further, another object of the present invention is to provide a low moisture-permeable cured product obtained by hardening the above-mentioned low moisture-permeable resin composition.

還有，本發明之其他目的係於提供一種密封劑，其形成具有優異的低透濕性之低透濕性封閉材及密封材之封閉劑及密封劑。Further, another object of the present invention is to provide a sealant which forms a sealer and a sealant for a low moisture permeability sealant and a sealant having excellent low moisture permeability.

另外還有，本發明之其他目的係於提供一種有機電致發光元件、電子紙、太陽能電池，其係藉由利用上述低透濕性封閉材或密封材封閉或密封電子裝置而減低濕氣之影響。In addition, another object of the present invention is to provide an organic electroluminescence device, an electronic paper, and a solar cell, which are capable of reducing moisture by enclosing or sealing an electronic device by using the above-mentioned low moisture permeability sealing material or sealing material. influences.

本發明人等為了解決上述課題而鑽研的結果，發現下列事實而完成本發明：藉由將具有特定構造且具有1個反應性官能基之化合物摻合於具有2個以上反應性官能基之化合物中而使其聚合，來使樹脂硬化物之交聯密度變小，另一方面源自聚合物中之具有1個該特定構造反應性基的材料之側鏈展現填塞自由體積之效果；也藉由硬化僅由具有該2個以上反應性官能之樹脂所構成的樹脂之硬化物而改善透濕度，特別有用於有機電致發光元件、電子紙、太陽能電池等之被要求有低透濕性之電子裝置用。In order to solve the above problems, the inventors of the present invention have found the present invention by incorporating a compound having a specific structure and having one reactive functional group into a compound having two or more reactive functional groups. Polymerizing to reduce the crosslink density of the cured resin, and on the other hand, the side chain of the material having one of the specific structural reactive groups in the polymer exhibits the effect of packing the free volume; The moisture permeability is improved by hardening a resin composed only of a resin having the two or more reactive functions, and particularly used for an organic electroluminescence device, an electronic paper, a solar battery, or the like, which is required to have low moisture permeability. For electronic devices.

亦即，本發明係提供一種被要求有低透濕性的電子裝置用低透濕性樹脂組成物，其特徵為含有：1分子中具有2個以上反應性官能基(a)之化合物(A)、1分子中具有1個反應性官能基(b)且分子量為50至1000之化合物(B)、與聚合起始劑(C)。That is, the present invention provides a low moisture permeability resin composition for an electronic device which is required to have low moisture permeability, and is characterized by containing: a compound having two or more reactive functional groups (a) in one molecule (A) a compound (B) having one reactive functional group (b) in one molecule and having a molecular weight of from 50 to 1,000, and a polymerization initiator (C).

上述該化合物(A)與/或該化合物(B)較佳為具有1個以上環狀骨架。The compound (A) and/or the compound (B) preferably have one or more cyclic skeletons.

另外，上述環狀骨架較佳為相同或不同的苯環或環己烷環。Further, the above cyclic skeleton is preferably the same or different benzene ring or cyclohexane ring.

相對於100重量份之上述化合物(A)，上述化合物(B)之含量較佳為1至1000重量份，進一步較佳為10至250重量份。The content of the above compound (B) is preferably from 1 to 1,000 parts by weight, still more preferably from 10 to 250 parts by weight, per 100 parts by weight of the above compound (A).

上述電子裝置用低透濕性樹脂組成物也可以進一步含有無機填料(D)。The low moisture permeability resin composition for an electronic device may further contain an inorganic filler (D).

另外，上述電子裝置用低透濕性樹脂組成物也可以進一步含有矽烷偶合劑(E)。Further, the low moisture permeability resin composition for an electronic device may further contain a decane coupling agent (E).

上述聚合起始劑(C)較佳為光或熱陽離子聚合起始劑、或是光或熱自由基聚合起始劑。The above polymerization initiator (C) is preferably a photo or thermal cationic polymerization initiator or a photo or thermal radical polymerization initiator.

另外，在上述電子裝置用低電子裝置用低透濕性樹脂組成物中之電子裝置較佳為有機電致發光元件、電子紙或太陽能電池。Further, the electronic device in the low moisture permeability resin composition for a low electronic device for an electronic device is preferably an organic electroluminescence device, an electronic paper or a solar cell.

另外，本發明係提供一種硬化物，其係將上述電子裝置用低透濕性樹脂組成物硬化而成。Further, the present invention provides a cured product obtained by hardening the above-mentioned electronic device with a low moisture-permeable resin composition.

另外，本發明係提供一種封閉劑，其含有上述電子裝置用低透濕性樹脂組成物。Further, the present invention provides a blocking agent comprising the above-mentioned low moisture permeable resin composition for an electronic device.

另外，本發明係提供一種密封劑，其含有上述電子裝置用低透濕性樹脂組成物。Further, the present invention provides a sealant comprising the above-mentioned low moisture permeability resin composition for an electronic device.

另外，本發明係提供一種有機電致發光元件，其含有上述硬化物。Further, the present invention provides an organic electroluminescence element comprising the above-mentioned cured product.

另外，本發明係提供一種電子紙，其含有上述硬化物。Further, the present invention provides an electronic paper containing the above cured product.

另外，本發明係提供一種太陽能電池，其含有上述硬化物。Further, the present invention provides a solar cell comprising the above cured product.

若根據本發明，則可以獲得一種樹脂組成物及其硬化物，該樹脂組成物改善有機電致發光元件、電子紙、太陽能電池等之被要求有低透濕性之電子裝置用的透濕度，並賦予具有100至200℃之耐熱性的硬化物。另外，若根據本發明，則可以獲得一種封閉劑及密封劑，能夠形成有機電致發光元件、電子紙、太陽能電池等之被要求有低透濕性之電子裝置用的具有優異之低透濕性的硬化物(封閉材、密封材)。含有有關本發明之低透濕性樹脂組成物硬化物之有機電致發光元件、電子紙、太陽能電池係將濕度之影響抑制至最小限度。According to the present invention, it is possible to obtain a resin composition which improves the moisture permeability of an electronic device which is required to have low moisture permeability, such as an organic electroluminescence device, an electronic paper, a solar battery, and the like, and a cured product thereof. And a cured product having heat resistance of 100 to 200 ° C is imparted. Further, according to the present invention, it is possible to obtain a sealant and a sealant, and it is possible to form an excellent low moisture permeability for an electronic device requiring low moisture permeability such as an organic electroluminescence device, an electronic paper, or a solar battery. Sexual hardened material (closed material, sealing material). The organic electroluminescence device, the electronic paper, and the solar cell system containing the cured product of the low moisture-permeable resin composition of the present invention minimize the influence of humidity.

[用於實施發明之形態][Formation for implementing the invention] ＜電子裝置用低透濕性樹脂組成物＞<Low moisture permeable resin composition for electronic devices>

本發明之電子裝置用低透濕性樹脂組成物，其特徵為含有以1分子中具有2個以上反應性官能基(a)之化合物(A)、1分子中具有1個反應性官能基(b)且分子量為50至1000之化合物(B)、與聚合起始劑(C)作為必要成分。The low moisture-permeable resin composition for an electronic device according to the present invention, which comprises a compound (A) having two or more reactive functional groups (a) in one molecule, and one reactive functional group in one molecule ( b) The compound (B) having a molecular weight of 50 to 1000 and the polymerization initiator (C) are essential components.

一般而言，硬化含有交聯性多官能基之樹脂材料的硬化物(樹脂硬化物)係具有來自於材料骨架之固有的透濕度，通常在將所謂稀釋劑之含有1官能基的材料摻合於上述樹脂材料中之情形，由於使共聚合之聚合物的交聯點距離變長，一般也較在樹脂單體中之透濕度變得更高。另外，認為樹脂硬化物係通常藉由將聚合起始劑摻合於具有2個以上反應性官能基之樹脂中，利用熱或光來使聚合起始劑活化而使其交聯硬化後製得，但主要水蒸氣係從進行材料交聯之際所形成的自由體積而穿透出。In general, a cured product (resin cured product) which hardens a resin material containing a crosslinkable polyfunctional group has a moisture permeability inherent from a material skeleton, and is usually blended with a material containing a 1-functional group of a diluent. In the case of the above resin material, since the crosslinking point distance of the copolymerized polymer becomes long, the moisture permeability in the resin monomer generally becomes higher. Further, it is considered that a resin cured product is usually obtained by blending a polymerization initiator in a resin having two or more reactive functional groups, and activating the polymerization initiator by heat or light to obtain a cross-linking and hardening. However, the main water vapor is penetrated from the free volume formed when the material is crosslinked.

於本發明中，藉由使1分子中具有1個反應性官能基(b)且分子量為50至1000之化合物(B)摻合於1分子中具有2個以上反應性官能基(a)之化合物(A)中來使其聚合，而使得樹脂硬化物之交聯密度變小，另一方面，聚合物中之源自該化合物(B)的單體單位展現聚合物之側鏈填塞自由體積之效果，也較硬化僅由該化合物(A)所構成的樹脂之硬化物更能夠改善透濕度。In the present invention, a compound (B) having one reactive functional group (b) in one molecule and having a molecular weight of 50 to 1000 is blended in one molecule and has two or more reactive functional groups (a). The compound (A) is polymerized to make the crosslinking density of the cured product of the resin small, and on the other hand, the monomer unit derived from the compound (B) in the polymer exhibits a free packing volume of the side chain of the polymer. The effect is also that the moisture permeability can be improved more than the hardened material of the resin composed only of the compound (A).

以下，示意顯示在本發明之聚合物的自由體積的填塞構造。標記A之橢圓係源自化合物(A)之單體單位(2官能之情形)、標記B之橢圓係源自化合物(B)之單體單位、兩側之波狀線係表示聚合物之主鏈。認為源自化合物(B)之單體單位填埋源自化合物(A)之單體單位的間隙而將自由體積予以填塞。Hereinafter, the free-volume packing structure of the polymer of the present invention is schematically shown. The ellipsoid of the label A is derived from the monomer unit of the compound (A) (in the case of the bifunctional group), the ellipsoid of the label B is derived from the monomer unit of the compound (B), and the wavy line system on both sides indicates the main component of the polymer. chain. It is considered that the monomer unit derived from the compound (B) is filled with a gap derived from the monomer unit of the compound (A) to fill the free volume.

若該化合物(A)及/或該化合物(B)(化合物(A)及化合物(B)中任一種或兩種)具有1個以上環狀骨架時，聚合物中之自由體積容易減少，更能夠改善透濕度而較佳。認為環狀骨架主要表示脂環式環狀骨架或芳香族環狀骨架，相乘性地源自脂環式環狀骨架及芳香族環狀骨架之疏水性、還有在芳香族環狀骨架之π-π堆積效果(積層芳香族環狀骨架)而達成透濕度之改善。在該化合物(A)與該化合物(B)皆具有環狀骨架之情形，各自的環狀骨架可以相同或不同。另外，化合物(A)或化合物(B)具有2個以上環狀骨架之情形，複數個環狀骨架也可以相同或不同。When the compound (A) and/or the compound (B) (either one or both of the compound (A) and the compound (B)) has one or more cyclic skeletons, the free volume in the polymer is easily reduced, and It is better to improve the moisture permeability. It is considered that the cyclic skeleton mainly represents an alicyclic cyclic skeleton or an aromatic cyclic skeleton, and is multiplied by the hydrophobicity of the alicyclic cyclic skeleton and the aromatic cyclic skeleton, and also in the aromatic cyclic skeleton. The π-π stacking effect (layered aromatic ring skeleton) achieves an improvement in moisture permeability. In the case where both the compound (A) and the compound (B) have a cyclic skeleton, the respective cyclic skeletons may be the same or different. Further, when the compound (A) or the compound (B) has two or more cyclic skeletons, the plurality of cyclic skeletons may be the same or different.

具體而言，環狀骨架可舉例：苯環、萘環、蒽環、菲環、茀環等之單環或縮合多環之芳香族環；環戊烷環、環己烷環、十氫萘環、降莰烷環、金剛烷環等之單環或多環之脂肪族環。還有，於本發明專利說明書中，將縮合n個環等之多環環狀骨架的數目係設為n個。化合物(A)1分子中之環狀骨架的數目例如為1至30個，較佳為1至10個，進一步較佳為1至6個，特佳為1至5個。化合物(B)1分子中之環狀骨架的數目例如為1至10個，較佳為1至6個，進一步較佳為1至3個。Specifically, the cyclic skeleton may, for example, be a monocyclic or condensed polycyclic aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring or an anthracene ring; a cyclopentane ring, a cyclohexane ring or a decahydronaphthalene; A monocyclic or polycyclic aliphatic ring of a ring, a norbornane ring, an adamantane ring or the like. Further, in the patent specification of the present invention, the number of the polycyclic ring skeletons condensing n rings or the like is set to n. The number of the cyclic skeleton in the molecule of the compound (A) is, for example, 1 to 30, preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 5. The number of the cyclic skeletons in the molecule of the compound (B) is, for example, 1 to 10, preferably 1 to 6, more preferably 1 to 3.

於化合物(A)中，環狀骨架較佳為含有苯環、萘環、茀環或環己烷環。另外，於化合物(B)中，環狀骨架較佳為含有苯環或環己烷環。In the compound (A), the cyclic skeleton preferably contains a benzene ring, a naphthalene ring, an anthracene ring or a cyclohexane ring. Further, in the compound (B), the cyclic skeleton preferably contains a benzene ring or a cyclohexane ring.

＜化合物(A)＞<compound (A)>

只要化合物(A)為1分子中具有2個以上反應性官能基(a)之化合物的話，並未予以特別限定。具體而言，反應性官能基(a)可舉例：環氧基、環氧丙基、乙烯基醚基等之具有陽離子基聚合性之基；(甲基)丙烯醯基等之具有自由基聚合性之基等。乙烯基醚基也有具有自由基聚合性之情形。反應性官能基(a)能夠較佳使用具有陽離子基聚合性之基，進一步較佳為環氧基，特佳為環氧丙基。化合物(A)1分子中之反應性官能基(a)的數目例如為2至30個，較佳為2至10個，進一步較佳為2至6個，特佳為2至3個。複數個反應性官能基(a)也可以為相同或不同。雖然化合物(A)之分子量並未予以特別限制，但重量平均分子量例如能夠設為100至100000，較佳設為100至50000。化合物(A)能夠使用單獨1種或組合2種以上而使用。The compound (A) is not particularly limited as long as it is a compound having two or more reactive functional groups (a) in one molecule. Specifically, the reactive functional group (a) may, for example, be a cationically polymerizable group such as an epoxy group, a propylene group or a vinyl ether group; or a radical polymerization having a (meth) acrylonitrile group or the like. The basis of sex. The vinyl ether group also has a case of radical polymerization. The reactive functional group (a) can preferably be a group having a cationic polymerizable group, more preferably an epoxy group, and particularly preferably a glycidyl group. The number of the reactive functional groups (a) in the molecule of the compound (A) is, for example, 2 to 30, preferably 2 to 10, further preferably 2 to 6, and particularly preferably 2 to 3. The plurality of reactive functional groups (a) may also be the same or different. Although the molecular weight of the compound (A) is not particularly limited, the weight average molecular weight can be, for example, from 100 to 100,000, preferably from 100 to 50,000. The compound (A) can be used alone or in combination of two or more.

例如，化合物(A)可舉例：1分子中具有2個以上陽離子聚合性官能基與芳香族環之化合物(A-1)；1分子中具有2個以上自由基聚合性官能基與芳香族環之化合物(A-2)；1分子中具有2個以上陽離子聚合性官能基與脂肪族環之化合物(A-3)；與1分子中具有2個以上自由基聚合性官能基與脂肪族環之化合物(A-4)等。For example, the compound (A) is exemplified by a compound (A-1) having two or more cationically polymerizable functional groups and an aromatic ring in one molecule; and two or more radical polymerizable functional groups and an aromatic ring in one molecule. Compound (A-2); a compound having two or more cationically polymerizable functional groups and an aliphatic ring in one molecule (A-3); and two or more radical polymerizable functional groups and an aliphatic ring in one molecule Compound (A-4) and the like.

