TW201103973A - Encapsulant composition and method for fabricating encapsulant - Google Patents

Abstract

An encapsulant composition is provided, including 100 parts by weight of resin monomers, 0.1-15 parts by weight of a filler and 0.1-5 parts by weight of an initiator. The resin monomers comprise an epoxy-acrylic resin monomer, a silicone-acrylic resin monomer and an urethane-diacrylic resin monomer. A method for fabricating an encapsulant is also provided.

Description

201103973 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for manufacturing a packaging material, which has a high-resistance effect, and a package for a product and a package material is suitable for solid-state illumination. Yuan [Prior Art] In recent years, with the development of the optoelectronic industry, light-emitting diodes, light-emitting diodes, and various optoelectronic products such as organic have come out. However, the photoelectric devices such as batteries in such photovoltaic devices are also affected by the influence of water vapor and oxygen, and the # sub-components are highly susceptible to air. The photovoltaic devices need to be properly sealed to prevent their useful life. Therefore, 'the water and oxygen of these circles, tons of ❹I lt; electronic components are in contact with the external materials, the resin monomer is heated to some process materials and hardeners are mixed, this system = fat , can be completed when adding a fill. In addition, (4) even above ten (t) in the above (4): control the reaction conditions of resin synthesis and the safety of the process. Therefore, the manufacturing cost of the packaging material is not easily reduced. The resin components in the packaging materials are mainly divided into three categories: acrylic tree sap, epoxy resin, and silky resin. The sealing material in JP7304846 is made of epoxy resin, which has high thermal stability and can maintain stability even in environments above 3 °C. The encapsulating material in U.S. Patent No. 2,005,042,462 is a silicone resin having high adhesion and high heat stability to maintain stability in an environment above 250 °C. In US2005006296 201103973, the packaging materials department borrowed

In 172, the encapsulating material is applied to a light-emitting diode device, and the package (4) used is an epoxy resin cut. In the ·33522, the packaging material was applied to a solar cell device, and the sealing materials used were acrylic resin, epoxy resin or enamel resin. SUMMARY OF THE INVENTION The disclosed package material composition comprises: 1 part by weight of resin monomer, including epoxy-acrylic (Ej) 〇 xy_Acrylics resin monomer, ruthenium acrylate resin monomer And a bisethane urethane-diacrylics resin monomer; 0.1 to 15 parts by weight of a filler; and 0.1 to 5 parts by weight of a starter. The disclosed method for manufacturing a package material comprises: providing a package material composition comprising: 100 parts by weight of a resin monomer, including an epoxy resin (Epoxy-Acrylics) resin monomer, and a ruthenium resin resin monomer. And a bifunctional urethane-diacrylics resin monomer; 〇·ι_ΐ 5 parts by weight of the filler; and 0.1-5 parts by weight of the initiator; the first procedure polymerizes the package material composition, Wherein the first program comprises: a heating program, a 201103973 ultraviolet light irradiation program, an optical program program curing the package material sequence, or a combination thereof; and a second second program comprising: a fat product to form the packaging material, wherein In order to make the present invention easy to understand, the following is a more detailed description of the following, and the advantages can be more clearly described as follows: 乂 钿 钿 , , , , , , , , 配合 配合 配合 配合 配合 配合 配合 配合 配合 【 【 【 Features - _ process, can be quickly 敎 ^ by resin monomer material matching on-site (in-situ, material manufacturing methods, j &5; performance of the packaging material. The disclosed seal is prepared under rapid conditions + lower Reduction (4) Materials with higher safety and superior water resistance. The exposed electrical products such as luminescent bipolar and permeability are suitable for various fillings ===: The main component is a resin monomer 1 rate and colorless transparent packaging material;::: formulated to have a high permeability of the monomer to account for 100 parts by weight, the package material composition extract weight and about 0. M # The bismuth agent is about 0.1~1: 1 〇〇 by weight, respectively. The heart Λ is based on the singularity of the resin monomer t = single gram strength, - dust gram force (EX-S) paste month early Body acryl resin monomer and urethane-diacrylics resin monomer. The above epoxy-acrylic resin monomer has the following chemical formula: 201103973 ο R2\ /c\ /r1\ \〇' CH——CH2 || \/ ch2 0 wherein R1 and R2 are each independently a stupid base, an alkylphenyl group having a carbon number of 1 to 12, an alkyl group having a carbon number of 1 to 12, An alkoxy group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, or a cycloalkoxy group having a carbon number of 1 to 12. An epoxy-acrylic resin single system is used. Polymer substrate, Lifting the encapsulating material is then properties of the above-described bifunctional urethane acrylic monomer having the formula: R6

HC

CH

R4 - OCN

R3—NCO

R7 CH wherein R3, R4 and R5 are each independently a phenyl group, an alkylphenyl group having a carbon number of from 1 to 12, an alkyl group having a carbon number of from 1 to 12, and a carbon number of from 1 to 12; An ether group, an alkoxy group having a carbon number of 1 to 12 or a cycloalkoxy group having a carbon number of 1 to 12; and R6 and R7 each independently a stupid group and having an alkyl group having a carbon number of 1 to 12 a phenyl group, an alkyl group having a carbon number of 1 to 12, an ether group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, and a ring having a carbon number of 1 to 12 Alkoxy or hydrogen. The bifunctional urethane acryl single system acts as a polymer matrix to enhance the encapsulating properties of the encapsulating material. The above ruthenium resin monomer has the following chemical formula: 201103973 R9 R8-