具有芳香族環與2個以上陽離子聚合性官能基之化合物(A-1)，例如，可舉例：雙酚型二環氧丙基醚、雙酚A型二環氧丙基醚、雙酚F型二環氧丙基醚、雙酚S型二環氧丙基醚、四甲基雙酚型二環氧丙基醚等之具有苯環與2個環氧基之化合物；萘二醇二環氧丙基醚、雙酚茀二環氧丙基醚、雙甲酚茀二環氧丙基醚、雙苯氧基乙醇茀二環氧丙基醚等之具有縮合環與2個環氧基之化合物；具有如酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、含雙酚骨架之酚醛型環氧樹脂、含萘骨架之酚醛型環氧樹脂之重複單位的聚苯基環氧丙基醚類等之具有苯環及/或縮合環與2個以上環氧基之化合物；雙酚F雙(3-乙基環氧丙烷-3-基甲基)醚等之具有芳香族環與2個環氧丙基之化合物；雙酚二乙烯基醚、雙酚A二乙烯基醚、雙酚F二乙烯基醚、雙酚F雙(2-乙烯氧乙基)醚、雙酚S二乙烯基醚、四甲基雙酚二乙烯基醚等之具有苯環與2個乙烯基醚基之化合物；萘二醇二乙烯基醚、雙酚茀二乙烯基醚、雙甲酚茀二乙烯基醚、雙苯氧基乙醇茀二乙烯基醚等之具有縮合環與2個乙烯基醚基之化合物；及此等之鹵化物、或此等之C1-9烷基取代物等。在C1-9烷基取代物中之C1-9烷基取代基，可舉例：甲基、乙基、丙基、三級丁基等。鹵化物中之鹵素可舉例：F、Cl、Br等。The compound (A-1) having an aromatic ring and two or more cationically polymerizable functional groups may, for example, be bisphenol type diepoxypropyl ether, bisphenol A type diepoxypropyl ether, bisphenol F. a compound having a benzene ring and two epoxy groups, such as diglycidyl propyl ether, bisphenol S type diglycidyl ether, tetramethyl bisphenol type diglycidyl ether; Oxypropyl propyl ether, bisphenol quinone diepoxypropyl ether, biscresol quinone diepoxypropyl ether, bisphenoxyethanol hydrazine diepoxypropyl ether, etc. having a condensed ring and two epoxy groups a compound; a polyphenyl epoxypropyl group having a repeating unit such as a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a phenolic type epoxy resin containing a bisphenol skeleton, and a novolac type epoxy resin containing a naphthalene skeleton; a compound having a benzene ring and/or a condensed ring and two or more epoxy groups such as an ether; a bisphenol F bis(3-ethyl propylene oxide-3-ylmethyl) ether having an aromatic ring and 2 Epoxypropyl compound; bisphenol divinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, bisphenol F bis(2-vinyloxyethyl) ether, bisphenol S diethylene Ether, tetramethyl a compound having a benzene ring and two vinyl ether groups such as phenol divinyl ether; naphthalenediol divinyl ether, bisphenol quinone divinyl ether, biscresol quinone divinyl ether, bisphenoxyethanol a compound having a condensed ring and two vinyl ether groups such as stilbene vinyl ether; and such a halide or a C 1-9 alkyl substituent or the like. The C 1-9 alkyl substituent in the C 1-9 alkyl substituent may, for example, be a methyl group, an ethyl group, a propyl group, a tertiary butyl group or the like. The halogen in the halide can be exemplified by F, Cl, Br, and the like.

具有芳香族環與2個以上自由基聚合性官能基之化合物(A-2)，例如，可舉例：雙酚二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸酯、雙酚F二(甲基)丙烯酸酯、雙酚S二(甲基)丙烯酸酯、四甲基雙酚二(甲基)丙烯酸酯等之具有苯環與2個(甲基)丙烯醯基之化合物；萘二醇二(甲基)丙烯酸酯、雙酚茀二(甲基)丙烯酸酯、雙甲酚茀二(甲基)丙烯酸酯、雙苯甲氧乙醇茀二(甲基)丙烯酸酯等之具有縮合環與2個(甲基)丙烯醯基之化合物；及此等之鹵化物、或此等之C1-9烷基取代物等。在C1-9烷基取代物中之C1-9烷基取代基，可舉例：甲基、乙基、丙基、三級丁基等。在鹵化物中之鹵素可舉例：F、Cl、Br等。The compound (A-2) having an aromatic ring and two or more radical polymerizable functional groups may, for example, be bisphenol di(meth)acrylate, bisphenol A di(meth)acrylate, or bisphenol. a compound having a benzene ring and two (meth) acrylonitrile groups, such as F di(meth)acrylate, bisphenol S di(meth)acrylate, tetramethyl bisphenol di(meth)acrylate; Naphthalenediol di(meth)acrylate, bisphenolquinone di(meth)acrylate, biscresol quinone di(meth)acrylate, bisbenzyloxyethanol quinone di(meth)acrylate, etc. a compound of a condensed ring and two (meth)acryl fluorenyl groups; and such halides, or such C 1-9 alkyl substituents, and the like. The C 1-9 alkyl substituent in the C 1-9 alkyl substituent may, for example, be a methyl group, an ethyl group, a propyl group, a tertiary butyl group or the like. The halogen in the halide can be exemplified by F, Cl, Br and the like.

具有脂肪族環與2個以上陽離子聚合性官能基之化合物(A-3)，例如，可舉例：氫化雙酚A二環氧丙基醚、氫化雙酚F二環氧丙基醚、氫化雙酚S二環氧丙基醚、二環己基二環氧丙基醚、雙(3,4-環氧環己基)甲基、3’,4’-環氧環己基-3,4-環氧環己烷等之具有環己烷環與2個環氧基之化合物；具有環己烷環與2個環氧丙基之化合物；及氫化雙酚A二乙烯基醚基、氫化雙酚F二乙烯基醚、氫化雙酚S二乙烯基醚、二環己基二乙烯基醚等之具有環己烷環與2個乙烯基醚之化合物等。The compound (A-3) having an aliphatic ring and two or more cationically polymerizable functional groups may, for example, be hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated double Phenol S diglycidyl ether, dicyclohexyl diepoxypropyl ether, bis(3,4-epoxycyclohexyl)methyl, 3',4'-epoxycyclohexyl-3,4-epoxy a compound having a cyclohexane ring and two epoxy groups, such as cyclohexane; a compound having a cyclohexane ring and two epoxy propyl groups; and a hydrogenated bisphenol A divinyl ether group, hydrogenated bisphenol F II A compound having a cyclohexane ring and two vinyl ethers, such as vinyl ether, hydrogenated bisphenol S divinyl ether, and dicyclohexyl divinyl ether.

具有脂肪族環與2個以上自由基聚合性官能基之化合物(A-4)，例如，可舉例：氫化雙酚A二(甲基)丙烯酸酯、氫化雙酚F二(甲基)丙烯酸酯、氫化雙酚S二(甲基)丙烯酸酯、二環己基二(甲基)丙烯酸酯等之具有環己烷環與2個(甲基)丙烯醯基之化合物等。A compound (A-4) having an aliphatic ring and two or more radical polymerizable functional groups, for example, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate And a compound having a cyclohexane ring and two (meth) acrylonitrile groups, such as bisphenol S di(meth)acrylate or dicyclohexyl di(meth)acrylate.

另外，化合物(A)係例如以下式(1)所示之化合物：Further, the compound (A) is, for example, a compound represented by the following formula (1):

[式(1)中，Z1係表示從m價之多元羥基化合物(Z1(OH)m)除去m個OH基之基，R1係表示環氧丙基、也可以具有取代基之環氧丙基甲基、乙烯基、或(甲基)丙烯醯基。m係2以上之整數]。上述Z1較佳為具有環狀骨架之基。環狀骨架可舉例前述例示之物。[In the formula (1), Z 1 represents a group in which m OH groups are removed from an m-valent polyvalent hydroxy compound (Z 1 (OH) m ), and R 1 represents a glycidyl group, and may have a ring of a substituent. Oxypropylmethyl, vinyl, or (meth)acrylonitrile. m is an integer of 2 or more]. The above Z 1 is preferably a group having a cyclic skeleton. The cyclic skeleton can be exemplified by the aforementioned examples.

m價之多元羥基化合物Z1(OH)m可舉例：雙酚、雙酚A、雙酚F、雙酚S等之具有2個苯環之化合物、及此等之鹵化物或此等之C1-9烷基取代物；萘二醇、雙酚茀、雙甲酚茀、雙苯氧基乙醇茀等之具有縮合環之化合物、及此等之鹵化物或此等之C1-9烷基取代物；氫化雙酚A、氫化雙酚F、氫化雙酚S、二環己基等之具有2個環己烷環之化合物；甲酚酚醛清漆、酚酚醛清漆等之具有3個以上苯環等之芳香族環化合物及此等之鹵化物，或此等之C1-9烷基取代物等。在C1-9烷基取代物中之C1-9烷基取代基，可舉例：甲基、乙基、丙基、三級丁基等。在鹵化物中之鹵素可舉例：F、Cl、Br等。The m-valent polyvalent hydroxy compound Z 1 (OH) m can be exemplified by a compound having two benzene rings such as bisphenol, bisphenol A, bisphenol F or bisphenol S, and such a halide or the like a 1-9 alkyl-substituted compound; a compound having a condensed ring such as naphthalenediol, bisphenol oxime, biscresol oxime, bisphenoxyethanol oxime, etc., and such a halide or such a C 1-9 alkane a base compound; a compound having two cyclohexane rings such as hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, dicyclohexyl or the like; cresol novolac, phenol novolac, etc. having three or more benzene rings An aromatic ring compound or the like, or a C 1-9 alkyl substituent or the like. The C 1-9 alkyl substituent in the C 1-9 alkyl substituent may, for example, be a methyl group, an ethyl group, a propyl group, a tertiary butyl group or the like. The halogen in the halide can be exemplified by F, Cl, Br and the like.

另外，化合物(A)係例如以下式(I)所示之化合物：Further, the compound (A) is, for example, a compound represented by the following formula (I):

[式(I)中，X係表示單鍵或連結基(具有1個以上原子之2價的基)，上述連結基係2價之烴基、羰基、醚鍵、酯鍵、碳酸酯基、醯胺鍵、或此等複數個連接而成之基]。In the formula (I), X represents a single bond or a linking group (having a divalent group of one or more atoms), and the linking group is a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, or a hydrazine. An amine bond, or a plurality of such linked bases].

於上式(1)所示之化合物中，作為連結基所例示的2價烴基較佳為碳數1至18之直鏈狀或分枝鏈狀之伸烷基、2價之脂環式烴基(尤其是2價之伸環烷基)等。碳數1至18之直鏈狀或分枝鏈狀之伸烷基，例如，可舉例：亞甲基、甲基亞甲基、二甲基亞甲基、伸乙基、伸丙基、三亞甲基等。2價之脂環式烴基，例如，可舉例：1,2-伸環戊基、1,3-伸環戊基、環亞戊基、1,2-伸環己基、1,3-伸環己基、1,4-伸環己基、環亞己基等2價之伸環己基(包含伸環亞己基)等。In the compound represented by the above formula (1), the divalent hydrocarbon group exemplified as the linking group is preferably a linear or branched chain alkyl group having a carbon number of 1 to 18, and a divalent alicyclic hydrocarbon group. (especially a divalent cycloalkylene group) and the like. A linear or branched chain alkyl group having 1 to 18 carbon atoms, and examples thereof include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylidene group, a propyl group, and a Sanya group. Methyl and the like. The divalent alicyclic hydrocarbon group may, for example, be 1,2-cyclopentyl, 1,3-cyclopentyl, cyclopentylene, 1,2-extended cyclohexyl, 1,3-extension ring A divalent cyclohexylene group (including a stretched cyclohexylene group) such as a hexyl group, a 1,4-cyclohexylene group or a cyclohexylene group.

以上式(I)所示之脂環式環氧化合物的代表例，可舉例：下式(I-1)至(I-7)所示之化合物等。上式(I)所示之脂環式環氧化合物，例如，也能夠使用Celloxide 2021P、Celloxide 2081、Celloxide 8000(Daicel化學工業股份有限公司製)等之市售品。還有下式中，n係表示1至30之整數。若使用此等之脂環式環氧化合物時，也能夠期待對硬化物之透明性或玻璃轉移溫度提高的影響。Representative examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-7). For the alicyclic epoxy compound represented by the above formula (I), for example, commercially available products such as Celloxide 2021P, Celloxide 2081, and Celloxide 8000 (manufactured by Daicel Chemical Industry Co., Ltd.) can be used. Further, in the following formula, n represents an integer of 1 to 30. When such an alicyclic epoxy compound is used, the influence on the transparency of the cured product or the improvement of the glass transition temperature can be expected.

化合物(A)較佳為具有各2個環氧基、環氧丙基、乙烯基醚基、或(甲基)丙烯醯基、苯環或環己烷環之化合物。具體而言，化合物(A)較佳能夠使用雙酚F二環氧丙基醚、四甲基雙酚二環氧丙基醚、或雙酚苯氧基乙醇茀二環氧丙基醚等之具有2至4個苯環之二環氧丙基醚；雙酚F(3-乙基環氧丙烷-3-基甲基)醚等之具有2至4個苯環之二環氧丙基醚；雙酚F二乙烯基醚等之具有2至4個苯環之二乙烯基醚；或雙酚F二(甲基)丙烯酸酯等之具有2至4個苯環之(甲基)丙烯酸酯等。化合物(A)特佳為具有各2個環氧丙基與苯環之化合物。The compound (A) is preferably a compound having two epoxy groups, a glycidyl group, a vinyl ether group, or a (meth)acryl fluorenyl group, a benzene ring or a cyclohexane ring. Specifically, the compound (A) can preferably be a bisphenol F diglycidyl ether, a tetramethyl bisphenol diepoxypropyl ether, or a bisphenol phenoxyethanol quinone diepoxypropyl ether. Di-epoxypropyl ether having 2 to 4 benzene rings; diglycidyl ether having 2 to 4 benzene rings such as bisphenol F (3-ethyl propylene oxide-3-ylmethyl) ether a divinyl ether having 2 to 4 benzene rings such as bisphenol F divinyl ether; or a (meth) acrylate having 2 to 4 benzene rings such as bisphenol F di(meth) acrylate Wait. The compound (A) is particularly preferably a compound having two epoxypropyl groups and a benzene ring.

本發明之電子紙用低透濕性樹脂組成物中之化合物(A)之含量例如為5至95wt%，較佳為10至90wt%，進一步較佳為20至85wt%。若化合物(A)之含量為如此之範圍內，能夠提供一種硬化物，其係使樹脂組成物之塗布性提高，具有優異之低透濕性、硬度。The content of the compound (A) in the low moisture-permeable resin composition for electronic paper of the present invention is, for example, 5 to 95% by weight, preferably 10 to 90% by weight, further preferably 20 to 85% by weight. When the content of the compound (A) is within such a range, it is possible to provide a cured product which improves the coatability of the resin composition and has excellent low moisture permeability and hardness.

＜化合物(B)＞<compound (B)>

化合物(B)係在1分子中具有1個反應性官能基(b)，分子量為50至1000。若化合物(B)之分子量為50至1000時，使其硬化之情形下，能夠有效地發現聚合物之側鏈填塞自由體積的效果。化合物(B)之分子量較佳為50至500。化合物(B)係在1分子中例如為具有1個以上，較佳為具有1至4個、進一步較佳為具有2至4個之環狀骨架。複數個環狀骨架可以相同或不同。在化合物(B)之環狀骨架可舉例：以上述化合物(A)例示之物。其中，較佳為苯環、環己烷環。還有，化合物(B)能夠使用單獨一種或組合二種以上而使用。The compound (B) has one reactive functional group (b) in one molecule and a molecular weight of 50 to 1,000. When the molecular weight of the compound (B) is from 50 to 1,000, it is effective to find the effect of packing the free volume of the side chain of the polymer. The molecular weight of the compound (B) is preferably from 50 to 500. The compound (B) has, for example, one or more, preferably 1 to 4, and more preferably 2 to 4 cyclic skeletons in one molecule. The plurality of annular skeletons may be the same or different. The cyclic skeleton of the compound (B) can be exemplified by the compound (A). Among them, a benzene ring or a cyclohexane ring is preferred. Further, the compound (B) can be used singly or in combination of two or more.

反應性官能基(b)可舉例以上述反應性官能基(a)例示之物。上述反應性官能基(a)具有陽離子聚合性官能基之情形下，反應性官能基(b)也為陽離子聚合性官能基；上述反應性官能基(a)為自由基聚合性官能基之情形下，反應性官能基(b)也較佳為自由基聚合性官能基。反應性官能基(a)與反應性官能基(b)的組合較佳皆為環氧基，同時特佳皆為環氧丙基。The reactive functional group (b) can be exemplified by the above-mentioned reactive functional group (a). When the reactive functional group (a) has a cationically polymerizable functional group, the reactive functional group (b) is also a cationically polymerizable functional group; and the reactive functional group (a) is a radically polymerizable functional group. Next, the reactive functional group (b) is also preferably a radical polymerizable functional group. The combination of the reactive functional group (a) and the reactive functional group (b) is preferably an epoxy group, and particularly preferably a glycidyl group.

例如，化合物(B)可舉例：具有芳香族環與陽離子聚合性官能基之化合物(B-1)；具有芳香族環與自由基聚合性官能基之化合物(B-2)；具有脂肪族環與陽離子聚合性官能基之化合物(B-3)；具有脂肪族環與自由基聚合性官能基之化合物(B-4)；具有烷基與陽離子聚合性官能基之化合物(B-5)；及具有烷基與自由基聚合性官能基之化合物(B-6)等。For example, the compound (B) can be exemplified by a compound (B-1) having an aromatic ring and a cationically polymerizable functional group; a compound (B-2) having an aromatic ring and a radical polymerizable functional group; and having an aliphatic ring a compound (B-3) having a cationically polymerizable functional group; a compound (B-4) having an aliphatic ring and a radical polymerizable functional group; and a compound (B-5) having an alkyl group and a cationically polymerizable functional group; And a compound (B-6) having an alkyl group and a radical polymerizable functional group.