I

Si-R10 R11

I o R, <fc ? ^仏心为^和... Each independently is a phenyl-containing stone, the phenyl group in the i~12, the carbon number in the W2, the carbon content = The ether group of 1 to 12, the carbon number is between 12 and the carbon number; and the ring is alkoxy groups of 1 to 12. Shishi Acrylic Resin Single System as a polymer base II, the subsequent properties of the material. In addition, Shishi Acrylic Resin alone can avoid micro-discrimination should be produced too fast, Lai New should be better controlled. The ear ratio is! :! ~3.^3 1 Acrylic resin monomer in which each monomer is Mo, .丄 3 ' is preferably 1: 2 : 1 to 3, more preferably 2. 2. 2. The present invention uses the above three kinds of ^. = strength, refractive index and, ===; = oxidation = coffin;: the filler in the product is, for example, oxygen cutting or nitriding, metal or: carbon: == The metal, for example, the heat:::in: the initiator contains a photoinitiator, , ' σ thermal initiator such as peroxide, even 201103973 nitrogen compound, 1-cyclohexyl phenyl ketone A free radical initiator such as (l-Hydroxy-cyclohexyl-pheny 1-ketone). The photoinitiator may be a cationic initiator such as iodonium, (4-methylphenyl) [4-(2-methylpropyl)phenyl]-hexafluorophos phate) or a cyclopentadienyl transition metal complex such as Bis (eta 5). -2,4-cyclopentadien-l-yl) Bis[2,6-difluoro-3-(lH-pyrrol-lyl)phenyl]titanium. After the above-mentioned encapsulating material composition is mixed, a polymerization process and a curing process are sequentially performed in a fieldwise manner to form the encapsulating material of the present invention. The above polymerization procedure may be a heating procedure, an ultraviolet irradiation procedure, a microwave procedure, or a combination of the foregoing. In one embodiment, the polymerization procedure is an ultraviolet light irradiation procedure or a microwave procedure. The procedure is performed in-situ by a deep ultraviolet light source or in-situ by a microwave reactor. The prepared encapsulating material has a viscosity of 1 to 100,000 cps at 25 Torr, preferably 5,0 因, depending on the length of the illumination or microwave time and the power of the light source or microwave reactor used. ~30, 〇〇〇cps, and light transmittance of more than 85%' is suitable for packaging applications such as light-emitting elements such as organic light-emitting diodes or light-emitting diodes, and electronic components such as solar cells. The UV polymerization process is carried out for a period of time of about K200 minutes, preferably about 1 to 20 minutes' power of about 1 to 10,000 watts, preferably 丨~(7)(10) watts. The application time of the microwave polymerization procedure is about 丨~ plus ^ minutes, preferably about M0 minutes, and the power is about U0000 watts, preferably 丨~(7)(9) watts. If polymerization is carried out using a heating program, it can be continuously heated at 60-150 for 201103973 1-100 hours. Compared with heating (4), the use of ultraviolet light and microwave polymerization has the advantages of short synthesis time, solvent-free and low cost. The prepared packaging material is also excellent in gas barrier rate and adhesion strength, which can be attributed to ultraviolet light. The polymerization time with the microwave method is short (especially microwave), and the excessive length of the polymer chain can be prevented from hindering the dispersion of the filler. As the filler reaches a sufficient uniformity, the gas barrier capacity and the subsequent strength are improved. The microwave polymerization method is different from the conventional heating method of Φ. The use of microwave deep heating characteristics instead of the traditional synthetic heat convection transfer method can reduce unnecessary heat energy loss. Moreover, the reactant molecules will rotate dipolely according to the change of the microwave field, thereby increasing the number of collisions and the probability of effective collision, increasing the reaction yield, increasing the reaction rate, and not using an organic solvent in the process. For the preparation of the high-resistance water-barrier encapsulant, the filler is sufficiently uniform due to the shortening of the polymerization time of the polymer, and the gas barrier capability and the subsequent strength are unexpectedly increased. The currently known microwave heating method is only used for small molecule synthesis (such as "Synthesis of φ Phthalocyanines by microwave irradiation" US Patent 6,491,796); its application in the polymerization of macromolecules may be difficult, the reason may be that the microwave is a fast The heating procedure, when synthesizing a polymer, is liable to gelation due to the polymerization rate being too fast. The disclosed embodiments can overcome this problem by appropriate monomer selection, particularly the slower reaction of the Shiki acrylic precursor to better control the microwave response. On the other hand, if the epoxy-acrylic resin monomer and the difunctional urethane acrylic resin monomer are directly subjected to microwave reaction, the reaction is too fast to control and gelation is easy. After the above resin monomers are copolymerized, a curing process is carried out. The production of the packaging material is completed by 201103973. For example, an illumination procedure can be utilized to cause a crosslinking reaction in the epoxy group in the resin. The light source of the illumination program can be selected according to the type of photoinitiator used in the encapsulating material composition to be implemented, for example, one of an ultraviolet light source, a visible light source or an infrared light source, and the illumination procedure takes about 1 time. ~2〇〇 minutes, the applied light source power is about 1~20,000 watts. The curing process is, for example, an illumination program in which the light source is an ultraviolet light source, and the illumination procedure is performed for about 1-100 minutes, preferably about 1-20 minutes, and the light source power is about 1-10000 watts. The good condition is between 1 and 1000 watts. The disclosed encapsulating material composition can be used to adjust the light transmittance of the formed encapsulating material by the formulation of the filler to prepare a transparent encapsulating material having a light transmittance of more than 85% and even 90%. Adhesiveness up to 2.5 Kg/cm; and its excellent water and gas barrier properties help to improve the service life of electronic components'. It is especially suitable for various optoelectronic products such as inorganic light-emitting diodes, organic light-emitting diodes, solar cells, etc. . In addition, the encapsulating material of the present invention may also be used in some of the water-proof and food-drinking packagings of the Minsheng industry, such as wood-plastics, which are resistant to water and gas. The preferred embodiment of the present invention has the following advantages: (1) It is only necessary to continuously stir the illuminated encapsulating material composition in the process and control the power performance of the used light source without controlling the reaction pressure and reaction temperature of the system, thereby greatly increasing Simplify the setting of the system. (2) No solvent is required in the process and no heating is required, which saves energy and reduces accidents. (3) Shorten the process time. In one embodiment, the polymerization can be completed in 20 minutes using the ultraviolet light program 201103973. In another embodiment, the polymerization can be completed in 10 minutes using a microwave program. (4) The dispersibility of the filler in the obtained encapsulating material is excellent, and the water-blocking gas barrier performance of the encapsulating material can be improved, thereby improving the service life of the packaged component. The formulations and preparations of the various embodiments of the disclosed encapsulating material composition and the encapsulating material, and the formulation and preparation of the comparative examples are as follows. Table 1 shows information about the materials used for the optics. Table 1: Applied Photovoltaic Materials Photovoltaic Materials Sources Weishang Description / Remarks ΝΡΒ Aldrich Co. Hole Transport Materials Alq3 Aldrich Co. Luminescent Materials PEDOT Aldrich Co. Hole Transfer Materials P3HT Aldrich Co. P-Type Semiconductor Materials PCBM Aldrich Co. n-type semiconductor material The chemical formulas of the above-mentioned photovoltaic element materials are as follows (where η represents the number of repeating monomers): 11 201103973

[Comparative Example 1] 117 g of Benzyl methacrylate (BZMA), 86 g of Methyl Methacrylate (MAA), 130 g of 2· 2-hydroxyl ethyl mathacrylate (2-HEMA), 100 g of propylene glycol monomethyl ether acetate, 39 g of sulphur dioxide and 6 g The initiator azobisisobutyronitrile (AIBN; azobisisobutyronitrile) was placed in a container, and the above materials were stirred and mixed with a mechanical stirrer under normal temperature and pressure to obtain a package material composition. Then, it was heated to 100 ° C, and the heating time was 8 hours. After being allowed to stand at room temperature, 6 g of 1-184 (Ciba Co.; photoinitiator) was added to synthesize an acrylic copolymer. I. Here, the above-mentioned encapsulating material composition is polymerized into the copolymer according to the reaction represented by the following reaction formula (1) (wherein x, y, and z represent the repeat number of the monomers 12 201103973).

ο II + H2C=C- c-OH + I CH3 AIBN, cerium oxide, PGMEA heat (100 ° C, 8 hr)

O II a h2c = c ——c-o 〆一'’ I ch3 1-184 stir, 30 min

Immmi

OH Reaction Formula (1) Next, the physical properties such as viscosity, molecular weight, adhesion strength, hardness, light transmittance, and refractive index of the obtained acrylic copolymer I were measured, and the results obtained are shown in Tables 3 and 4. . The measuring instrument/measurement method for the physical properties of the polymer is shown in Table 2 below, wherein the measurement of the viscosity and the molecular weight can directly measure the appropriate amount of the copolymer, and regarding the adhesion strength, hardness, light transmittance, The properties of the refractive index and the like can be measured by applying the prepared polymer to a substrate such as a slide glass to a sample of 5 cm X 5 cm square, and passing the sample through a source of deep ultraviolet light. After 3 minutes of light, it is hardened, and then the subsequent physical measurement is performed by the measuring instrument and measuring method. Table 2: Measuring instruments/measuring methods of physical properties Physical mass measuring instruments/measuring methods 13 201103973 Physical mass measuring instruments/measurement methods Viscosity Viscolite 700 (measuring temperature is 25° 〇 molecular weight Waters Alliance GPC V2000 ( Reference: Polystyrene; @ 25°C) Adhesive strength universal tensile machine (HungTaCo.) (measurement method: ASTM D1002) Hardness pencil hardness tester (ZSH 2090) (measurement method: ASTM D-2240A) Light transmittance HITACHnj-3300 ( Measuring temperature is 25 ° C) Refractive index Filmetrics F20 (measuring temperature is 25 ° C) [Comparative Example 2] 165 g of glycidyl methacrylate (GMA), 168 g of bisphenol A Bisphenol A dimethacrylate, 100 g of propylene glycol monomethyl ether acetate, 39 g of cerium oxide and 6 g of the initiator azobisisobutyronitrile (AIBN; Azobisisobutyronitrile) and the above materials are placed in a container. The material is stirred and mixed with a mechanical stirrer at normal temperature and pressure to obtain a package material composition, which is then heated to 100. 匚, After heating for 8 hours', after standing at room temperature, 6 g of I-250 (Ciba Co.; photoinitiator) was added to further synthesize an acryl/epoxy copolymer I. Here, the above-mentioned encapsulating material red compound is polymerized into the copolymer according to the reaction represented by the following reaction formula (2) (where n and m represent the number of repetitions of the monomer).