具有芳香族環與陽離子聚合性官能基之化合物(B-1)，例如，可舉例：環氧丙基苯基醚、苯基酚環氧丙基醚、二苯基酚環氧丙基醚、三苯基酚環氧丙基醚等之具有苯環與環氧基之化合物；環氧丙基甲基苯基醚、環氧丙基乙基苯基醚、環氧丙基丙基苯基醚、環氧丙基正丁基苯基醚、環氧丙基三級丁基苯基醚等之具有烷基取代苯環與環氧基之化合物(例如，具有C1-9烷基取代苯環與環氧基之化合物)；甲基苯基酚環氧丙基醚、乙基苯基酚環氧丙基醚、丙基苯基酚環氧丙基醚、正丁基苯基酚環氧丙基醚、三級丁基苯基酚環氧丙基醚等之烷基取代苯基酚環氧丙基醚(例如，C1-9烷基取代苯基酚環氧丙基醚)；苄基(R)-(-)-環氧丙基醚、苯基苄基環氧丙基醚等之苄基環氧丙基醚化合物；苯基苄基環氧丙基醚等之苄基環氧丙基醚化合物；苯基乙烯基醚、苯基酚乙烯基醚、苯氧基甲基乙烯基醚、(苯基苯氧基)甲基乙烯基醚、(2-苯氧基)乙基乙烯基醚、(2-苯基苯氧基)乙基乙烯基醚等之具有1或2個苯環之乙烯基醚化合物；苯基環氧丙烷、苯基酚環氧丙烷、苯氧基甲基環氧丙烷、(苯基苯氧基)甲基環氧丙烷、(2-苯氧基)乙基環氧丙烷、(2-苯基苯氧基)乙基環氧丙烷等之具有1或2個苯環之環氧丙烷化合物及此等之鹵化物等。上述C1-9烷基取代基可舉例：甲基、乙基、丙基、三級丁基等。The compound (B-1) having an aromatic ring and a cationically polymerizable functional group may, for example, be epoxidized phenyl ether, phenylphenol epoxypropyl ether or diphenylphenol epoxypropyl ether. a compound having a benzene ring and an epoxy group, such as a triphenylphenol epoxypropyl ether; a glycidyl methylphenyl ether, an epoxypropylethylphenyl ether, or a propyl propyl phenyl ether a compound having an alkyl-substituted benzene ring and an epoxy group, such as a glycidyl n-butylphenyl ether or a propyl propyl tertiary butyl phenyl ether (for example, having a C 1-9 alkyl-substituted benzene ring) Compound with epoxy group); methyl phenylphenol epoxy propyl ether, ethyl phenyl phenol epoxy propyl ether, propyl phenyl phenol epoxy propyl ether, n-butyl phenyl phenol propylene Alkyl-substituted phenylphenol epoxypropyl ethers such as alkyl ethers, tertiary butyl phenyl phenol glycopropyl ethers (for example, C 1-9 alkyl-substituted phenylphenol epoxy propyl ether); benzyl a benzyl epoxypropyl ether compound such as (R)-(-)-epoxypropyl ether or phenylbenzylepoxypropyl ether; benzyl epoxide C such as phenylbenzylepoxypropyl ether Ether ether compound; phenyl vinyl ether, phenylphenol vinyl ether, benzene Methyl vinyl ether, (phenylphenoxy) methyl vinyl ether, (2-phenoxy) ethyl vinyl ether, (2-phenylphenoxy) ethyl vinyl ether, etc. 1 or 2 phenyl ring vinyl ether compounds; phenyl propylene oxide, phenylphenol propylene oxide, phenoxymethyl propylene oxide, (phenylphenoxy) methyl propylene oxide, (2- A propylene oxide compound having one or two benzene rings, such as phenoxy)ethyl propylene oxide or (2-phenylphenoxy)ethyl propylene oxide, and the like, and the like. The above C 1-9 alkyl substituent may, for example, be a methyl group, an ethyl group, a propyl group, a tertiary butyl group or the like.

具有芳香族環與自由基聚合性官能基之化合物(B-2)，例如，可舉例：(甲基)丙烯酸苯酯、(甲基)丙烯酸苯基酚酯、(甲基)丙烯酸苯氧基甲酯、(甲基)丙烯酸(苯基苯氧基)甲酯、(甲基)丙烯酸(2-苯氧基)乙酯、(甲基)丙烯酸(2-苯基苯氧基)乙酯等之具有1個或2個苯環與(甲基)丙烯醯基之化合物；及此等之鹵化物、或此等之C1-9烷基取代基等。在C1-9烷基取代物之C1-9烷基取代基可舉例：甲基、乙基、丙基、三級丁基等。在鹵化物中之鹵素可舉例：F、Cl、Br等。The compound (B-2) having an aromatic ring and a radical polymerizable functional group may, for example, be phenyl (meth) acrylate, phenyl phenol (meth) acrylate or phenoxy (meth) acrylate. Methyl ester, (phenylphenoxy)methyl (meth)acrylate, (2-phenoxy)ethyl (meth)acrylate, (2-phenylphenoxy)ethyl (meth)acrylate, etc. a compound having one or two benzene rings and a (meth) acrylonitrile group; and such a halide, or a C 1-9 alkyl substituent or the like. The C 1-9 alkyl substituent of the C 1-9 alkyl substituent may, for example, be methyl, ethyl, propyl, tert-butyl or the like. The halogen in the halide can be exemplified by F, Cl, Br and the like.

具有脂肪族環與陽離子聚合性官能基之化合物(B-3)，例如，可舉例：環己基環氧丙基醚、二環己基環氧丙基醚、三環己基環氧丙基醚等之C5-20環烷基環氧丙基醚化合物；環己基環氧丙基醚、二環己基環氧丙基醚、三環己基環氧丙基醚等之C5-20環烷基環氧丙基醚化合物；環己基乙烯基醚、二環己基乙烯基醚、三環己基乙烯基醚等之C5-20環烷基乙烯基醚化合物等。The compound (B-3) having an aliphatic ring and a cationically polymerizable functional group may, for example, be cyclohexylepoxypropyl ether, dicyclohexylepoxypropyl ether or tricyclohexylepoxypropyl ether. C 5-20 cycloalkyl group glycidyl ether compound; cyclohexyl glycidyl ether, hexyl glycidyl ether bicyclic, tricyclic hexyl glycidyl ether, etc. C 5-20 cycloalkyl epoxy A propyl ether compound; a C 5-20 cycloalkyl vinyl ether compound such as cyclohexyl vinyl ether, dicyclohexyl vinyl ether or tricyclohexyl vinyl ether.

具有脂肪族環與自由基聚合性官能基之化合物(B-4)，例如，可舉例：(甲基)丙烯酸環己酯、(甲基)丙烯酸二環己酯、(甲基)丙烯酸三環己酯等之(甲基)C5-20環烷酯化合物等。The compound (B-4) having an aliphatic ring and a radical polymerizable functional group may, for example, be cyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate or tricyclo(meth)acrylate. A (meth)C 5-20 cycloalkyl ester compound such as hexyl ester.

具有烷基與陽離子聚合性官能基之化合物(B-5)，例如，可舉例：環氧丙基甲基醚、環氧丙基乙基醚、環氧丙基丙基醚、丁基環氧丙基醚、2-乙基己基環氧丙基醚等之C1-9烷基環氧丙基醚化合物；甲基環氧丙基醚、乙基環氧丙基醚、丙基環氧丙基醚、丁基環氧丙基醚等之C1-9烷基環氧丙基醚化合物；甲基乙烯基醚、乙基乙烯基醚、丙基乙烯基醚、丁基乙烯基醚等之C1-9烷基乙烯基醚化合物等。The compound (B-5) having an alkyl group and a cationically polymerizable functional group may, for example, be epoxidized methyl ether, epoxypropyl ethyl ether, glycidyl propyl ether, butyl epoxy C 1-9 alkylepoxypropyl ether compound such as propyl ether or 2-ethylhexyl epoxypropyl ether; methyl epoxypropyl ether, ethyl epoxy propyl ether, propyl epoxide a C 1-9 alkylepoxypropyl ether compound such as a methyl ether or a butyl epoxypropyl ether; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether or the like A C 1-9 alkyl vinyl ether compound or the like.

具有烷基與自由基聚合性官能基之化合物(B-6)，例如，可舉例：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等之(甲基)丙烯酸C1-9烷酯化合物等。The compound (B-6) having an alkyl group and a radical polymerizable functional group may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, or (methyl) a (meth)acrylic acid C 1-9 alkyl ester compound such as butyl acrylate.

另外，化合物(B)係例如以下式(2)所示之化合物：Further, the compound (B) is, for example, a compound represented by the following formula (2):

Z2-OR2　(2)Z 2 -OR 2 (2)

[式(2)中，Z2係表示從1價之羥基合物(Z2OH)除去OH基之基，R2係與前述R1相同]。上述Z2較佳為具有環狀骨架之基。環狀骨架可舉例：前述例示之物。In the formula (2), Z 2 represents a group from which an OH group is removed from a monovalent hydroxy compound (Z 2 OH), and R 2 is the same as the above R 1 ]. The above Z 2 is preferably a group having a cyclic skeleton. The cyclic skeleton can be exemplified by the foregoing exemplified ones.

羥基化合物Z2OH，例如，可舉例：酚、苯基酚、二苯基酚、三苯基酚等之具有1至3個苯環之酚類；甲基酚、乙基酚、丙基酚、正丁基酚、三級丁基酚等之烷基取代酚(例如，C1-9烷基取代酚)；甲基苯基酚、乙基苯基酚、丙基苯基酚、正丁基苯基酚、三級丁基苯基酚等之烷基取代苯基酚(例如，C1-9烷基取代苯基酚)；甲醇、乙醇、丙醇、丁醇等之烷醇(例如，C1-9烷醇)；苄醇、苯基苄醇等之苄醇類；環己醇、二環己醇、三環己醇等之具有脂肪族環之醇類；及此等之鹵化物等。在上述C1-9烷基取代基可舉例：甲基、乙基、丙基、三級丁基等。在鹵化物中之鹵素可舉例：F、Cl、Br等。The hydroxy compound Z 2 OH may, for example, be a phenol having 1 to 3 benzene rings such as phenol, phenylphenol, diphenylphenol or triphenylphenol; methylphenol, ethylphenol, propylphenol An alkyl-substituted phenol such as n-butyl phenol or tert-butyl phenol (for example, a C 1-9 alkyl-substituted phenol); methyl phenyl phenol, ethyl phenyl phenol, propyl phenyl phenol, n-butyl An alkyl-substituted phenylphenol such as a phenylphenol or a tertiary butyl phenylphenol (for example, a C 1-9 alkyl-substituted phenylphenol); an alkyl alcohol such as methanol, ethanol, propanol or butanol (for example) , C 1-9 alkanol); benzyl alcohol such as benzyl alcohol or phenyl benzyl alcohol; alcohol having an aliphatic ring such as cyclohexanol, dicyclohexanol or tricyclohexanol; and halogenation thereof Things and so on. The above C 1-9 alkyl substituent may, for example, be a methyl group, an ethyl group, a propyl group, a tertiary butyl group or the like. The halogen in the halide can be exemplified by F, Cl, Br and the like.

化合物(B)較佳為環氧基、環氧丙基、乙烯基醚基、或具有(甲基)丙烯醯基與苯環或環己烷環之化合物。具體而言，化合物(B)係環氧丙基苯基醚、或鄰苯基酚環氧丙基醚等之具有1至2個苯環之環氧丙基醚；(甲基)丙烯酸-2-(苯基苯氧基)乙酯等之具有1至2個苯環之(甲基)丙烯酸酯等。The compound (B) is preferably an epoxy group, a glycidyl group, a vinyl ether group, or a compound having a (meth)acryl fluorenyl group and a benzene ring or a cyclohexane ring. Specifically, the compound (B) is a glycidyl ether having 1 to 2 benzene rings, such as a glycidyl phenyl ether or an o-phenylphenol epoxypropyl ether; (meth)acrylic acid-2 (meth) acrylate having 1 to 2 benzene rings, etc., such as -(phenylphenoxy)ethyl ester.

相對於100重量份之該化合物(A)，化合物(B)之含量較佳為1至1000重量份，進一步較佳為10至250重量份。若化合物(B)之含量在於如此之範圍內時，能夠有效地填塞聚合物(硬化物)之自由空間(自由體積)，故能夠獲得低透濕性更優異的聚合物。The content of the compound (B) is preferably from 1 to 1,000 parts by weight, more preferably from 10 to 250 parts by weight, per 100 parts by weight of the compound (A). When the content of the compound (B) is within such a range, the free space (free volume) of the polymer (cured material) can be effectively packed, so that a polymer having more excellent moisture permeability can be obtained.

化合物(A)與化合物(B)之較佳的組合，例如，可舉例：化合物(A)具有2個環狀骨架、化合物(B)具有1個環狀骨架的組合；化合物(A)具有2個環狀骨架、化合物(B)具有2個環狀骨架的組合；化合物(A)具有5個環狀骨架、化合物(B)具有1個環狀骨架的組合；及化合物(A)具有5個環狀骨架、化合物(B)具有2個環狀骨架的組合。藉由作成如此的組合，可以獲得賦予具優越之更低透濕性之硬化物的電子裝置用低透濕性樹脂組成物。認為於如此組合中，因而更為有效地進行硬化物中之自由體積的填塞。A preferred combination of the compound (A) and the compound (B) is, for example, a compound (A) having two cyclic skeletons, a compound (B) having one cyclic skeleton, and a compound (A) having 2 a cyclic skeleton, a compound (B) having a combination of two cyclic skeletons; a compound (A) having five cyclic skeletons; a compound (B) having a combination of one cyclic skeleton; and a compound (A) having five The cyclic skeleton and the compound (B) have a combination of two cyclic skeletons. By such a combination, it is possible to obtain a low moisture-permeable resin composition for an electronic device which imparts a cured product having superior lower moisture permeability. It is considered that in such a combination, the free volume of the hardened material is more effectively filled.

尤其，於本發明之電子裝置用低透濕性樹脂組成物中，在有效地使硬化物之透濕性降低之觀點，相對於100重量份之化合物(A)，化合物(A)具有2個環狀骨架、化合物(B)具有1個環狀骨架的組合之情形的化合物(B)之含量並未予以特別限定，較佳為1至250重量份，更佳為10至200重量份，進一步較佳為20至150重量份，特佳為25至100重量份。In particular, in the low moisture permeability resin composition for an electronic device of the present invention, the compound (A) has two compounds (A) with respect to 100 parts by weight of the compound (A) from the viewpoint of effectively reducing the moisture permeability of the cured product. The content of the compound (B) in the case where the cyclic skeleton and the compound (B) have a combination of one cyclic skeleton is not particularly limited, and is preferably from 1 to 250 parts by weight, more preferably from 10 to 200 parts by weight, further. It is preferably 20 to 150 parts by weight, particularly preferably 25 to 100 parts by weight.

另外，於本發明之電子裝置用低透濕性樹脂組成物中，化合物(A)具有2個環狀骨架、化合物(B)具有2個環狀骨架的組合之情形的化合物(B)之含量並未予以特別限定，但在有效地使硬化物之透濕性降低之觀點，相對於100重量份之化合物(A)，較佳為1至350重量份，更佳為10至250重量份，進一步較佳為20至200重量份，特佳為30至150重量份。Further, in the low moisture-permeable resin composition for an electronic device of the present invention, the compound (A) has two cyclic skeletons, and the compound (B) has a combination of two cyclic skeletons. It is not particularly limited, but from the viewpoint of effectively lowering the moisture permeability of the cured product, it is preferably from 1 to 350 parts by weight, more preferably from 10 to 250 parts by weight, per 100 parts by weight of the compound (A). It is further preferably from 20 to 200 parts by weight, particularly preferably from 30 to 150 parts by weight.