Reaction Formula (2) Next, the acrylic/epoxy copolymer I obtained in Comparative Example 2 was subjected to physical property measurement in the same manner as in Example 1, and the results obtained are shown in Tables 4 and 5. [Comparative Example 3] Weigh 130 g of glycidyl methacrylate (GMA), 203 g of polyurethane-acrylic comonomer I, 100 g of propylene glycol methyl acetate (PGMEA; propylene glycol) Monomethyl ether acetate ), 39 g of cerium oxide and 6 g of the initiator azobisisobutyronitrile (AIBN; azobisisobutyronitrile) and placed in a container, stirred at room temperature and pressure with a mechanical stirrer The above materials are mixed to obtain a package material composition. Then, it was heated to 1 ° C, and the heating time was 8 hours. After being allowed to stand at room temperature, 6 g of I-250 (Ciba Co.; photoinitiator) and lg of Tinuvin 622 (Ciba Co.; The oxidant) was further synthesized to produce a pressurization 201103973 force/epoxy/polyurethane copolymer i. Here, the above-mentioned encapsulating material composition is polymerized into the copolymer according to the reaction represented by the following reaction formula (3) (where η and m represent the number of repetitions of the monomer). I ο 〇 , (/ + R-c fly

Reaction Formula (3) Next, physical properties of the acrylic/epoxy/polyurethane copolymer I obtained in Comparative Example 3 were measured in the same manner as in Comparative Example 1. The results obtained are shown in Tables 4 and 5. [Comparative Example 4] Weigh 130 g of Glycidylmethacrylate (GMA), 203 g of polyurethane-acrylic comonomer II, and 100 g of propylene glycol methyl ether acetate (PGMEA; Propylene glycol monomethyl ether acetate ), 39 g of cerium oxide and 6 g of the initiator azobisisobutyronitrile (AIBN; azobisisobutyronitrile) and the above materials are placed in a container and mechanically stirred at normal temperature and pressure. The above materials were stirred and mixed to obtain a package material composition. It was heated to 100 t at 201103973, and the heating time was 8 hours. After standing at room temperature, 6 g of I-250 (CibaCo.; photoinitiator) and lg of Tinuvin 622 (Ciba Co.; antioxidant) were added. ), and then an acrylic/epoxy/polyurethane copolymer II is synthesized. Here, the above-mentioned encapsulating material composition is polymerized into the copolymer according to the reaction represented by the following reaction formula (4) (wherein n and m represent the number of repetitions of the monomer).

Reaction Formula (4) Next, the acrylic/epoxy/polyurethane copolymer II obtained in Comparative Example 4 was subjected to physical property measurement in the same manner as in Comparative Example 1, and the results obtained are shown in Tables 4 and 5. [Comparative Example 5] Weigh 130 g of Glycidylmethacrylate (GMA), 203 g of polyurethane-acrylic comonomer III, and 100 g of propylene glycol myristic acetate (PGMEA; propylene glycol) Monomethyl ether acetate ) , 39 g of sulphur dioxide and 6 azobisisobutyronitrile (AIBN; azobisisobutyronitrile) 17 201103973 and the above materials are placed in a container, using a mechanical stirrer at normal temperature and pressure The above materials were stirred and mixed to obtain a package material composition. Then, it was heated to 100 ° C for 8 hours, and after standing at room temperature, 6 g of I-250 (CibaCo.; photoinitiator) and lg of Tinuvin 622 (Ciba Co.; antioxidant) were added. Further, an acryl/epoxy/polyurethane copolymer III was synthesized. Here, the above-mentioned encapsulating material composition is polymerized into the copolymer according to the reaction represented by the following reaction formula (5) (where n and m represent the number of repetitions of the monomer).

Reaction formula (5)

Next, the acrylic/epoxy/polyurethane copolymer III obtained in Comparative Example 5 was measured for physical properties in the same manner as in Comparative Example 1, and the results obtained are shown in Tables 4 and 5. [Comparative Example 6] Weighing 167 g of hydrazine monomer I, 167 g of polyurethane-acrylic co-monomer I, 100 g, propylene glycol methyl ether acetate (PGMEA; 201103973 propylene glycol monomethyl ether acetate ) 39 g of cerium oxide and 6 g of the initiator azobisisobutyronitrile (AIBN; azobisisobutyronitrile) and the above materials are placed in a container, and the above materials are stirred and mixed by a mechanical stirrer at normal temperature and pressure. A package material composition is obtained. Then, it was heated to 1 ° C, and the heating time was 8 hours. After being allowed to stand at room temperature, 6 g of 1-184 (Ciba Co.; photoinitiator) was added to further synthesize a press. Force / Polyurethane / Acrylic Copolymer I. Here, the above-mentioned encapsulating material composition is polymerized into a copolymer according to the reaction of the following reaction formula (6) (wherein x, y, ζ, η represents the number of repetitions of the monomer). CHs OCH3 -〇CHs I〖n. /~〇~e~ R—octj· 矽压力单单1

Polyurethane-acrylic co-monomer i OCHa CO- OCHs I 'Si( -OCH3 CH-CH2- :s & Ν, cerium oxide, PGMEA 1-184 heat (100 ° C, S hr) stir, 30 min (CH2)3 0 * "=0 c--CH2 r1 - 1 -* X CH—CH2— • - CH3 矽Acrylic/Polyurethane/Acrylic i5 (CH2)6

(CH2 > 6 Reaction Formula (6) Next, the ruthenium acrylic/urethane/acrylic copolymer I obtained in Comparative Example 6 was measured for physical properties in the same manner as in Comparative Example 1, and the obtained result 201103973 is shown in Table 4 And Table 5. [Example 1] Weigh 100 g of Glycidylmethacrylate (GMA), 100 g of polyurethane-acrylic co-monomer I, and 100 g of hydrazine comonomer (as shown in reaction formula (7)), 100 g of propylene glycol monomethyl ether acetate (PGME A; propylene glycol monomethyl ether acetate), 39 g of sulphur dioxide, and 6 g of initiator azobisisobutyronitrile ( AIBN; azobisisobutyronitrile) and the above materials are placed in a container, and the above materials are scrambled and mixed with a mechanical stirrer at normal temperature and pressure to obtain a package material composition, which is then heated to 100 ° C for a heating time of 8 After an hour, after standing at room temperature, 6 g of I-250 (Ciba Co.; photoinitiator) and 1 g of Tinuvin 622 (Ciba Co.; antioxidant) were added to synthesize an acrylic/ Epoxy/polyurethane/dream acrylic copolymer I. Here, the above Lu-based packaging material composition in accordance with the reaction shown in the following reaction formula (7) and polymerized to the copolymer (wherein x, y, z represent the number of repeats of the monomer). 20,201,103,973

Glycidyl methacrylate

Polyurethane*Acrylic Co-monomer I —Γ 1 + H2C=C —-C-Ο-(Cftt)3 Sand Acrylic Co-monomer OCH3I Si—OCH3I OCHs OCH3 HaCO-Si-OCH3

Reaction Formula (7) Next, the acrylic/epoxy copolymer j obtained in Example 1 was subjected to physical property measurement in the same manner as in Example 1, and the results obtained are shown in Tables 4 and 5. [Example 2] 100 g of thioglycolic acid glycidyl ester, 1 〇〇g of polyurethane-acrylic co-monomer 、, 100 g of shi chen eutectic monomer (such as reaction formula (8) ))), 100 g of propylene glycol monomethyl ether acetate (pGMEA; propylene glycol monomethyl ether acetate), 39 g of cerium oxide and 6 g of the initiator azobisisobutyronitrile (aibn; azobisisobutyronitrile) The above materials are placed in a container, and the above materials are stirred and mixed with a mechanical stirrer under normal temperature and pressure to obtain a composition of the encapsulating material. Then, it was heated to 1 ° C, and the heating time was 8 hours. After leaving to room temperature, 6 g of 1-25 乏 (Ciba C〇二光21 201103973 starter) and 1 g of Tinuvin 622 were added. (Ciba Co.; Antioxidant)' is further synthesized. An acryl/epoxy/polyurethane/ruthenium acrylate copolymer II is produced. Here, the above-mentioned encapsulating material composition is polymerized into the copolymer according to the reaction shown in the following reaction formula (8) (wherein x, y, and z represent the repeated number of monomers).

Glycidyl methacrylate Polyurethane-Acrylic Co-monomer II Sand Acrylic Co-monomer OCH3

OCH3 H3CO-Si-OCH3

Reaction Formula (8) Next, the acrylic/epoxy/polyurethane/ruthenium acrylate copolymer II obtained in Example 2 was subjected to physical property measurement in the same manner as in Comparative Example 1, and the results obtained are shown in Table 3 and Table. Four is shown. [Example 3] Weigh 100 g of methacrylic acid glycidol vinegar, 100 g of polyurethane-acrylic comonomer I, l〇〇g of 矽 克 eutectic monomer (such as reaction formula (9) Show), 39 g of cerium oxide and 6 g of photoinitiator 1-184 and place the above materials in a container, and stir and mix the above materials under normal temperature and pressure using a mechanical stirrer 22 201103973 stirrer A package material composition. Then, in-situ, a deep ultraviolet (UV) light source (having a power of about 100 W) is used to illuminate the encapsulating material composition for 20 minutes, and then placed at room temperature, and then added to 6 g. 1-250 (Ciba Co.; photoinitiator) and lg of Tinuvin 622 (CibaCo.; antioxidant), and then synthesized to prepare an acrylic / epoxy / polyurethane / 矽 acryl copolymer I UV. Here, the above-mentioned encapsulating material composition is polymerized into a copolymer according to the reaction represented by the following reaction formula (9) (wherein x, y, and z represent the number of repetitions of the monomer).

Glycidyl methacrylate polyurethane-acrylic co-monomer 1

OCHs 矽 克 共 O OCH3 OCHs H3CO-Si-OCH3 1-184, cerium oxide UV (100W, 20min)

Reaction formula (9) Next, the acrylic/epoxy/polyurethane/ruthenium acryl copolymer I UV obtained in Example 3 was measured for physical properties in the same manner as in Comparative Example 1, and the results obtained are shown in Table 3 and Table 4 shows. Γ Γ 1 23 201103973 [Example 4] Weigh 100 g of glycidyl methacrylate, 100 g of polyurethane, acrylic comonomer I, l〇〇g of hydrazine comonomer (such as reaction Formula (10)), 39 g of cerium oxide and 6 g of photoinitiator 1-184 and the above materials are placed in a container, and the above materials are stirred and mixed by a mechanical stirrer at normal temperature and pressure. A package material composition is obtained. Next, in-situ, a microwave program is performed by a microwave reactor (having a power of about 800 W) to microwave the package material composition for 10 minutes, and then placed at room temperature, and then 6 g of 1 is added. -250 (Ciba Co.; photoinitiator) and 1 g of Tinuvin 622 (Ciba Co.; antioxidant) were further synthesized to prepare an acrylic/epoxy/polyurethane/ruthenium acrylic copolymer I MW. Here, the above-mentioned encapsulating material composition is polymerized into the copolymer according to the reaction represented by the following reaction formula (10) (where t x , y and z represent the number of repetitions of the monomer).