化合物(A)與化合物(B)之較佳的組合，具體而言，可舉例：雙酚F二環氧丙基醚與環氧丙基苯基醚之組合、雙酚F二環氧丙基醚與鄰苯基酚環氧丙基醚的組合等。組合雙酚F二環氧丙基醚與環氧丙基苯基醚之情形，相對於100重量份之作為化合物(A)之雙酚F二環氧丙基醚，作為化合物(B)之環氧丙基苯基醚之含量特佳為1至90重量份。另外，雙酚F二環氧丙基醚與鄰苯基酚環氧丙基醚的組合之情形，相對於100重量份之作為化合物(A)之雙酚F二環氧丙基醚，作為化合物(B)之鄰苯基酚環氧丙基醚之含量特佳為1至250重量份。A preferred combination of the compound (A) and the compound (B), specifically, a combination of bisphenol F diglycidyl ether and epoxypropyl phenyl ether, bisphenol F digoxypropyl group Combination of ether and o-phenylphenol epoxypropyl ether, and the like. In the case of combining bisphenol F diglycidyl ether and epoxy propyl phenyl ether, as a ring of compound (B) with respect to 100 parts by weight of bisphenol F diglycidyl ether as compound (A) The content of the oxypropyl phenyl ether is particularly preferably from 1 to 90 parts by weight. Further, in the case of a combination of bisphenol F diglycidyl ether and o-phenylphenol epoxidopropyl ether, as a compound, relative to 100 parts by weight of bisphenol F diglycidyl ether as the compound (A) The content of the o-phenylphenol epoxypropyl ether of (B) is particularly preferably from 1 to 250 parts by weight.

＜聚合物起始劑(C)＞<Polymer initiator (C)>

於本發明之電子紙低透濕性樹脂組成物中，含有聚合物起始劑(C)。聚合物起始劑(C)並未予以特別限定，能夠使用習知慣用之聚合起始劑，較佳能夠使用光或熱陽離子聚合起始劑、或是光或熱自由基聚合起始劑。聚合起始劑能夠使用單獨一種，或是能夠組合二種以上而使用。The electronic paper low moisture permeable resin composition of the present invention contains a polymer initiator (C). The polymer initiator (C) is not particularly limited, and a conventional polymerization initiator can be used, and a photo or thermal cationic polymerization initiator or a photo or thermal radical polymerization initiator can be preferably used. The polymerization initiators can be used singly or in combination of two or more.

＜光陽離子聚合起始劑＞<Photocationic polymerization initiator>

例如，光陽離子聚合起始劑能夠使用Cyracure UVI-6970、Cyracure UVI-6974、Cyracure UVI-6990、Cyracure UVI-950(以上，美國Union Carbide公司製、商品名)；Irgacure 250、Irgacure 261、Irgacure 264(Ciba Specialty Chemicals公司製、商品名)；SP-150、SP-151、SP-170、Optomer SP-171(以下，旭電化工業股份有限公司製、商品名)；CG-24-61(Ciba Specialty Chemicals公司製、商品名)；DAICATII(Daicel化學工業股份有限公司製、商品名)；UVAC1590、UVAC1591(Daicel Cytec公司製、商品名)；CI-2064、CI-2639、CI-2624、CI-2481、CI-2734、CI-2855、CI-2823、CI-2758、CIT-1682(以上，日本曹達股份有限公司製品、商品名)；PI-2074(Rhodia公司製、商品名、五氟苯基硼酸鹽甲苯醯對異丙基苄錪鹽)；FFC509(3M公司製品、商品名)；BBI-102、BBI-101、BBI-103、MPI-103、TPS-103、MDS-103、DTS-103、NAT-103、NDS-103(Midori化學股份有限公司製、商品名)；CD-1010、CD-1011、CD-1012(美國、Sartomer公司製、商品名)；CPI-100P、CPI-101A(Sun Apro股份有限公司製、商品名)等之市售品所代表之二重氮鎓鹽、錪鹽、鎏鹽、鏻鹽、硒鹽、鹽、銨鹽等。For example, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, manufactured by Union Carbide, USA); Irgacure 250, Irgacure 261, Irgacure 264 can be used as the photocationic polymerization initiator. (manufactured by Ciba Specialty Chemicals Co., Ltd.); SP-150, SP-151, SP-170, Optomer SP-171 (hereinafter, manufactured by Asahi Kasei Kogyo Co., Ltd., trade name); CG-24-61 (Ciba Specialty) Chemicals company, trade name); DAICATII (Daicel Chemical Industry Co., Ltd., trade name); UVAC1590, UVAC1591 (Daicel Cytec company, trade name); CI-2064, CI-2639, CI-2624, CI-2481 , CI-2734, CI-2855, CI-2823, CI-2758, CIT-1682 (above, Japan Soda Co., Ltd. product, trade name); PI-2074 (Rhodia company, trade name, pentafluorophenyl boric acid Salt toluene 醯 isopropyl benzyl hydrazine salt; FFC 509 (3M company product, trade name); BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (made by Midori Chemical Co., Ltd., trade name); CD-1010, CD-1011, CD-1012 (US Diamine, strontium, barium, and strontium salts represented by commercially available products such as CPI-100P and CPI-101A (manufactured by Sun Apro Co., Ltd., trade name) Selenium salt, Salt, ammonium salt, etc.

＜熱陽離子聚合起始劑＞<Thermal cationic polymerization initiator>

例如，熱陽離子聚合起始劑能夠使用San Aid SI-45、San Aid SI-47、San Aid SI-60、San Aid SI-60L、San Aid SI-80、San Aid SI-80L、San Aid SI-100、San Aid SI-100L、San Aid SI-110L、San Aid SI-145、San Aid SI-150、San Aid SI-160、San Aid SI-170L、San Aid SI-180L(以上，三新化學工業股份有限公司製品、商品名)；CI-2921、CI-2920、CI-2946、CI-3128、CI-2624、CI-2639、CI-2064(以上，日本曹達股份有限公司製品、商品名)、PP-33、CP-66、CP-77(旭電化工業公司製品、商品名)、FC-509、FC-520(3M公司製品、商品名)等所代表之二重氮鎓鹽、錪鹽、鎏鹽、鏻鹽、硒鹽、鹽、銨鹽等。還有，也可以與鋁或鈦等之金屬與乙醯乙酸或是二酮類之螯合物與三苯基矽烷醇等之矽烷醇的化合物，或是鋁或鈦等之金屬與乙醯乙酸或是二酮類之螯合物與雙酚S等之酚類的化合物。For example, the thermal cationic polymerization initiator can use San Aid SI-45, San Aid SI-47, San Aid SI-60, San Aid SI-60L, San Aid SI-80, San Aid SI-80L, San Aid SI- 100, San Aid SI-100L, San Aid SI-110L, San Aid SI-145, San Aid SI-150, San Aid SI-160, San Aid SI-170L, San Aid SI-180L (above, Sanxin Chemical Industry) Co., Ltd. products, trade names); CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (above, Japan Soda Co., Ltd. products, trade names), PP-33, CP-66, CP-77 (products and trade names of Asahi Kasei Kogyo Co., Ltd.), FC-509, FC-520 (3M company products, trade names), etc. Barium salt, barium salt, selenium salt, Salt, ammonium salt, etc. Further, it may be a compound of a metal such as aluminum or titanium, a chelate compound of acetonitrile or a diketone, a decyl alcohol such as triphenyl decyl alcohol, or a metal such as aluminum or titanium and acetonitrile. It is a compound of a ketone of a diketone and a phenol of a bisphenol S or the like.

例如，相對於100重量份之在電子裝置用低透濕性樹脂組成物中所含之化合物(A)與化合物(B)的全部聚合性化合物，光或熱陽離子聚合起始劑之用量例如約0.01至15重量份，較佳為0.01至12重量份，特佳為0.05至10重量份，最好為0.1至10重量份左右。藉由於此範圍內使用而能夠獲得具優越之低透濕性的硬化物。For example, the amount of the photo- or cationic polymerization initiator is, for example, about 100 parts by weight of the total polymerizable compound of the compound (A) and the compound (B) contained in the low moisture-permeable resin composition for an electronic device. From 0.01 to 15 parts by weight, preferably from 0.01 to 12 parts by weight, particularly preferably from 0.05 to 10 parts by weight, particularly preferably from 0.1 to 10 parts by weight. A cured product having superior low moisture permeability can be obtained by use in this range.

＜硬化加速劑＞<hardening accelerator>

本發明之電子裝置用低透濕性樹脂組成物係於藉光或熱陽離子聚合起始劑而硬化聚合性化合物之際，也可以含有具有加速硬化速度之機能的硬化加速劑。能夠使用習知慣用之硬化加速劑做為硬化加速劑，例如，可舉例：1,8-二吖雙環[5.4.0]-7-十一烯(DBU)、及其鹽(例如，酚鹽、辛酸鹽、對甲苯磺酸鹽、甲酸鹽、四苯基硼酸鹽)；1,5-二吖雙環[4.3.0]-5-壬烯(DBN)及其鹽(例如，鏻鹽、鎏鹽、4級銨鹽、錪鹽)；苄基二甲基胺、2,4,6-三(二甲胺基甲基)酚、N,N-二甲基環己基胺等之3級胺；2-乙基-4-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑等之咪唑；磷酸酯、三苯基膦等之膦類；四苯基鏻四(對甲苯基)硼酸鹽等之鏻化合物；辛酸錫、辛酸鋅等之有機金屬鹽；金屬螯合物等。此等能夠單獨使用或混合二種以上而使用。The low moisture-permeable resin composition for an electronic device of the present invention may contain a curing accelerator having a function of accelerating the curing rate when the polymerizable compound is cured by a photo- or thermal cationic polymerization initiator. A conventional hardening accelerator can be used as the hardening accelerator, and for example, 1,8-dibicyclo[5.4.0]-7-undecene (DBU), and a salt thereof (for example, a phenate) can be exemplified. , octanoate, p-toluenesulfonate, formate, tetraphenyl borate); 1,5-dioxabicyclo[4.3.0]-5-decene (DBN) and salts thereof (eg, sulfonium salts,鎏 salt, grade 4 ammonium salt, strontium salt); benzyl dimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylcyclohexylamine, etc. An amine; an imidazole such as 2-ethyl-4-methylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole; a phosphate such as triphenylphosphine; a tetraphenylphosphonium tetra An anthracene compound such as (p-tolyl)borate; an organic metal salt such as tin octylate or zinc octylate; a metal chelate compound or the like. These can be used alone or in combination of two or more.

另外，硬化加速劑也能夠使用U-CAT SA 506、U-CAT SA 102、U-CAT 5003、U-CAT 18X、12XD(開發品)(任一種皆為Sun Apro股份有限公司製)；TPP-K、TPP-MK(任一種皆為北興化學工業股份有限公司製)；PX-4ET(日本化學工業股份有限公司製)等之市售品。In addition, U-CAT SA 506, U-CAT SA 102, U-CAT 5003, U-CAT 18X, and 12XD (developed products) (all of which are manufactured by Sun Apro Co., Ltd.) can also be used as the hardening accelerator; TPP- K, TPP-MK (all of which are manufactured by Kitai Chemical Industry Co., Ltd.); and PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.) and other commercial products.

例如，相對於100重量份之在電子裝置用低透濕性樹脂組成物中所含之全部聚合性化合物，硬化加速劑之用量例如為0.05至5重量份，較佳為0.1至3重量份，特佳為0.2至3重量份，最好為0.25至2.5重量份左右。若硬化加速劑之用量低於0.05重量份時，有硬化加速效果變得不充分之情形；另一方面，若硬化加速劑之用量超過5重量份時，有硬化物將著色而色調將變差之情形。For example, the curing accelerator is used in an amount of, for example, 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of all the polymerizable compounds contained in the low moisture-permeable resin composition for an electronic device. It is particularly preferably from 0.2 to 3 parts by weight, more preferably from 0.25 to 2.5 parts by weight. When the amount of the hardening accelerator is less than 0.05 parts by weight, the hardening acceleration effect becomes insufficient; on the other hand, if the amount of the hardening accelerator exceeds 5 parts by weight, the cured product will be colored and the color tone will be deteriorated. The situation.

＜光自由基聚合起始劑＞<Photoradical polymerization initiator>

例如，光自由基聚合起始劑可舉例：二苯甲酮、苯丙醯苯、苄基二甲基酮、苯偶因、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚、二甲氧基苯基苯乙酮、二甲氧基苯基苯乙酮、二乙氧基苯乙酮、二苯基二硫醚、鄰苯甲醯安息香酸甲酯、4-二甲胺基安息香酸乙酯(日本化藥股份有限公司製Kayacure EPA等)、2,4-二乙基氧硫(日本化藥股份有限公司製Kayacure DETX等)、2-甲基-1-[4-(甲基)苯基]-2-啉基丙酮-1(Ciba Geigy股份有限公司製Irgacure 907等)、2-二甲胺基-2-(4-啉基)苯甲醯-1-苯基丙烷等之2-胺基-2-苯甲醯-1-苯基烷化合物；四(三級丁過氧羰基)二苯甲酮、二苯甲醯、2-羥基-2-甲基-1-苯基-丙烷-1-酮、4,4-雙二乙胺基二苯甲酮等之胺基苯衍生物；2,2’-雙(2-氯苯基)-4,5,4’,5’-四苯基-1,2’-聯咪唑(保土谷化學股份有限公司製B-CIM等)等之咪唑化合物；2,6-雙(三氯甲基)-4-(4-甲氧基萘-1-基)-1,3,5-三等之鹵甲基化三化合物；2-三氯甲基-5-(2-苯并呋喃-2-基-乙烯基)-1,3,4-二唑合物等之鹵甲基二唑化合物等。此等之光自由基聚合起始劑能夠單獨使用，或混合二種以上而使用。另外，必要時能夠添加光增感劑。從感度及耐藥品性等之觀點，光自由基聚合起始劑較佳為咪唑化合物與胺基苯衍生物之組合、2-胺基-2-苯甲醯-1-苯基烷化合物、鹵甲基化三合物、鹵甲基化二唑化合物等。For example, the photoradical polymerization initiator can be exemplified by benzophenone, benzophenone, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Isopropyl ether, dimethoxyphenylacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfide, methyl phthalate benzoate, 4 -Methyl dimethyl benzoate (Kayacure EPA, manufactured by Nippon Kayaku Co., Ltd.), 2,4-diethyl oxysulfide (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), 2-methyl-1-[4-(methyl)phenyl]-2- Phytosylacetone-1 (Irgacure 907, manufactured by Ciba Geigy Co., Ltd.), 2-dimethylamino-2-(4- 2-Amino-2-benzylidene-1-phenylalkane compound such as phenyl)benzimidazole-1-phenylpropane; tetrakis(tertiary butylperoxycarbonyl)benzophenone, benzophenone , an aminobenzene derivative such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one or 4,4-bisdiethylaminobenzophenone; 2,2'-bis (2) Imidazolyl compound such as -chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (B-CIM, manufactured by Hodogaya Chemical Co., Ltd.); 2,6-double (trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-three Halogen methylation Compound; 2-trichloromethyl-5-(2-benzofuran-2-yl-vinyl)-1,3,4- Halomethyl group Diazole compounds and the like. These photoradical polymerization initiators can be used singly or in combination of two or more. Further, a photosensitizer can be added as necessary. The photoradical polymerization initiator is preferably a combination of an imidazole compound and an aminobenzene derivative, a 2-amino-2-benzoguanidin-1-phenylalkane compound, or a halogen, from the viewpoints of sensitivity and chemical resistance. Methylation three Halide methylation Diazole compounds and the like.

＜熱自由基聚合起始劑＞<Thermal radical polymerization initiator>

例如，熱自由基聚合起始劑可舉例：有機過氧化物類。有機過氧化物類能夠使用二烷基過氧化物、醯基過氧化物、鹵素過氧化物、酮過氧化物、過氧化酯等。有機過氧化物之具體例，可舉例：過氧化苯甲醯、三級丁過氧-2-乙基己酯、2,5-二甲基-2,5-二(2-乙基己醯基)過氧化己烷、三級丁基過氧苯甲酸酯、過氧化三級丁基、氫過氧化異丙苯、氫過氧化二異丙苯基、二(過氧化三級丁基)、2,5-二甲基-2,5-二(過氧化三級丁基)己烷、過氧化2,4-二氯苯甲醯基、二(過氧化三級丁基)異丙基苯、1,1-雙(過氧化三級丁基)-3,3,5-三甲基環己烷、過氧化甲基乙基酮、1,1,3,3-過氧化四甲基丁基-2-乙基己酸酯等。For example, the thermal radical polymerization initiator can be exemplified by an organic peroxide. As the organic peroxide, a dialkyl peroxide, a mercapto peroxide, a halogen peroxide, a ketone peroxide, a peroxyester or the like can be used. Specific examples of the organic peroxide include, for example, benzamidine peroxide, tertiary butyrate-2-ethylhexyl ester, and 2,5-dimethyl-2,5-di(2-ethylhexanide). Base) perylene oxide, tertiary butyl peroxybenzoate, tertiary butyl peroxide, cumene hydroperoxide, dicumyl hydroperoxide, di(tertiary butyl peroxide) , 2,5-Dimethyl-2,5-di(tributylbutyl peroxide)hexane, 2,4-dichlorobenzhydryl peroxide, di(tert-butylperoxy) isopropyl Benzene, 1,1-bis(tributylbutyl peroxide)-3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylperoxide Butyl-2-ethylhexanoate and the like.