Glycidyl methacrylate Polyurethane-acrylic co-monomer I CH3 〇 OCH3I II I H2C =C —C — 0—(CH2)3—Si—0CH3

I 矽Acrylic co-monomer OCH3 0CH3 H3CO-Si-OCH3 AIBN, cerium oxide Microwave (800W, 1〇 min)

Reaction formula (10) 24 201103973 Next, the acrylic/epoxy/polyurethane/ruthenium acryl copolymer IMW obtained in Example 4 was measured for physical properties in the same manner as in Comparative Example 1, and the results obtained are shown in Table 3. As shown in Table 4. Table 3: Viscosity and Molecular Weight of Packaging Materials Packaging Material Viscosity (cps) Weight Molecular Weight (Mw) Quantity Molecular Weight (Mn) Mw/ Mn Comparative Example 1 18,500 292,500 124,700 2.35 Comparative Example 2 21,800 318,500 149,000 2.14 Comparative Example 3 20,3〇〇 311,200 141,400 2.20 Comparative Example 4 19,400 304,300 137,200 2.22 Comparative Example 5 21,200 312,100 147,500 2.12 Comparative Example 6 15,100 263,900 113,900 2.32 Example 1 23,700 371,200 164,100 2.15 Example 2 22,800 397,600 153,600 2.21 Example 3 25,800 371,200 174,800 2.12 Example 4 28, 3〇〇397,600 193,700 2.05

From the results of Table 3, it is understood that the viscosity of the encapsulating material obtained by using the in-situ ultraviolet light (Example 3) and the in-situ microwave (Example 4) in the polymerization procedure is higher than that of the encapsulating material obtained by the heating procedure. Table 4: Physical Properties of Packaging Materials · 25 201103973 Adhesive Strength of Packaging Materials (Kg/cm) Hardness Transmittance (%) Refractive Index (η) Comparative Example 1 0.32 2H 92 1.38 Comparative Example 2 0.83 3H 86 1.45 Comparative Example 3 2.35 3H 87 1.51 Comparative Example 4 2.07 Η 91 1.49 Comparative Example 5 2.16 2Η 88 1.49 Comparative Example 6 1.73 Β 92 1.56 Example 1 2.58 Η 89 1.62 Example 2 2.27 ΗΒ 90 1.60 Example 3 2.93 Η 91 1.61 Example 4 3.26 Η 89 1.61 It can be seen from the results in Table 4 that the resin monomer contained in the encapsulating material is composed of epoxy-acrylic resin monomer, hydrazine acrylate resin monomer and bifunctional urethane acrylic resin monomer. 1, 2, 3 and 4) their adhesion strength and refractive index are relatively better. Further, the polymerization process obtained by using the in-situ ultraviolet light (Example 3) and the in-situ microwave (Example 4) had better adhesion strength and refractive index. [Example 5] A glass substrate 26 201103973 100 (50/mouth) formed with an indium tin oxide (ITO) layer 102 was immersed in a clean solution containing acetone, methanol and deionized (weight ratio = 2:1:1). Wash with ultrasound for five minutes. After treatment with oxygen plasma (1) 2 plasma) for 90 seconds, an electron transport layer 104 (using a germanium material, a thickness of 5 nanometers) and a light-emitting layer 1 are formed by vapor deposition. 〇6 (using Alq3, thickness 50 nm), an electron injection layer 1〇8 (using gasification, thickness of 3 nm) and a cathode 1 using aluminum, thickness of 80 nm). Then, the acrylic/epoxy/polyurethane/ruthenium acryl copolymer j mw prepared in the above Example 4 was applied as a sealing material to the cathode 11 () and coated with the above. The sidewall of the stacked film layer (stage I: 1500 rpm 20 seconds; stage II: 3500 rpm 30 seconds) was then irradiated with ultraviolet light for 1Q seconds to cure on the top and side wall surfaces of the stacked film layer. An encapsulation layer 170 is formed and the package of the organic light emitting diode device is completed as shown in FIG. Here, the organic light emitting diode device can emit light such as green light in a direction away from the broken substrate 100. Table 5: The polymer obtained in Example 4 and other materials are applied to the 〇LEd seal.

The encapsulation state is not encapsulated EPO-TEK OG112-4 (Epoxy Co.) 33 Example 4 Decay time* (hour) Defined as the time required for the brightness to decay to half of the original 27 115 201103973 χ人 t表五结果, we can see that The commercial material EP〇-TEKOG112-4 poly a program uses m_situ microwave and contains epoxy-acrylic resin monomer, Shixi acrylic resin monomer and bifunctional pure lycopene resin monomer together, and The encapsulating material of the resin monomer (Example 4) has a longer half-life of the shell length in the 〇lED application, thereby increasing the life of the component. [Embodiment 6]

By using the preparation step of the fifth example, only the glass substrate 1 〇〇 = was replaced by a PET (P〇lyethylene terephthalate) substrate 2, and thus φ completed the packaging of the flexible organic photodiode device. Here, in FIG. 2, the components in the flexible organic light-emitting diode (LED) device are the same as those in the fifth embodiment except for the PET substrate 200, and the components in the second drawing are labeled. The number in the i-th figure plus 1 〇〇 indicates that 'it represents the same component. Further, as shown in Fig. 2, the flexible organic light-emitting diode (OLED) device emits a light 280 such as green light toward the direction away from the pET substrate 2'. X

28 201103973 Polymerization process using in-situ microwaves and encapsulating materials comprising resin monomers consisting of epoxy-acrylic resin monomer, hydrazine acrylate resin monomer and difunctional urethane acrylate resin monomer (Example 4), in the application of the flexible organic light emitting diode, the half decay period is longer, thereby increasing the component life. [Example 7] Fluorescent powders (manufactured by Nichia Co., Ltd.) were each blended in the encapsulating materials of the polymers prepared in Examples 1, 3 and 4 (weight ratio: phosphor powder: copolymer = 16: 84) ). The materials were then poured into one of the holders 302 of the blue wafer 304 (thickness 460 nm, 15 mil square size, manufactured by Tekcore Co., Taiwan), wherein the blue wafer 304 was connected by a bonding wire 306. In the other part of the bracket 302. The above mixed material was then cured with UV light for one minute. Next, the package material having the blue light wafer 304 and the phosphor powder is placed in the projectile-type light-transmitting outer casing 300. Then, the encapsulating layers 370 of the above three copolymer materials are completely filled inside the shell-type outer casing 300 and irradiated with UV light for 5 minutes to be solidified, thereby completing the construction of a shell-type light-emitting diode, such as the third. The figure shows. Further, as shown in Fig. 3, the bullet-type light-emitting diode can emit a light 380 such as white light toward the direction away from the holder 302. Here, the encapsulating layer 370 of the acryl-polyurethane-acrylic copolymer material retains a light transmittance of 85% or more in curing, and does not deteriorate the luminous efficiency of the bullet-type light-emitting diode. 29 201103973 The obtained polymer and commercial materials are sealed in LED results

Table 7: Examples 1, 3 and 4 ^ ', extract * Bu hole ^ηΜ〇ην„, 疋义为,” 77 extract and 77 _ respectively represent the light-emitting rate and total reflectance nchip and γ respectively represent the blue wafer and The refractive index of the encapsulant ** is the time required for the shell to decay to half the original

As can be seen from the results in Table 7, compared to the commercial product Dow Corning SR 7010 (Dow Chemical Co.), epoxy-acrylic resin monomer, hydrazine acrylate resin monomer and bifunctional urethane acrylate resin The encapsulating material of the resin monomer composed of the monomers has a longer decay period in the application of the LED, thereby increasing the service life of the component. Among them, the use of in-situ microwaves in the polymerization procedure (Example 4) works best. [Example 8] The ITO glass (5 卩/mouth) 400 was immersed in acetone, methanol, and deionized 30 201103973 clean solution (weight ratio = 2:1:1), and then ultrasonically washed for five minutes. After treatment with oxygen plasma (〇2 plasma) for 90 seconds, a hole transport layer 402 (using PEDOT material) and an active layer 404 (using P3HT/PCBM material) were sequentially formed on the ITO glass 400 by spin coating. The weight ratio is 1:1). The spin coating conditions of the above film layer are hole transport layer 402 stage I: 1500 r.p.m. 20 seconds; stage Π: 3500 r.p.m. 30 seconds, active layer 404 is stage I: 1000 r.p.m. 20 seconds; stage II: 2000 r.p.m. 30 seconds. Next, an electron injecting layer 4?6 (using lithium fluoride) and a cathode 408 (using aluminum) are sequentially formed on the active layer 4?4 by evaporation. Then, the acrylic/epoxy/polyurethane/(tetra) gram copolymer Mw material encapsulating material prepared in the foregoing Example 4 was applied by spin coating to the cathode 408 and coated with the above stack. The side wall of the film layer (spin coating condition is stage I: 1500 rpm 2n 20 seconds; stage II: 35 〇〇rp m 3 〇 second)' then irradiated with ultraviolet light on the 封装 沭After curing, an encapsulation layer 7 is formed on the top s", and the sidewall surface of the stacked film layer, and the encapsulation of the organic solar cell device is completed, as shown in Fig. 4. Here, the organic solar power Receive external light 48〇. The device can pass 1T glass _ conditional table 8: column package test result * rate (%) attenuation ratio 31 201103973 〇 hours (unpackaged) 3.85 — 24 hours (unpackaged) 1.82 52.7 % 48 hours (unpackaged) 0.81 79.0 % Table 9: Package test results using EPO-TEK OG112-4 material Conditional efficiency (%) Attenuation ratio 〇 hours (package) 4.01 - 24 hours (package) 3.02 24.7% 48 hours (package) ) 1.76 56.1% of the table : Packaging test results using the polymer obtained in Example 4 Conditional efficiency (%) Attenuation ratio 〇 hours (package) 4.06 - 24 hours (package) 3.63 10.6 % 48 hours (package) 3.52 13.3 % From the results of Table 10, the phase Compared to the commercial product EPO-TEK OG112-4, the polymerization procedure uses in-situ microwaves and contains epoxy-acrylic resin monomers, hydrazine acrylate resin monomers and difunctional urethane acrylate resin monomers. The encapsulating material of the resin monomer (Example 4) having the same composition has excellent water-blocking gas barrier properties, and in the application of the organic solar cell device, * the attenuation rate of the conversion efficiency of 32 201103973 can be significantly reduced, and the service life of the component is greatly improved. The present invention has been described above by way of a preferred embodiment, and is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application attached.