還有，與上述熱自由基聚合起始劑一起，也能夠併用環烷酸鈷、環烷酸錳、環烷酸鋅、辛烯酸鈷等之環烷酸或辛烯酸之鈷、錳、鉛、鋅、鈀等之金屬鹽。同樣地，也能夠使用二甲基苯胺等之3級胺。Further, together with the above-mentioned thermal radical polymerization initiator, cobalt or manganese of naphthenic acid or octenoic acid such as cobalt naphthenate, manganese naphthenate, zinc naphthenate or cobalt octylate may be used in combination. A metal salt such as lead, zinc or palladium. Similarly, a tertiary amine such as dimethylaniline can also be used.

光或熱自由基聚合起始劑可以使用單獨一種，也可以任意之比例混合二種以上而使用。相對於100重量份之樹脂組成物，通常其用量例如為0.1重量份至5重量份，較佳為0.5重量份至4重量份。The light or thermal radical polymerization initiator may be used singly or in combination of two or more kinds in any ratio. The amount is usually, for example, from 0.1 part by weight to 5 parts by weight, based on 100 parts by weight of the resin composition, preferably from 0.5 part by weight to 4 parts by weight.

＜無機填料(D)＞<Inorganic filler (D)>

本發明之電子裝置用低透濕性樹脂組成物也可以進一步含有無機填料(D)。無機填料(D)並未予以特別限定，可舉例：二氧化矽、氧化鋁、雲母、合成雲母、滑石、氧化鈣、碳酸鈣、氧化鋯、氧化鈦、鈦酸鋇、高嶺土、膨土、矽藻土、氮化硼、氮化鋁、碳化矽、氧化鋅、氧化鈰、氧化銫、氧化鎂、玻璃珠、玻璃纖維、石墨、氫氧化鈣、氫氧化鎂、氫氧化鋁、纖維素等。無機填料(D)能夠使用單獨一種，也能夠組合二種以上而使用。The low moisture permeable resin composition for an electronic device of the present invention may further contain an inorganic filler (D). The inorganic filler (D) is not particularly limited, and examples thereof include cerium oxide, aluminum oxide, mica, synthetic mica, talc, calcium oxide, calcium carbonate, zirconium oxide, titanium oxide, barium titanate, kaolin, bentonite, and strontium. Algae, boron nitride, aluminum nitride, tantalum carbide, zinc oxide, cerium oxide, cerium oxide, magnesium oxide, glass beads, glass fiber, graphite, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, cellulose, and the like. The inorganic filler (D) may be used alone or in combination of two or more.

此等之無機填料(D)能夠利用例如國際公開專利第96/31572號所記載之火焰水解法或火焰熱分解法、電漿法等之習知方法而製造。較佳的無機填料(D)能夠使用經安定化的膠體狀無機粒子之奈米分散溶膠類等，市售品能夠購自BAYER公司製之矽膠、Goldschmidt公司製之SnO2溶膠類、MERCK公司製之TiO2溶膠類、Nissan Chemicals公司製之SiO2、ZrO2、Al2O3及Sb2O3溶膠或DEGUSSA公司製之Aerosil分散物類等之市售品。The inorganic filler (D) can be produced by a conventional method such as a flame hydrolysis method, a flame thermal decomposition method, or a plasma method described in International Patent Publication No. 96/31572. A preferred inorganic filler (D) can be a nano-dispersed sol of stabilized colloidal inorganic particles, and the like can be obtained from a silicone resin manufactured by BAYER Co., Ltd., a SnO 2 sol manufactured by Goldschmidt Co., Ltd., and a MERCK company. Commercial products such as TiO 2 sols, SiO 2 , ZrO 2 , Al 2 O 3 and Sb 2 O 3 sols manufactured by Nissan Chemicals Co., Ltd., or Aerosil dispersions manufactured by DEGUSSA.

無機填料(D)能夠藉由表面之改質而使此等之黏度行為改變。粒子之表面改質能夠使用習知之表面改質劑。例如，如此之表面改質劑能夠使用與存在於無機填料(D)之表面的官能基能夠形成共價鍵或錯合物等之相互作用的化合物、或能夠與聚合物陣列相互作用的化合物。例如，如此之表面改質劑能夠使用分子內具有羧基、(第1級、第2級、第3級)胺基、4級銨基、羰基、環氧丙基、乙烯基、(甲基)丙烯醯氧基、巰基等之官能基的化合物等。如此之表面改質劑，通常在標準溫度及壓力條件下為液體，分子內之碳數係例如為15以下，較佳為10以下，特佳為8以下之低分子有機化合物所構成。該低分子有機化合物之分子量例如為500以下，較佳為350以下，特佳為200以下。The inorganic filler (D) is capable of changing the viscosity behavior of the surface by modification of the surface. The surface modification of the particles can use conventional surface modifiers. For example, such a surface modifying agent can use a compound capable of forming an interaction of a covalent bond or a complex or the like with a functional group present on the surface of the inorganic filler (D), or a compound capable of interacting with the polymer array. For example, such a surface modifying agent can have a carboxyl group, a (first, second, third) amine group, a 4- to ammonium group, a carbonyl group, a glycidyl group, a vinyl group, a (methyl) group. A compound having a functional group such as an acryloxy group or a fluorenyl group. Such a surface modifying agent is usually a liquid under standard temperature and pressure conditions, and the carbon number in the molecule is, for example, 15 or less, preferably 10 or less, and particularly preferably a low molecular organic compound of 8 or less. The molecular weight of the low molecular organic compound is, for example, 500 or less, preferably 350 or less, and particularly preferably 200 or less.

例如，較佳的表面改質劑可舉例：甲酸、乙酸、丙酸、丁酸、戊酸、己酸、丙烯酸、甲基丙烯酸、巴豆酸、檸檬酸、己二酸、琥珀酸、戊二酸、草酸、順丁烯二酸及反丁烯二酸等之碳數1至12之飽和或不飽和單或聚羧酸類(較佳為單羧酸類)；及此等之酯類(較佳為甲基丙烯酸甲酯等之C1至C4烷基酯類)；醯胺類；乙醯丙酮、2,4-己二酮、3,5-庚二酮、乙醯乙酸及C1至C4烷基乙醯乙酸類等之β-二羰基化合物等。另外，並未予以特別限定，也能夠使用習用之矽烷偶合劑作為表面改質劑。For example, preferred surface modifiers are exemplified by formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic acid, succinic acid, glutaric acid. a saturated or unsaturated mono- or polycarboxylic acid (preferably a monocarboxylic acid) having 1 to 12 carbon atoms such as oxalic acid, maleic acid or fumaric acid; and such esters (preferably C 1 to C 4 alkyl esters such as methyl methacrylate; guanamine; acetamidine, 2,4-hexanedione, 3,5-heptanedione, acetoacetic acid and C 1 to C A β-dicarbonyl compound such as a 4 -alkylacetonitrileacetic acid or the like. Further, it is not particularly limited, and a conventional decane coupling agent can also be used as the surface modifier.

無機填料(D)之粒徑通常為0.01 nm至200μm左右，較佳為0.1nm至100μm，特佳為0.1nm至50μm左右。The particle diameter of the inorganic filler (D) is usually from about 0.01 nm to about 200 μm, preferably from 0.1 nm to 100 μm, particularly preferably from about 0.1 nm to about 50 μm.

若將化合物(A)及化合物(B)之合計含量設為100重量份時，無機填料(D)之含量較佳為1至2000重量份，進一步較佳為10至1000重量份。另外，相對於電子裝置用低透濕性樹脂組成物之全部量，無機填料(D)之含量例如為5至95wt%，較佳為10至90wt%。When the total content of the compound (A) and the compound (B) is 100 parts by weight, the content of the inorganic filler (D) is preferably from 1 to 2,000 parts by weight, more preferably from 10 to 1,000 parts by weight. Further, the content of the inorganic filler (D) is, for example, 5 to 95% by weight, preferably 10 to 90% by weight, based on the total amount of the low moisture-permeable resin composition for an electronic device.

＜矽烷偶合劑(E)＞<decane coupling agent (E)>

本發明之電子裝置用低透濕性樹脂組成物為了要使與基板等之被接著物之接著性提高，進一步也可以含有矽烷偶合劑(E)。矽烷偶合劑(E)並未予以特別限定，能夠使用習知慣用之矽烷偶合劑。例如，矽烷偶合劑(E)係由下列矽烷等之水溶液中較安定者之中所選出：四甲氧基矽烷、四乙氧基矽烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、甲基三乙氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基參(甲氧基乙氧基矽烷)、苯基三甲氧基矽烷、二苯基二甲氧基矽烷、乙烯基三乙醯氧基矽烷、γ-(甲基)丙烯醯氧丙基三乙氧基矽烷、γ-(甲基)丙烯醯氧丙基三甲氧基矽烷、γ-(甲基)丙烯醯氧丙基甲基二甲氧基矽烷、γ-(甲基)丙烯醯氧丙基甲基二乙氧基矽烷、3-環氧丙基丙基三甲氧基矽烷、3-環氧丙基丙基甲基二甲氧基矽烷、3-環氧丙基丙基三乙氧基矽烷、3-環氧丙基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、對苯乙烯基三甲氧基矽烷、3-丙烯醯氧丙基三甲氧基矽烷、N-(β-胺乙基)-γ-胺丙基甲基二甲氧基矽烷、N-(β-胺乙基)-γ-胺丙基甲基二乙氧基矽烷、N-(β-胺乙基)-γ-胺丙基三甲氧基矽烷、N-(β-胺乙基)-γ-胺丙基三乙氧基矽烷、N-苯基-γ-胺丙基三甲氧基矽烷、γ-胺丙基三甲氧基矽烷、γ-胺丙基三乙氧基矽烷、3-巰丙基三甲氧基矽烷、3-巰丙基三乙氧基矽烷、3-巰丙基甲基二甲氧基矽烷、四硫化雙(三乙氧基矽烷丙基)、3-異氰酸酯丙基三乙氧基矽烷等。The low moisture permeability resin composition for an electronic device of the present invention may further contain a decane coupling agent (E) in order to improve adhesion to a substrate or the like. The decane coupling agent (E) is not particularly limited, and a conventionally used decane coupling agent can be used. For example, the decane coupling agent (E) is selected from among the more stable ones of the following decanes and the like: tetramethoxy decane, tetraethoxy decane, methyl triethoxy decane, dimethyl diethoxy Base decane, methyl triethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, vinyl ginseng (methoxy ethoxy decane), phenyl trimethoxy decane, diphenyl diol Methoxy decane, vinyl triethoxy decane, γ-(meth) propylene oxypropyl triethoxy decane, γ-(methyl) propylene oxypropyl trimethoxy decane, γ-( Methyl) propylene oxime propyl methyl dimethoxy decane, γ-(meth) propylene methoxypropyl methyl diethoxy decane, 3-epoxypropyl propyl trimethoxy decane, 3- Glycidylpropylmethyldimethoxydecane, 3-epoxypropylpropyltriethoxydecane, 3-epoxypropylpropylmethyldiethoxydecane, 2-(3,4 -Epoxycyclohexyl)ethyltrimethoxydecane, p-styryltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-(β-aminoethyl)-γ-aminepropyl Dimethoxyoxane, N-(β-aminoethyl)-γ -aminopropylmethyldiethoxydecane, N-(β-aminoethyl)-γ-aminopropyltrimethoxydecane, N-(β-aminoethyl)-γ-aminopropyltriethoxy Baseline, N-phenyl-γ-aminopropyltrimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3 - mercaptopropyltriethoxydecane, 3-mercaptopropylmethyldimethoxydecane, bis(triethoxydecanepropyl) tetrasulfide, 3-isocyanatepropyltriethoxydecane, and the like.

相對於100重量份之無機填料(D)之含量，矽烷偶合劑(E)之用量較佳為0.1至20重量份左右，更佳為0.3至8重量份，進一步較佳為0.5至5重量份之範圍。若低於0.1重量份，缺乏因矽烷偶合劑(E)所造成的樹脂之交聯效果，因而無法獲得緻密之薄膜，另外缺乏對金屬基材之偶合效果，緊貼性差，難以獲得所欲之耐鹼性與防鏽力。較20重量份為多之情形，因水解所造成的耐水、耐鹼性等各種性能顯著降低，製膜性上會發生問題，另外在經濟性之點，也容易變得不利。The amount of the decane coupling agent (E) is preferably from 0.1 to 20 parts by weight, more preferably from 0.3 to 8 parts by weight, still more preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the inorganic filler (D). The scope. If it is less than 0.1 part by weight, the crosslinking effect of the resin due to the decane coupling agent (E) is lacking, so that a dense film cannot be obtained, and the coupling effect to the metal substrate is lacking, and the adhesion is poor, and it is difficult to obtain the desired Alkali resistance and rust resistance. When the amount is more than 20 parts by weight, various properties such as water resistance and alkali resistance due to hydrolysis are remarkably lowered, problems occur in film formability, and it is likely to be disadvantageous in terms of economy.

＜其他添加劑＞<Other additives>

於本發明之電子裝置用低透濕性樹脂組成物中，依照所需，能夠使用聚合抑制劑、抗氧化劑、光安定劑、可塑劑、平坦劑、消泡劑、顏料、有機溶劑、紫外線吸收劑、離子吸附物、顏料、螢光體、脫模劑等之習用添加劑。In the low moisture permeable resin composition for an electronic device of the present invention, a polymerization inhibitor, an antioxidant, a light stabilizer, a plasticizer, a flat agent, an antifoaming agent, a pigment, an organic solvent, and an ultraviolet absorbing agent can be used as needed. Conventional additives such as agents, ion adsorbents, pigments, phosphors, mold release agents, and the like.

＜電子裝置用低透濕性樹脂組成物之製造法＞<Manufacturing Method of Low Moisture Permeability Resin Composition for Electronic Devices>

本發明之電子裝置用低透濕性樹脂組成物係藉由均勻混合上述各成分所獲得。為了獲得本發明之電子裝置用低透濕性樹脂組成物，宜使用自公轉式攪拌脫泡裝置、均質機、行星式攪拌器、3輥磨機、珠磨機等之一般已知之混合用機器而盡可能地使各成分成為均一的方式來進行攪拌、溶解、混合、分散等。The low moisture permeable resin composition for an electronic device of the present invention is obtained by uniformly mixing the above components. In order to obtain the low moisture-permeable resin composition for an electronic device of the present invention, a commonly known mixing machine such as a self-rotating agitating defoaming device, a homogenizer, a planetary agitator, a 3-roll mill, a bead mill or the like is preferably used. Stirring, dissolving, mixing, dispersing, and the like are carried out in such a manner that the components are as uniform as possible.

＜硬化物＞<hardened matter>

本發明之電子裝置用低透濕性樹脂組成物能夠藉光或熱而使其硬化。藉光而使其硬化之情形，例如，能夠利用水銀燈等進行1000mJ/cm2以上之光照射。另外，藉熱而使其硬化之情形，能夠以例如溫度為50至200℃，較佳為50至190℃，進一步較佳為50至180℃；例如硬化時間10至600分鐘，較佳為10至480分鐘，進一步較佳為15至360分鐘之條件下使其硬化。硬化溫度與硬化時間較上述範圍之下限值為低之情形，硬化變得不充分；相反地，較上述範圍之上限值為高之情形，因為有引起樹脂成分分解之情形，有任一種皆為不佳之情形。硬化溫度高之情形係縮短硬化時間；硬化溫度低之情形係拉長硬化時間等而能夠進行適當調整。藉由使本發明之電子裝置用低透濕性樹脂組成物硬化而可以獲得具優越之低透濕性的硬化物。The low moisture permeable resin composition for an electronic device of the present invention can be cured by light or heat. In the case where it is hardened by light, for example, it is possible to irradiate light of 1000 mJ/cm 2 or more with a mercury lamp or the like. Further, the case where it is hardened by heat can be, for example, a temperature of 50 to 200 ° C, preferably 50 to 190 ° C, further preferably 50 to 180 ° C; for example, a hardening time of 10 to 600 minutes, preferably 10 It is hardened to 480 minutes, further preferably 15 to 360 minutes. When the hardening temperature and the hardening time are lower than the lower limit of the above range, the hardening becomes insufficient; on the contrary, the upper limit is higher than the above range, because there is a case where the resin component is decomposed, and any one is used. All are bad. When the hardening temperature is high, the hardening time is shortened; when the hardening temperature is low, the hardening time is elongated and the like can be appropriately adjusted. By hardening the electronic device of the present invention with a low moisture-permeable resin composition, a cured product having superior low moisture permeability can be obtained.

由硬化本發明之電子裝置用低透濕性樹脂組成物而成之硬化物係低透濕性，且具優越之防濕性。硬化物之透濕度係依照JIS L1099及JIS Z0208，藉由在60℃ 90%RH條件下測定調整成厚度100 μm之樹脂硬化物的透濕量而能夠獲得。本發明之硬化物係利用上述方法所測出的透濕度例如為50g/m2‧atm‧day以下(例如，0至50g/m2‧atm‧day)，較佳為30g/m2‧atm‧day以下(例如，0至30g/m2‧atm‧day)，進一步較佳為25g/m2‧atm‧day以下(例如，0至25g/m2‧atm‧day)。另外，藉由添加無機填料(D)，若例如為20g/m2‧atm‧day以下(例如0至20g/m2‧atm‧day)，特佳為15g/m2‧atm‧day以下(例如0至15g/m2‧atm‧day)時，能夠進一步使透濕度提高The cured product obtained by curing the low moisture-permeable resin composition for an electronic device of the present invention has low moisture permeability and superior moisture resistance. The moisture permeability of the cured product can be obtained by measuring the moisture permeability of the cured resin having a thickness of 100 μm under the conditions of 60 ° C and 90% RH in accordance with JIS L1099 and JIS Z0208. The cured product of the present invention has a moisture permeability measured by the above method of, for example, 50 g/m 2 ‧ atm ‧ day or less (for example, 0 to 50 g/m 2 ‧ atm ‧ day), preferably 30 g/m 2 ‧ atm It is ‧ days or less (for example, 0 to 30 g/m 2 ‧ atm ‧ day), and further preferably 25 g / m 2 ‧ atm ‧ day or less (for example, 0 to 25 g / m 2 ‧ atm ‧ day) Further, by adding the inorganic filler (D), for example, it is 20 g/m 2 ‧ atm ‧ day or less (for example, 0 to 20 g/m 2 ‧ atm ‧ day), particularly preferably 15 g/m 2 ‧ atm ‧ day or less ( For example, 0 to 15 g/m 2 ‧atm‧day), the moisture permeability can be further improved

＜有機電致發光元件、電子紙、或太陽能電池＞<Organic electroluminescent element, electronic paper, or solar cell>

作為在本發明之電子裝置用低透濕性樹脂組成物中之電子裝置較佳可舉例：有機電致發光元件、電子紙或太陽能電池。若根據本發明之電子裝置用低透濕性樹脂組成物，則能夠使在此等電子裝置中之濕度影響成為最小限度。The electronic device as the low moisture-permeable resin composition for an electronic device of the present invention is preferably exemplified by an organic electroluminescence device, an electronic paper or a solar cell. According to the low moisture permeable resin composition for an electronic device of the present invention, the influence of humidity in such an electronic device can be minimized.

＜封閉材、密封材＞<Closed material, sealing material>

本發明之電子裝置用低透濕性樹脂組成物之硬化物能夠作為具優越之水蒸氣障壁性的有機電致發光元件、電子紙、或太陽能電池等之以低透濕性為必要的電子構件用之封閉材、密封材等使用。具體而言，藉由使以本發明之電子裝置用低透濕性樹脂組成物作為必要成分所含之封閉劑、本發明之電子裝置用低透濕性樹脂組成物作為必要成分所含之密封劑硬化而能夠形成低透濕性之封閉材、密封材。硬化之際的條件能夠採用獲得上述硬化物之際的條件。另外，本發明之電子裝置用低透濕性樹脂組成物也能夠作為接著劑使用。The cured product of the low moisture-permeable resin composition for an electronic device of the present invention can be used as an electronic component having low vapor permeability, such as an organic electroluminescence device having excellent water vapor barrier properties, an electronic paper, or a solar cell. It is used for sealing materials, sealing materials, etc. Specifically, the sealing agent contained in the low moisture permeable resin composition for an electronic device according to the present invention, and the low moisture permeable resin composition for an electronic device of the present invention are contained as a sealing component. The agent is hardened to form a sealing material and a sealing material having low moisture permeability. The conditions at the time of hardening can be the conditions at the time of obtaining the hardened|cured material mentioned above. Further, the low moisture permeable resin composition for an electronic device of the present invention can also be used as an adhesive.

實施例Example

以下，根據實施例而更詳細地說明本發明，但並不受此等實施例所限定。Hereinafter, the present invention will be described in more detail based on examples, but is not limited by the examples.

製造例1Manufacturing example 1 [氫化雙酚A二乙烯基醚之合成][Synthesis of hydrogenated bisphenol A divinyl ether]

具備附Dean & Stark之冷卻管、攪拌器及溫度計之2L的4口燒瓶中，添加碳酸鈉(31.8g、300.0mmol)、甲苯(537.2g)、丙酸乙烯酯(199.9.g、2.00mol)、氫化雙酚A(62.0g、257.7mmol)、及[IrCI(cod)]2(5.04g、7.50mmol)，安裝至130℃之油浴中而加熱回流。一邊將由反應進行而生成出的水向反應系統外抽離，且一邊攪拌4小時。其後，將反應液放冷直到室溫，加水後移入分液漏斗中。利用乙酸乙酯而萃取水層，將飽和食鹽水加入有機層中而洗淨。其後，分離有機層，利用無水硫酸鎂脫水後，蒸餾去除溶劑而獲得液狀之粗生成物。利用減壓蒸餾而精製此粗生成物(160℃、30Pa)，獲得以下式(3)所示之氫化雙酚A二乙烯基醚的無色透明液體71.6g(產率95%、純度99%)。Sodium carbonate (31.8g, 300.0mmol), toluene (537.2g), and vinyl propionate (199.9.g, 2.00mol) were added to a 2-liter 4-neck flask equipped with a Dean & Stark cooling tube, stirrer and thermometer. Hydrogenated bisphenol A (62.0 g, 257.7 mmol) and [IrCI(cod)] 2 (5.04 g, 7.50 mmol) were placed in an oil bath at 130 ° C and heated to reflux. The water produced by the reaction was extracted outside the reaction system and stirred for 4 hours. Thereafter, the reaction solution was allowed to cool to room temperature, and water was added and then transferred to a separating funnel. The aqueous layer was extracted with ethyl acetate, and saturated brine was added to the organic layer to be washed. Thereafter, the organic layer was separated, dehydrated with anhydrous magnesium sulfate, and the solvent was evaporated to give a liquid crude product. This crude product (160 ° C, 30 Pa) was purified by distillation under reduced pressure to obtain 71.6 g of a colorless transparent liquid of hydrogenated bisphenol A divinyl ether represented by the following formula (3) (yield 95%, purity 99%). .

1H-NMR(500 MHz,CDCl3)：δ0.72-0.76(m,6H)、1.01-1.46(m,12H)、1.70-1.76(m,3H)、2.00-2.12(m,3H)、3.60-3.66(m,1H)、3.97-4.04(m,3H)、4.27-4.30(d,J=15.0 Hz,2H)、6.31-6.34(m,2H) 1 H-NMR (500 MHz, CDCl 3 ): δ 0.72-0.76 (m, 6H), 1.01-1.46 (m, 12H), 1.70-1.76 (m, 3H), 2.00-2.12 (m, 3H), 3.60-3.66 (m, 1H), 3.97-4.04 (m, 3H), 4.27-4.30 (d, J = 15.0 Hz, 2H), 6.31-6.34 (m, 2H)

製造例2Manufacturing Example 2 [(2-苯基苯氧基)乙基乙烯基醚之合成]Synthesis of [(2-phenylphenoxy)ethyl vinyl ether]

具備裝設冷卻管、攪拌器及溫度計之2L的4口燒瓶中，添加氫化鈉(55%於礦物油中)(15.4g、352.9mmol)、及DMSO(510.6g)，冷卻至0℃後，將鄰苯基酚(50.6g、297.3mmol)溶解於DMSO(191.0g)而成之溶液滴入其中。其後，安裝至60℃之油浴中，將2-氯乙基乙烯基醚(38.2g、358.5mmol)溶解於DMSO(61.4g)而成之溶液滴入。攪拌反應液6小時後，冷卻至0℃後慢慢地滴入水而急冷，移入分液漏斗中。利用乙酸乙酯萃取水層，將飽和食鹽水加入有機層中而洗淨。其後，分離有機層，利用無水硫酸鈉脫水後，蒸餾去除溶劑而獲得液狀之粗生成物。利用矽膠管柱層析法而精製此粗生成物(己烷/乙酸乙酯=10/1)，獲得以下式(4)所示之(2-苯基苯氧基)乙基乙烯基醚的無色透明液體55.5g(產率78%、純度98%)。Sodium hydride (55% in mineral oil) (15.4 g, 352.9 mmol) and DMSO (510.6 g) were placed in a 2-liter 4-neck flask equipped with a cooling tube, a stirrer, and a thermometer, and after cooling to 0 ° C, A solution obtained by dissolving o-phenylphenol (50.6 g, 297.3 mmol) in DMSO (191.0 g) was added dropwise thereto. Thereafter, the mixture was placed in an oil bath of 60 ° C, and a solution obtained by dissolving 2-chloroethyl vinyl ether (38.2 g, 358.5 mmol) in DMSO (61.4 g) was added dropwise. After stirring the reaction liquid for 6 hours, it was cooled to 0 ° C, and water was slowly added dropwise thereto to be quenched, and transferred to a separatory funnel. The aqueous layer was extracted with ethyl acetate, and saturated brine was added to the organic layer and washed. Thereafter, the organic layer was separated, dehydrated with anhydrous sodium sulfate, and the solvent was evaporated to give a liquid crude product. This crude product (hexane/ethyl acetate = 10/1) was purified by a silica gel column chromatography to obtain (2-phenylphenoxy)ethyl vinyl ether represented by the following formula (4). Colorless transparent liquid 55.5 g (yield 78%, purity 98%).

1H-NMR(500 MHz,CDCl3)：δ3.96(t,J=5.0 Hz,2H)、4.17-4.21(m,3H)、6.44(dd,J=14.1,6.5 Hz,1H)、6.98-7.01(m,1H)、7.04-7.07(m,1H)、7.28-7.41(m,6H)、7.56-7.57(m,2H) 1 H-NMR (500 MHz, CDCl 3 ): δ 3.96 (t, J = 5.0 Hz, 2H), 4.17-4.21 (m, 3H), 6.44 (dd, J = 14.1, 6.5 Hz, 1H), 6.98 -7.01 (m, 1H), 7.04-7.07 (m, 1H), 7.28-7.41 (m, 6H), 7.56-7.57 (m, 2H)

製造例3Manufacturing Example 3 [雙酚F雙(3-乙基環氧丙烷-3-基甲基)醚之合成][Synthesis of bisphenol F bis(3-ethyl epoxypropan-3-ylmethyl) ether]

具備裝設冷卻管、攪拌器、溫度計之1L的4口燒瓶中，添加氫化鈉(55%於礦物油中)(13.5g、309.4mmol)、DMSO(295.0g)，冷卻至0℃後，將雙酚F(25.8g、128.9mmol)溶解於DMSO(104.1g)而成之溶液滴入其中。其後，安裝至80℃之油浴中，將甲烷磺酸-3-乙基-3-環氧丙烷甲酯(50.0g、257.4mmol)溶解於DMSO(100.6g)而成之溶液滴入。攪拌反應液4小時後，冷卻至0℃後慢慢地滴入水而急冷，移入分液漏斗中。利用乙酸乙酯而萃取水層，將飽和食鹽水加入有機層中而洗淨。其後，分離有機層，利用無水硫酸鎂脫水後，蒸餾去除溶劑而獲得液狀之粗生成物。利用矽膠管柱層析法而精製此粗生成物(己烷/乙酸乙酯=2/1→1/1)，獲得以下式(5)所示之雙酚F雙(3-乙基環氧丙烷-3-基甲基)醚的無色透明液體38.5g(產率75%、純度95%)。Sodium hydride (55% in mineral oil) (13.5 g, 309.4 mmol) and DMSO (295.0 g) were added to a 4-liter flask equipped with a cooling tube, a stirrer, and a thermometer. After cooling to 0 ° C, the mixture was cooled. A solution of bisphenol F (25.8 g, 128.9 mmol) dissolved in DMSO (104.1 g) was added dropwise thereto. Thereafter, the mixture was placed in an oil bath at 80 ° C, and a solution obtained by dissolving methanesulfonic acid-3-ethyl-3-propylene oxide methyl ester (50.0 g, 257.4 mmol) in DMSO (100.6 g) was added dropwise. After stirring the reaction liquid for 4 hours, it was cooled to 0 ° C, and water was slowly added dropwise thereto to be quenched, and transferred to a separatory funnel. The aqueous layer was extracted with ethyl acetate, and saturated brine was added to the organic layer to be washed. Thereafter, the organic layer was separated, dehydrated with anhydrous magnesium sulfate, and the solvent was evaporated to give a liquid crude product. This crude product (hexane/ethyl acetate = 2/1 → 1/1) was purified by a silica gel column chromatography to obtain a bisphenol F bis(3-ethyl epoxy) represented by the following formula (5). The colorless transparent liquid of propan-3-ylmethyl)ether was 38.5 g (yield 75%, purity 95%).

1H-NMR(500 MHz,CDCl3)：δ0.85-0.94(m,6H)、1.78-1.89(m,4H)、3.87-3.96(m,2H)、4.03-4.05(m,4H)、4.38-4.57(m,8H)、6.81-7.23(m,8H) 1 H-NMR (500 MHz, CDCl 3 ): δ 0.85-0.94 (m, 6H), 1.78-1.89 (m, 4H), 3.87-3.96 (m, 2H), 4.03-4.05 (m, 4H), 4.38-4.57 (m, 8H), 6.81-7.23 (m, 8H)

製造例4Manufacturing Example 4 [1,1’-雙酚-2-基(3-乙基環氧丙烷-3-基甲基)醚之合成]Synthesis of [1,1'-bisphenol-2-yl(3-ethylepoxypropan-3-ylmethyl)ether]

具備裝設冷卻管、攪拌器、溫度計之1L的4口燒瓶中，添加氫化鈉(55%於礦物油中)(6.8g、154.7mmol)、及DMSO(145.0g)，冷卻至0℃後，將鄰苯基酚(21.9g、128.7mmol)溶解於DMSO(104.1g)而成之溶液滴入其中。其後，安裝至80℃之油浴中，將甲烷磺酸-3-乙基-環氧丙烷甲酯(25.0g、128.9mmol)溶解於DMSO(50.3g)而成之溶液滴入。攪拌反應液5小時後，冷卻至0℃後慢慢地滴入水而急冷，移入分液漏斗中。利用乙酸乙酯而萃取水層，將飽和食鹽水加入有機層中而洗淨。其後，分離有機層，利用無水硫酸鎂脫水後，蒸餾去除溶劑而獲得液狀之粗生成物。利用矽膠管柱層析法而精製此粗生成物(己烷/乙酸乙酯=2/1→1/1)，獲得以下式(6)所示之1,1’-聯苯-2-基(3-乙基環氧丙烷-3-基甲基)醚的無色透明液體29.4 g(產率85%、純度98%)。Sodium hydride (55% in mineral oil) (6.8 g, 154.7 mmol) and DMSO (145.0 g) were added to a 4-liter flask equipped with a cooling tube, a stirrer, and a thermometer, and after cooling to 0 ° C, A solution obtained by dissolving o-phenylphenol (21.9 g, 128.7 mmol) in DMSO (104.1 g) was added dropwise thereto. Thereafter, the mixture was placed in an oil bath at 80 ° C, and a solution obtained by dissolving methanesulfonic acid-3-ethyl-propylene oxide methyl ester (25.0 g, 128.9 mmol) in DMSO (50.3 g) was added dropwise. After stirring the reaction liquid for 5 hours, it was cooled to 0 ° C, and water was slowly added dropwise thereto to be quenched, and transferred to a separatory funnel. The aqueous layer was extracted with ethyl acetate, and saturated brine was added to the organic layer to be washed. Thereafter, the organic layer was separated, dehydrated with anhydrous magnesium sulfate, and the solvent was evaporated to give a liquid crude product. This crude product (hexane/ethyl acetate = 2/1 → 1/1) was purified by a silica gel column chromatography to obtain 1,1'-biphenyl-2-yl group represented by the following formula (6). Colorless transparent liquid of (3-ethyl propylene oxide-3-ylmethyl)ether (29.4 g (yield 85%, purity 98%).