33 201103973 [Simplified description of the drawings] Fig. 1 shows an organic light emitting diode device according to an embodiment of the invention; Fig. 2 shows a flexible organic light emitting diode device according to an embodiment of the invention; A bullet-type light emitting diode device according to an embodiment of the present invention is shown; and FIG. 4 shows an organic solar cell device according to an embodiment of the present invention. [Description of main components] 100~glass substrate; 102, 202~ITO layer; 104, 204~ electron transport layer; 106, .206~ light emitting layer; 108, 208~ electron injection layer; 110, 210~ cathode; 270, 370, 470~ encapsulation layer; 180, 280, 380, 480~ light; 200~PET substrate; 300~ shell-type transparent shell; 302~ bracket; 304~blue wafer, 306~ bonding wire; 201103973 400~ITO Glass; 402~ hole transport layer; 404~ active layer; 406~ electron injection layer; 40 8~ cathode.

Claims (1)

201103973 VII. Patent application scope: 1. A package material composition, including: (a) 100 parts by weight of resin monomer, including (al) epoxy-acrylic resin monomer (a2) a ruthenium resin monomer and (a3) a difunctional urethane-diacrylics resin monomer; (b) 0.1 to 15 parts by weight of a filler; and (c) 0.1 to 5 parts by weight Starting agent. 2. The encapsulating material composition of claim 1, wherein the encapsulating material composition has a viscosity of from 1 to 100,000 cps at 25 °C. 3. The encapsulating material composition of claim 1, wherein the encapsulating material composition has a light transmittance of greater than 85%. 4. The encapsulating material composition as described in the scope of the patent application, wherein the resin monomer molar ratio (al): (a2): (a3) = 1 : 1 to 3 : 1 to 3. 5. The encapsulating material composition of claim 1, wherein the epoxy-acrylic resin monomer has the following chemical formula: Wherein R1 and R2 are each independently a phenyl group, a phenyl group having a carbon number of 12, a yard group having a carbon number of 1 to 12, an ether group having a hindrance of 1 to a, and a carbon The number of alkoxy groups having a number of from 1 to 12 or a cycloalkoxy group having a carbon number of from 丨 to 12 is used. < 6. The composition of the sealing material according to the scope of the invention of claim 3, wherein the bifunctional urethane acryl monomer has the following chemical formula: R6 Ο 0 0 OR7 丨―II 4 II 3 II 5 丨丨H—I HC——CH——C——Ο——R4——OCN-R3—NCO——R5—Ο——C——C-CH Η Η , where R3, R4 and R5 Each is independently a phenyl group, an alkylphenyl group having a carbon number of 1 to 12, an alkyl group having a carbon number of 1 to 12, an ether group having a carbon number of 1 to 12, and a carbon number of 1 Alkoxy group of 12 or a cycloalkoxy group having a carbon number of 1 to 12; R6 and R7 are each independently a phenyl group, an alkylphenyl group having a carbon number of 1 to 12, and a carbon number of 1 An alkyl group of ～12, an ether group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, a cycloalkoxy group having a carbon number of 1 to 12 or hydrogen. 7. The encapsulating material composition of claim 1, wherein the hydrazine acrylate resin monomer has the following chemical formula: R9 R8-Si-R10 I" I 0 I c = 〇c = ch2 r12 , wherein R8, R9, R1G, R11 and R12 are each independently a phenyl group, an alkylphenyl group having a carbon number of from 1 to 12, an alkyl group having a carbon number of from 1 to 12, and a carbon number of from 1 to 12; An ether group, an alkoxy group having a carbon number of from 1 to 12, or a carbon number of 37 201103973. A cycloalkoxy group of from 1 to 12, 8. The encapsulating material composition according to claim 1, wherein The filler comprises an oxidized metal, an imidized metal or a metal nitride. 9. The encapsulating material composition of claim 1, wherein the initiator comprises (cl) a photoinitiator and (c2) The encapsulating material composition according to claim 9, wherein the thermal initiator comprises a radical initiator. 11. The encapsulating material composition according to claim 10 Wherein the free radical initiator is a peroxide or an azo compound. 12. The package material according to claim 9 a composition, wherein the photoinitiator comprises: a cationic initiator or a cyclopentadienyl transition metal complex. 13. The encapsulating material composition according to claim 1, which is used for a photovoltaic element. 14. The encapsulating material composition according to claim 13, wherein the illuminating element is an organic light emitting diode, an inorganic light emitting diode, or a solar cell. 15. A method of manufacturing a packaging material And comprising: providing an encapsulating material composition according to any one of claims 1-14; polymerizing the encapsulating material composition in a first procedure, wherein the first program comprises: a heating program, an ultraviolet irradiation program, a microwave program Or a combination of the foregoing; and curing the encapsulating material composition in a second process to form the encapsulating material 38 201103973, wherein the second process comprises: an illumination procedure. 16. The package of claim 15 The manufacturing method of the material, wherein the heating procedure is carried out for a period of time ranging from 1 to 100 hours. 17. The manufacture of the packaging material as described in claim 16 of the patent application. The method of manufacturing the encapsulating material according to the fifteenth aspect of the invention, wherein the ultraviolet irradiation procedure is performed for a period of time ranging from 1 to 200 minutes. 19. The method of manufacturing an encapsulating material according to claim 18, wherein the ultraviolet light irradiation process has a power of 1 to 1 〇, 〇〇〇 watt. 20. As claimed in claim 15 The manufacturing method of the packaging material, wherein the microwave program is carried out for a period of time ranging from 1 to 200 minutes. 21. The method of manufacturing an encapsulating material according to claim 20, wherein the microwave program has a power of between 1 and 20,000 watts. 22. The method of fabricating an encapsulating material according to claim 15, wherein the illumination source is an ultraviolet light source, a visible light source or an infrared light source. 39