1H-NMR(500 MHz,CDCl3)：δ0.85(t,J=7.6 Hz,3H)、1.75(m,2H)、4.10(s,2H)、4.49(d,J=6.1 Hz,2H)、4.50(d,J=6.1 Hz,2H)、7.10-7.25(m,2H)、7.31-7.42(m,5H)、7.51(d,J=7.6 Hz,2H) 1 H-NMR (500 MHz, CDCl 3 ): δ 0.85 (t, J = 7.6 Hz, 3H), 1.75 (m, 2H), 4.10 (s, 2H), 4.49 (d, J = 6.1 Hz, 2H ), 4.50 (d, J = 6.1 Hz, 2H), 7.10-7.25 (m, 2H), 7.31 - 7.42 (m, 5H), 7.51 (d, J = 7.6 Hz, 2H)

製造例5Manufacturing Example 5 [雙酚F二乙烯基醚之合成][Synthesis of bisphenol F divinyl ether]

具備附Dean & Stark之冷卻管、攪拌器及溫度計之2L的4口燒瓶中，添加碳酸鈉(31.8g、300.0mmol)、甲苯(537.2g)、丙酸乙烯酯(199.9g、2.00mol)、雙酚F(51.6g、257.7mmol)、及[IrCI(cod)]2(5.04g、7.50mmol)，安裝至130℃之油浴中而加熱回流。一邊將由反應進行而生成出的水向反應系統外抽離，且一邊攪拌4小時。其後，將反應液放冷直到室溫，加水後移入分液漏斗中。利用乙酸乙酯而萃取水層，將飽和食鹽水加入有機層中而洗淨。其後，分離有機層，利用無水硫酸鎂脫水後，蒸餾去除溶劑而獲得液狀之粗生成物。利用減壓蒸餾而精製此粗生成物(142℃、30Pa)，獲得以下式(7)所示之雙酚F二乙烯基醚的無色透明液體63.0g(產率97%、純度99%)。Sodium carbonate (31.8 g, 300.0 mmol), toluene (537.2 g), and vinyl propionate (199.9 g, 2.00 mol) were added to a 2-liter 4-neck flask equipped with a Dean & Stark cooling tube, a stirrer, and a thermometer. Bisphenol F (51.6 g, 257.7 mmol) and [IrCI(cod)] 2 (5.04 g, 7.50 mmol) were placed in an oil bath at 130 ° C and heated to reflux. The water produced by the reaction was extracted outside the reaction system and stirred for 4 hours. Thereafter, the reaction solution was allowed to cool to room temperature, and water was added and then transferred to a separating funnel. The aqueous layer was extracted with ethyl acetate, and saturated brine was added to the organic layer to be washed. Thereafter, the organic layer was separated, dehydrated with anhydrous magnesium sulfate, and the solvent was evaporated to give a liquid crude product. This crude product (142 ° C, 30 Pa) was purified by vacuum distillation to obtain 63.0 g (yield: 97%, purity: 99%) of a colorless transparent liquid of bisphenol F divinyl ether represented by the following formula (7).

1H-NMR(500 MHz,CDCl3)：δ3.90-4.01(m,2H)、4.36-4.40(m,2H)、4.63-4.74(m,2H)、6.57-6.63(m,2H)、6.93-7.00(m,4H)、7.10-7.21(m,4H) 1 H-NMR (500 MHz, CDCl 3 ): δ 3.90-4.01 (m, 2H), 4.36-4.40 (m, 2H), 4.63-4.74 (m, 2H), 6.57-6.63 (m, 2H), 6.93-7.00 (m, 4H), 7.10-7.21 (m, 4H)

製造例6Manufacturing Example 6 [鄰苯基酚乙烯基醚之合成][Synthesis of o-phenylphenol vinyl ether]

具備附Dean & Stark之冷卻管、攪拌器及溫度計之2 L的4口燒瓶中，添加碳酸鈉(18.9g、178.3mmol)、甲苯(557.2g)、丙酸乙烯酯(267.5g、2.67mol)、鄰苯基酚(50.0g、293.7mmol)、及[IrCI(cod)]2(3.02 g、4.50 mmol)，安裝至130℃之油浴中而加熱回流。一邊將由反應進行而生成出的水向反應系統外抽離，且一邊攪拌4小時。其後，將反應液放冷直到室溫，加水後移入分液漏斗中。利用乙酸乙酯而萃取水層，將飽和食鹽水加入有機層中而洗淨。其後，分離有機層，利用無水硫酸鎂脫水後，蒸餾去除溶劑而獲得液狀之粗生成物。利用Kugelrohr減壓蒸餾而精製此粗生成物(240℃、50 Pa)，獲得以下式(8)所示之鄰苯基酚乙烯基醚的無色透明液體52.3g(產率91%、純度99%)。Sodium carbonate (18.9g, 178.3mmol), toluene (557.2g), and vinyl propionate (267.5g, 2.67mol) were added to a 2-L four-necked flask equipped with a Dean & Stark cooling tube, stirrer, and thermometer. O-phenylphenol (50.0 g, 293.7 mmol) and [IrCI(cod)] 2 (3.02 g, 4.50 mmol) were placed in an oil bath at 130 ° C and heated to reflux. The water produced by the reaction was extracted outside the reaction system and stirred for 4 hours. Thereafter, the reaction solution was allowed to cool to room temperature, and water was added and then transferred to a separating funnel. The aqueous layer was extracted with ethyl acetate, and saturated brine was added to the organic layer to be washed. Thereafter, the organic layer was separated, dehydrated with anhydrous magnesium sulfate, and the solvent was evaporated to give a liquid crude product. This crude product (240 ° C, 50 Pa) was purified by Kugelrohr vacuum distillation to obtain 52.3 g of a colorless transparent liquid of o-phenylphenol vinyl ether represented by the following formula (8) (yield 91%, purity 99%). ).

1H-NMR(500 MHz,CDCl3)：δ4.33(d,J=6.1 Hz,1H)、4.59(d,J=13.8 Hz,1H)、6.56(dd,J=13.8,6.1 Hz,1H)、7.10(d,J=7.6 Hz,1H)、7.18(t,J=7.6 Hz,1H)、7.31-7.35(m,2H)、7.39-7.42(m,3H)、7.51(d,J=7.6 Hz,2H) 1 H-NMR (500 MHz, CDCl 3 ): δ 4.33 (d, J = 6.1 Hz, 1H), 4.59 (d, J = 13.8 Hz, 1H), 6.56 (dd, J = 13.8, 6.1 Hz, 1H) ), 7.10 (d, J = 7.6 Hz, 1H), 7.18 (t, J = 7.6 Hz, 1H), 7.31 - 7.35 (m, 2H), 7.39 - 7.42 (m, 3H), 7.51 (d, J = 7.6 Hz, 2H)

製造例7Manufacturing Example 7 [雙酚F雙(2-乙烯氧乙基)醚之合成][Synthesis of bisphenol F bis(2-vinyloxyethyl) ether]

具備裝設冷卻管、攪拌器及溫度計之2L的4口燒瓶中，添加氫化鈉(55%於礦物油中)(30.8g、705.8mmol)、及DMSO(509.4g)，冷卻至0℃後，將雙酚F(50.2g、250.7mmol)溶解於DMSO(171.6g)而成之溶液滴入其中。其後，安裝至60℃之油浴中，將2-氯乙基乙烯基醚(58.6g、550.0mmol)溶解於DMSO(46.0g)而成之溶液滴入。攪拌反應液4小時後，冷卻至0℃後慢慢地滴入水而急冷，移入分液漏斗中。利用乙酸乙酯而萃取水層，將飽和食鹽水加入有機層中而洗淨。其後，分離有機層，利用無水硫酸鈉脫水後，蒸餾去除溶劑而獲得液狀之粗生成物。利用矽膠管柱層析法而精製此粗生成物(己烷/乙酸乙酯=10/1)，獲得以下式(9)所示之雙酚F雙(2-乙烯氧乙基)醚的白色固體37.5g(產率44%、純度99%)。Sodium hydride (55% in mineral oil) (30.8 g, 705.8 mmol) and DMSO (509.4 g) were added to a 2-liter 4-neck flask equipped with a cooling tube, a stirrer, and a thermometer, and after cooling to 0 ° C, A solution obtained by dissolving bisphenol F (50.2 g, 250.7 mmol) in DMSO (171.6 g) was added dropwise thereto. Thereafter, the mixture was placed in an oil bath of 60 ° C, and a solution obtained by dissolving 2-chloroethyl vinyl ether (58.6 g, 550.0 mmol) in DMSO (46.0 g) was added dropwise. After stirring the reaction liquid for 4 hours, it was cooled to 0 ° C, and water was slowly added dropwise thereto to be quenched, and transferred to a separatory funnel. The aqueous layer was extracted with ethyl acetate, and saturated brine was added to the organic layer to be washed. Thereafter, the organic layer was separated, dehydrated with anhydrous sodium sulfate, and the solvent was evaporated to give a liquid crude product. This crude product (hexane/ethyl acetate = 10/1) was purified by a silica gel column chromatography to obtain white bisphenol F bis(2-vinyloxyethyl)ether represented by the following formula (9). The solid was 37.5 g (yield 44%, purity 99%).

1H-NMR(500 MHz,CDCl3)：δ3.85=4.05(m,6H)、4.14-4.16(m,4H)、4.22-4.25(m,2H)、6.47-6.54(m,2H)、6.80-6.89(m,2H)、7.06-7.09(m,4H)、7.12-7.16(m,4H) 1 H-NMR (500 MHz, CDCl 3 ): δ 3.85 = 4.05 (m, 6H), 4.14 - 4.16 (m, 4H), 4.22-4.25 (m, 2H), 6.47-6.54 (m, 2H), 6.80-6.89 (m, 2H), 7.06-7.09 (m, 4H), 7.12-7.16 (m, 4H)

實施例1Example 1

將69.3重量份之雙酚F二環氧丙基醚(商品名RE-303S；日本化藥股份有限公司製)、29.7重量份之環氧丙基苯基醚(商品名G0098；東京化成工業股份有限公司製)、1重量份之PI-2074倒入自公轉式攪拌脫泡裝置(型式AR-250；Thinky股份有限公司製)內，進行攪拌、溶解、混合、分散，調製樹脂組成物之溶液。69.3 parts by weight of bisphenol F diglycidyl ether (trade name: RE-303S; manufactured by Nippon Kayaku Co., Ltd.), 29.7 parts by weight of epoxypropyl phenyl ether (trade name G0098; Tokyo Chemical Industry Co., Ltd.) 1 part by weight of PI-2074 is poured into a self-revolving stirring and defoaming device (type AR-250; manufactured by Thinky Co., Ltd.), and stirred, dissolved, mixed, and dispersed to prepare a solution of the resin composition. .

實施例2至4Examples 2 to 4

以表1所示之量而使用表1所示之化合物(A)、化合物(B)、聚合起始劑(C)、及無機填料(D)，與實施例1同樣地調製樹脂組成物之溶液。還有，針對作為無機填料(D)之二氧化矽，使用藉矽烷偶合劑(商品名KBM-403；信越化學工業股份有限公司製)將商品名Adomafine SC4500(Adomatechs股份有限公司製)表面改質而成者。另外，針對作為無機填料(D)之滑石，使用商品名MST High Talc；竹原化學工業股份有限公司製。The resin composition was prepared in the same manner as in Example 1 except that the compound (A), the compound (B), the polymerization initiator (C), and the inorganic filler (D) shown in Table 1 were used in an amount shown in Table 1. Solution. In addition, the surface of the product of Adomafine SC4500 (manufactured by Adomatech Co., Ltd.) was modified with a decane coupling agent (trade name: KBM-403; manufactured by Shin-Etsu Chemical Co., Ltd.) for the cerium oxide as the inorganic filler (D). Founder. Further, as the talc as the inorganic filler (D), a trade name of MST High Talc; manufactured by Takehara Chemical Industry Co., Ltd. was used.

實施例5Example 5

除了化合物(B)係使用鄰苯基酚環氧丙基醚(商品名SY-OPG；阪本藥品工業股份有限公司製)以取代環氧丙基醚以外，進行相同於實施例1之方式而調製樹脂組成物之溶液。The same procedure as in Example 1 was carried out except that the compound (B) was prepared by using o-phenylphenol epoxypropyl ether (trade name: SY-OPG; manufactured by Sakamoto Pharmaceutical Co., Ltd.) in place of the epoxypropyl ether. A solution of the resin composition.

實施例6至8Examples 6 to 8

以表1所示之量而使用表1所示之化合物(A)、化合物(B)、聚合起始劑(C)、及無機填料(D)，與實施例5同樣地調製樹脂組成物之溶液。還有，針對作為無機填料(D)之二氧化矽，使用藉矽烷偶合劑(商品名KBM-403；信越化學工業股份有限公司製)將商品名Adomafine SC4500(Adomatechs股份有限公司製)表面改質而成者。The compound (A), the compound (B), the polymerization initiator (C), and the inorganic filler (D) shown in Table 1 were used in the amounts shown in Table 1, and the resin composition was prepared in the same manner as in Example 5. Solution. In addition, the surface of the product of Adomafine SC4500 (manufactured by Adomatech Co., Ltd.) was modified with a decane coupling agent (trade name: KBM-403; manufactured by Shin-Etsu Chemical Co., Ltd.) for the cerium oxide as the inorganic filler (D). Founder.

實施例9Example 9

除了化合物(A)係使用以上式(I-3)所表示之3,4,3’,4’-二環氧雙環己基(商品名「Celloxide 8000」、Daicel化學工業股份有限公司製)以取代雙酚F二環氧丙基醚，如表1的方式來變更各成分之摻合量以外，進行相同於實施例5之方式而調製樹脂組成物之溶液。In addition to the compound (A), 3,4,3',4'-diepoxybicyclohexyl (trade name "Celloxide 8000", manufactured by Daicel Chemical Industry Co., Ltd.) represented by the above formula (I-3) is used instead. The bisphenol F diglycidyl ether was prepared in the same manner as in Example 5 except that the blending amount of each component was changed as shown in Table 1.

實施例10Example 10

除了化合物(A)係使用在製造例1所獲得之氫化雙酚A二乙烯基醚(式(3))以取代雙酚F二環氧丙基醚，化合物(B)係使用在製造例2所獲得之(2-苯基苯氧基)乙基乙烯基醚(式(4))以取代環氧丙基醚，化合物(C)係使用SI-60以取代PI-2074，如表1的方式來變更各成分之摻合量以外，進行相同於實施例1之方式而調製樹脂組成物之溶液。In addition to the compound (A), the hydrogenated bisphenol A divinyl ether (formula (3)) obtained in Production Example 1 was used in place of the bisphenol F diglycidyl ether, and the compound (B) was used in Production Example 2. The obtained (2-phenylphenoxy)ethyl vinyl ether (formula (4)) was substituted for the epoxy propyl ether, and the compound (C) was replaced with SI-60 by using SI-60, as shown in Table 1. In the same manner as in the above, the solution of the resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed.

實施例11Example 11

除了化合物(A)係使用在製造例3所獲得之雙酚F雙(3-乙基環氧丙烷-3-基甲基)醚(式(5))以取代在製造例1所獲得之氫化雙酚A二乙烯基醚，化合物(B)係使用在製造例4所獲得之1,1’-聯苯-2-基(3-乙基環氧丙烷-3-基甲基)醚(式(6))以取代在製造例2所獲得之(2-苯基苯氧基)乙基乙烯基醚，如表1的方式來變更各成分之摻合量以外，進行相同於實施例10之方式而調製樹脂組成物之溶液。In addition to the compound (A), the bisphenol F bis(3-ethyl propylene oxide-3-ylmethyl) ether (formula (5)) obtained in Production Example 3 was used in place of the hydrogenation obtained in Production Example 1. Bisphenol A divinyl ether, compound (B) was used in the 1,1'-biphenyl-2-yl (3-ethyl propylene oxide-3-ylmethyl) ether obtained in Production Example 4 (6)) The same procedure as in Example 10 was carried out except that (2-phenylphenoxy)ethyl vinyl ether obtained in Production Example 2 was changed as shown in Table 1 except that the blending amount of each component was changed. A solution of the resin composition is prepared in a manner.

實施例12Example 12

除了化合物(A)係使用在製造例5所獲得之雙酚F二乙烯基醚(式(7))以取代在製造例1所獲得之氫化雙酚A二乙烯基醚，使用在製造例6所獲得之鄰苯基酚乙烯基醚(式(8))以取代在製造例2所獲得之(2-苯基苯氧基)乙基乙烯基醚以外，進行相同於實施例10之方式而調製樹脂組成物之溶液。In addition to the compound (A), the bisphenol F divinyl ether (formula (7)) obtained in Production Example 5 was used in place of the hydrogenated bisphenol A divinyl ether obtained in Production Example 1, and used in Production Example 6 The o-phenylphenol vinyl ether (formula (8)) obtained was substituted in the same manner as in Example 10 except that (2-phenylphenoxy)ethyl vinyl ether obtained in Production Example 2 was used. A solution of the resin composition is prepared.

實施例13Example 13

除了化合物(A)係使用在製造例7所獲得之雙酚F雙(2-乙烯氧基乙基)醚(式(9))以取代在製造例5所獲得之雙酚F二乙烯基醚以外，進行相同於實施例12之方式而調製樹脂組成物之溶液。In place of the compound (A), the bisphenol F bis(2-vinyloxyethyl)ether (formula (9)) obtained in Production Example 7 was used in place of the bisphenol F divinyl ether obtained in Production Example 5. A solution in which the resin composition was prepared in the same manner as in Example 12 was carried out.

實施例14Example 14

除了化合物(A)係使用在製造例7所獲得之雙酚F雙(2-乙烯氧基乙基)醚(式(9))以取代在製造例1所獲得之氫化雙酚A二乙烯基醚以外，進行相同於實施例10之方式而調製樹脂組成物之溶液。In place of the compound (A), the bisphenol F bis(2-vinyloxyethyl)ether (formula (9)) obtained in Production Example 7 was used in place of the hydrogenated bisphenol A divinyl group obtained in Production Example 1. A solution of the resin composition was prepared in the same manner as in Example 10 except for the ether.

實施例15Example 15

除了化合物(A)係使用雙酚F二丙烯酸酯(Nard研究所股份有限公司合成品)，化合物(B)係使用2-(鄰苯基苯氧基)丙烯酸乙酯(商品名HRD-01、日本蒸餾工業股份有限公司製)，化合物(C)係使用1,1,3,3-過氧化四甲基丁基-2-乙基己酸酯(商品名Perocta O、日本油脂股份有限公司製)，如表1的方式來變更各成分之摻合量以外，進行相同於實施例1之方式而調製樹脂組成物之溶液。In addition to the compound (A), bisphenol F diacrylate (synthesized product of Nard Research Co., Ltd.) was used, and the compound (B) was ethyl 2-(o-phenylphenoxy)acrylate (trade name HRD-01, Japan Distillation Industry Co., Ltd.), compound (C) uses 1,1,3,3-tetramethylbutyl-2-ethylhexanoate peroxide (trade name Perocta O, manufactured by Nippon Oil & Fat Co., Ltd.) The solution of the resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 1.

實施例16Example 16

除了化合物(A)係使用酚醛清漆環氧丙基醚樹脂(酚酚醛清漆型環氧樹脂)(商品名jER-152、三菱化學股份有限公司製)以外，進行相同於實施例1之方式而調製樹脂組成物之溶液。The same procedure as in Example 1 was carried out except that the novolak epoxy epoxide resin (phenol novolak type epoxy resin) (trade name: jER-152, manufactured by Mitsubishi Chemical Corporation) was used as the compound (A). A solution of the resin composition.

比較例1至9Comparative Examples 1 to 9

以表1所示之量而使用表1所示之化合物(A)及聚合起始劑(C)，進行與實施例2同樣之方式來調製樹脂組成物之溶液。The compound (A) shown in Table 1 and the polymerization initiator (C) were used in the amounts shown in Table 1, and a solution of the resin composition was prepared in the same manner as in Example 2.

＜樹脂組成物之硬化＞<hardening of resin composition>

藉由利用水銀燈而對實施例1、2、4至9、16、比較例1至3、9所獲得之樹脂組成物進行5000 mJ/cm2之光照射，接著在加熱乾燥機內，於100℃加熱1小時而製得硬化物。The resin compositions obtained in Examples 1, 2, 4 to 9, 16, and Comparative Examples 1 to 3, 9 were irradiated with light of 5000 mJ/cm 2 by using a mercury lamp, followed by heating in a heating dryer at 100 The cured product was obtained by heating at ° C for 1 hour.

對實施例3、10至15、比較例4至8所獲得之樹脂組成物，於150℃進行2小時之加熱而製成硬化物。The resin compositions obtained in Examples 3, 10 to 15, and Comparative Examples 4 to 8 were heated at 150 ° C for 2 hours to obtain a cured product.

＜透濕度之評估＞<Evaluation of moisture permeability>

硬化物之透濕度係依照JIS L1099及JIS Z0208，在60℃90%RH條件下，測定調整至厚度100 μm之樹脂硬化物的透濕度。The moisture permeability of the cured product was measured according to JIS L1099 and JIS Z0208, and the moisture permeability of the cured resin of the resin adjusted to a thickness of 100 μm was measured under the conditions of 60 ° C and 90% RH.

表1中顯示針對實施例1至16、比較例1至9所獲得之樹脂組成物之硬化物的透濕度之測定結果。Table 1 shows the results of measurement of the moisture permeability of the cured product of the resin compositions obtained in Examples 1 to 16 and Comparative Examples 1 to 9.

化合物(A)與化合物(B)之共聚物的實施例1至8所獲得之樹脂組成物之硬化物與僅由任一種化合物(A)製得的聚合物(比較例1)作一比較，可以獲得低透濕度之硬化物。同樣地，實施例9之硬化物係較比較例3之硬化物、實施例10之硬化物係較比較例4之硬化物、實施例11之硬化物係較比較例5之硬化物、實施例12之硬化物係較比較例6之硬化物、實施例13、14之硬化物係較比較例7之硬化物、實施例15之硬化物係較比較例8之硬化物、實施例16之硬化物係較比較例9之硬化物顯示更低的透濕度(低透濕性)。The cured product of the resin composition obtained in Examples 1 to 8 of the copolymer of the compound (A) and the compound (B) was compared with the polymer obtained by only the compound (A) (Comparative Example 1). A cured product having a low moisture permeability can be obtained. Similarly, the cured product of Example 9 was compared with the cured product of Comparative Example 3, the cured product of Example 10, the cured product of Comparative Example 4, the cured product of Example 11, and the cured product of Comparative Example 5, and the examples. The cured product of 12 is harder than the hardened material of Comparative Example 6, the cured product of Examples 13 and 14 is harder than the cured product of Comparative Example 7, the cured product of Example 15 is harder than the cured product of Comparative Example 8, and the hardening of Example 16. The cured product of Comparative Example 9 showed lower moisture permeability (low moisture permeability).

[產業上利用之可能性][Possibility of industrial use]

使本發明之電子裝置用低透濕性樹脂組成物硬化所獲得之硬化物係具優越之水蒸氣障壁性，能夠作為有機電致發光元件、電子紙、或太陽能電池等之需要低透濕性的電子構件用之封閉材、密封材等使用。另外，本發明之電子裝置用低透濕性樹脂組成物也能夠作為接著劑使用。The cured product obtained by curing the low moisture permeability resin composition of the electronic device of the present invention has superior water vapor barrier properties, and can be used as an organic electroluminescence device, an electronic paper, or a solar cell, etc., which requires low moisture permeability. The electronic component is used for a sealing material, a sealing material, or the like. Further, the low moisture permeable resin composition for an electronic device of the present invention can also be used as an adhesive.

Claims (14)

一種電子裝置用樹脂組成物，其特徵為含有：1分子中具有2個以上環氧基且具有2個芳香族環或2個脂肪族環之化合物(A)；1分子中具有1個環氧基及具有1或2個芳香族環或1或2個脂肪族環，且分子量為50至1000之化合物(B)；及聚合起始劑(C)；其中相對於100重量份之該化合物(A)，該化合物(B)之含量係1~1000重量份。 A resin composition for an electronic device, which comprises a compound (A) having two or more epoxy groups and having two aromatic rings or two aliphatic rings in one molecule; and one epoxy in one molecule And a compound (B) having 1 or 2 aromatic rings or 1 or 2 aliphatic rings and having a molecular weight of 50 to 1000; and a polymerization initiator (C); wherein the compound is relative to 100 parts by weight A) The content of the compound (B) is 1 to 1000 parts by weight. 如申請專利範圍第1項之電子裝置用樹脂組成物，其中該芳香族環為苯環，該脂肪族環為環己烷環。 The resin composition for an electronic device according to claim 1, wherein the aromatic ring is a benzene ring, and the aliphatic ring is a cyclohexane ring. 如申請專利範圍第1項之電子裝置用樹脂組成物，其中相對於100重量份之該化合物(A)，該化合物(B)之含量為10至250重量份。 The resin composition for an electronic device according to claim 1, wherein the compound (B) is contained in an amount of 10 to 250 parts by weight based on 100 parts by weight of the compound (A). 如申請專利範圍第1至3項中任一項之電子裝置用樹脂組成物，其進一步含有無機填料(D)。 The resin composition for an electronic device according to any one of claims 1 to 3, further comprising an inorganic filler (D). 如申請專利範圍第1至3項中任一項之電子裝置用樹脂組成物，其進一步含有矽烷偶合劑(E)。 The resin composition for an electronic device according to any one of claims 1 to 3, further comprising a decane coupling agent (E). 如申請專利範圍第1至3項中任一項之電子裝置用樹脂組成物，其中該聚合起始劑(C)為光或熱陽離子聚合起始劑、或是光或熱自由基聚合起始劑。 The resin composition for an electronic device according to any one of claims 1 to 3, wherein the polymerization initiator (C) is a photo or thermal cationic polymerization initiator or an optical or thermal radical polymerization initiation Agent. 一種如申請專利範圍第1至6項中任一項之電子裝置用樹脂組成物之用途，其係用於製造有機電致發光元件、電子紙或太陽能電池之電子裝置。 The use of a resin composition for an electronic device according to any one of claims 1 to 6, which is an electronic device for manufacturing an organic electroluminescence device, an electronic paper or a solar cell. 一種硬化物，其係將如申請專利範圍第1至6項中任一項之電子裝置用樹脂組成物硬化而成。 A cured product obtained by hardening a resin composition for an electronic device according to any one of claims 1 to 6. 如申請專利範圍第8項之硬化物，其依照JIS L1099及JIS Z0208，藉由在60℃ 90%RH條件下測定厚度調整成100μm之硬化物的透濕量之透濕度為50g/m2‧atm‧day以下。 According to JIS L1099 and JIS Z0208, the moisture permeability of the cured product whose thickness is adjusted to 100 μm is 50 g/m 2 in accordance with JIS L1099 and JIS Z0208. Below atm‧day. 一種封閉劑，其含有如申請專利範圍第1至6項中任一項之電子裝置用樹脂組成物。 A sealant comprising the resin composition for an electronic device according to any one of claims 1 to 6. 一種密封劑，其含有如申請專利範圍第1至6項中任一項之電子裝置用樹脂組成物。 A sealant comprising the resin composition for an electronic device according to any one of claims 1 to 6. 一種有機電致發光元件，其含有如申請專利範圍第8或9項之硬化物。 An organic electroluminescent device comprising a cured product according to claim 8 or 9. 一種電子紙，其含有如申請專利範圍第8或9項之硬化物。 An electronic paper containing a cured product as in claim 8 or 9. 一種太陽能電池，其含有如申請專利範圍第8或9項之硬化物。 A solar cell comprising a cured product as in claim 8 or 9.
TW100128662A 2010-08-12 2011-08-11 Permeability resin composition, cured product and use thereof TWI591089B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010180704 2010-08-12

Publications (2)

Publication Number Publication Date
TW201211094A TW201211094A (en) 2012-03-16
TWI591089B true TWI591089B (en) 2017-07-11

Family

ID=45567657

Family Applications (1)

Application Number Title Priority Date Filing Date
TW100128662A TWI591089B (en) 2010-08-12 2011-08-11 Permeability resin composition, cured product and use thereof

Country Status (3)

Country Link
JP (1) JP5812993B2 (en)
TW (1) TWI591089B (en)
WO (1) WO2012020688A1 (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5829856B2 (en) * 2011-07-29 2015-12-09 丸善石油化学株式会社 Method for producing aromatic vinyl ether
JP6363508B2 (en) * 2012-11-28 2018-07-25 日本化薬株式会社 Resin composition and cured product thereof (1)
JP6228734B2 (en) * 2013-02-14 2017-11-08 日東電工株式会社 Resin sheet for encapsulating electronic components, resin-encapsulated semiconductor device, and method for producing resin-encapsulated semiconductor device
JP6474719B2 (en) * 2013-02-19 2019-02-27 株式会社ダイセル Curable composition, cured product thereof, optical member, and optical apparatus
KR101763058B1 (en) 2013-05-28 2017-07-28 주식회사 다이셀 Curable composition for sealing optical semiconductor
JP6278624B2 (en) * 2013-07-12 2018-02-14 株式会社日本触媒 Metal oxide particle-containing composition and optical member
JP5703429B1 (en) * 2013-10-30 2015-04-22 積水化学工業株式会社 Sealant for organic EL display element
KR102226349B1 (en) * 2013-10-30 2021-03-10 세키스이가가쿠 고교가부시키가이샤 Sealing agent for organic el display elements
JPWO2015087807A1 (en) * 2013-12-11 2017-03-16 積水化学工業株式会社 Curable resin composition for sealing organic electroluminescence display element, curable resin sheet for sealing organic electroluminescence display element, and organic electroluminescence display element
KR102418079B1 (en) * 2014-05-20 2022-07-06 세키스이가가쿠 고교가부시키가이샤 Sealing agent for organic electroluminescence display element
JP6527390B2 (en) * 2014-06-03 2019-06-05 積水化学工業株式会社 Sealant for organic electroluminescent display device
JP2016012021A (en) * 2014-06-27 2016-01-21 富士フイルム株式会社 Polarizing plate protective film, polarizing plate, image display device, and method for manufacturing polarizing plate protective film
JP6710125B2 (en) * 2016-08-04 2020-06-17 日本化薬株式会社 Liquid crystal sealant and liquid crystal display cell using the same
KR102431016B1 (en) * 2016-09-16 2022-08-09 세키스이가가쿠 고교가부시키가이샤 Encapsulant for organic electroluminescent display elements
JP6228289B1 (en) * 2016-12-28 2017-11-08 株式会社ダイセル Composition for sealing an organic electroluminescence device
TWI761583B (en) * 2017-08-24 2022-04-21 日商電化股份有限公司 Sealants for organic electroluminescent elements
WO2021059420A1 (en) * 2019-09-26 2021-04-01 積水化学工業株式会社 Photocurable resin composition for electronic devices
WO2021059419A1 (en) * 2019-09-26 2021-04-01 積水化学工業株式会社 Photocurable resin composition for electronic devices
KR20230021827A (en) * 2021-08-06 2023-02-14 (주)이녹스첨단소재 Thermosetting liquid composition for an encapsulant of organic light emitting device

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4502367B2 (en) * 2004-02-04 2010-07-14 旭化成イーマテリアルズ株式会社 Method for manufacturing cylindrical flexographic printing plate capable of laser engraving
JP4548415B2 (en) * 2004-03-04 2010-09-22 東亞合成株式会社 UV curable composition
JP4570417B2 (en) * 2004-08-06 2010-10-27 ナミックス株式会社 Liquid sealing resin composition
JP2007277467A (en) * 2006-04-10 2007-10-25 Sony Chemical & Information Device Corp Curable resin composition
JP4999393B2 (en) * 2006-07-31 2012-08-15 旭化成ケミカルズ株式会社 Cationic photosensitive composition and cured product thereof
JP5234562B2 (en) * 2006-08-10 2013-07-10 旭化成ケミカルズ株式会社 Photosensitive composition
JP2008059945A (en) * 2006-08-31 2008-03-13 Nagase Chemtex Corp Method of manufacturing electronic device
JP2010018797A (en) * 2008-06-11 2010-01-28 Sekisui Chem Co Ltd Curable composition for optical parts, adhesive agent for optical parts, and sealing agent for organic electroluminescence element
JP5683073B2 (en) * 2009-01-20 2015-03-11 三菱化学株式会社 Epoxy resin composition for solar cell encapsulant and solar cell
JP5684460B2 (en) * 2009-04-06 2015-03-11 株式会社ダイセル Cationic polymerizable resin composition and cured product thereof

Also Published As

Publication number Publication date
JP5812993B2 (en) 2015-11-17
TW201211094A (en) 2012-03-16
WO2012020688A1 (en) 2012-02-16
JPWO2012020688A1 (en) 2013-10-28

Similar Documents

Publication Publication Date Title
TWI591089B (en) Permeability resin composition, cured product and use thereof
TW201802134A (en) Curable composition and cured object obtained by curing same
TWI743055B (en) Polyfunctional epoxy compound and curable composition containing the same
TW201439189A (en) Curable epoxy resin composition
TWI582167B (en) Containing silicon hardened composition and hardened material
WO2018037565A1 (en) Epoxy resin composition and cured resin film with low curing shrinkage and excellent adhesion
TW201040203A (en) Olefin resin, epoxy resin, curable resin composition, and material resulting from curing same
TW201802176A (en) Epoxy compound, curable composition containing this, and cured product of curable composition
JP7160803B2 (en) Curable composition for adhesive, adhesive sheet, cured product, laminate, and device
JP2017008147A (en) Polyorganosilsesquioxane, curable composition, adhesive sheet, laminate and device
JP5827853B2 (en) Composition and cured product thereof
JP2017008145A (en) Curable composition, adhesive sheet, laminate and device
JP5839934B2 (en) Resin composition and cured product thereof
WO2016204014A1 (en) Curable composition
JP6211746B1 (en) Resin composition
JP2019001995A (en) Ultraviolet-curable resin composition, method of manufacturing organic el light-emitting device, and organic el light-emitting device
KR20210151819A (en) Curable composition and cured product thereof
US20230331688A1 (en) Diepoxy compound, curable composition, cured product, and optical member
WO2015030089A1 (en) Curable resin composition, curable resin composition for powder moulding, and optical semiconductor device
JP2018145430A (en) Ultraviolet-curable resin composition, method of manufacturing organic el light-emitting device, and organic el light-emitting device
JP2015124286A (en) Curable composition
TWI723175B (en) Epoxy compound, curable composition containing the same, cured product obtained by curing the curable composition, and method for producing the cured product
WO2012053377A1 (en) High refractive index resin composition and cured resin
JP2015109202A (en) Method for manufacturing optical semiconductor device
JP7468064B2 (en) Cationically polymerizable composition