JP6301643B2 - Light transmission module - Google Patents

Description

  The present invention relates to a light transmission module in which an element that is easily deteriorated by moisture is sealed using a fill material and a dam material.

  The organic EL element is composed of a structure in which a light emitting layer is sandwiched between a pair of counter electrodes, and electrons injected from one electrode and holes injected from the other electrode are recombined in the light emitting layer. Sometimes luminescence occurs. An organic EL module including the organic EL element is expected as a full-color flat panel display or an alternative to LED or plasma because of high impact resistance, high visibility, and a variety of emission colors.

  However, organic EL elements are more susceptible to moisture than other electronic components, and it is known that moisture that has penetrated into the organic EL elements causes oxidation of the electrodes, modification of organic substances, and the like, resulting in a significant decrease in light emission characteristics. It has been. As a method for preventing such a decrease in light emission characteristics, a method of covering an element with a glass layer capable of preventing moisture from entering, a method of sealing with a curable resin, and the like are known. However, in the method of covering with the glass layer, gas is confined with the element, the light extraction efficiency is lowered because the refractive index of the gas is lower than that of a transparent electrode such as ITO or glass, and in the case of a large display, the glass bends, The problem is that it is difficult to maintain the shape.

  The method of sealing with a curable resin is a method in which a dam is formed with a high viscosity curable resin (dam material) around the element, and a low viscosity curable resin (fill material) is poured into the element and cured. In this way, the device can be protected from moisture without containing gas. When a curable resin capable of forming a cured product having a high refractive index is used, the element can be protected without reducing the light extraction efficiency. Conventionally, epoxy resins have been frequently used as binder resins for dam materials and fill materials (Patent Documents 1 to 4). However, when an epoxy resin is used, it has not been satisfactory in terms of light extraction efficiency. Furthermore, when an epoxy resin having a glycidyl ether group at the ortho position such as 2- (glycidyloxy) biphenyl is used, acrolein gas is generated during curing, thereby deteriorating the device. Therefore, there has been a demand for a curable resin that can form a cured product with further excellent light extraction efficiency and hardly generates gas.

JP 2011-225773 A Japanese Patent No. 5153498 JP 2010-163666 A JP 2011-14485 A

  On the other hand, it is known that a phenyl sulfide derivative can form a cured product having a high refractive index. However, when a phenyl sulfide derivative is used as a fill material, if a dam material containing an epoxy resin that has been used conventionally as a binder resin is used, poor curing occurs at the portion where the phenyl sulfide derivative and the epoxy resin are mixed together. It turned out that it was difficult to seal the element because the dam broke down and the fill material leaked out.

  Accordingly, an object of the present invention is to transmit light sealed by a sealing material having a high refractive index, low outgas, and low moisture permeability, which is obtained by curing a phenyl sulfide derivative in an element that is easily deteriorated by moisture. To provide a mold module.

  As a result of intensive studies to solve the above problems, the present inventors have used a composition containing a phenyl sulfide derivative as a binder resin and a polymerization initiator as a fill material, and further added an inorganic filler to the binder resin and the polymerization initiator. When the composition obtained by adding the dam material is used as a dam material, it can be cured without causing poor curing, the dam formed by the dam material has excellent moisture resistance, and the sealing formed by the fill material It has been found that the material has a higher refractive index than the case where a filler material using a conventional epoxy resin as a binder resin is used, and has a superior light transmittance. The present invention has been completed based on these findings.

（式中、Ｒ^aは反応性官能基を示す。Ｒ^bはハロゲン原子、アルキル基、ハロアルキル基、アリール基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシアルキル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいスルホ基、ニトロ基、シアノ基、又は保護基で保護されていてもよいアシル基を示す。Ｒ^cは単結合又は連結基を示す。ｍは０〜４の整数を示し、ｎは０〜１０の整数を示す。尚、２つのＲ^aは、それぞれ同一であってもよく異なっていてもよい。また、Ｒ^b及びｍが複数ある場合は、それぞれ同一であってもよく異なっていてもよい） That is, the present invention provides a light transmission type module in which the periphery of an element is surrounded by a dam made of a cured product of the following dam material, and the elements in the dam are sealed with the cured product of the following fill material.
Dam material: 95 to 15% by weight of the compound (A) represented by the following formula (a), 3 to 83% by weight of the polymerization initiator (B) and the inorganic filler (C) Fill material: 99.99 to 50% by weight of the compound (A) represented by a) and a polymerization initiator (B)

(In the formula, R ^a represents a reactive functional group. R ^b represents a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, or an optionally protected group with a protecting group. A hydroxyalkyl group, an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protecting group; .R ^c indicating the optionally protected acyl group .m which represents single bond or a linking group represents an integer of 0 to 4, n is an integer of 0. the two R ^a is Each may be the same or different, and when there are a plurality of R ^b and m, they may be the same or different)

（式中、Ｒ^a、Ｒ^b、ｍは、前記に同じ） The present invention also provides the light transmission module, wherein the compound (A) is a compound represented by the following formula (a ′).

(Wherein R ^a , R ^b and m are the same as above)

  The present invention also provides the light transmission type module, wherein the polymerization initiator (B) is a photopolymerization initiator.

  In the present invention, the cured product (thickness: 10 μm) of the fill material has a light transmittance (wavelength: 450 nm) of 90% or more, and a refractive index (wavelength: 528 nm, at 23 ° C.) of 1.6 or more. The light transmission type module is provided.

  The present invention also provides the light transmissive module, wherein the light transmissive module is an organic electroluminescence module or a solar cell module.

（式中、Ｒ^aは反応性官能基を示す。Ｒ^bはハロゲン原子、アルキル基、ハロアルキル基、アリール基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシアルキル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいスルホ基、ニトロ基、シアノ基、又は保護基で保護されていてもよいアシル基を示す。Ｒ^cは単結合又は連結基を示す。ｍは０〜４の整数を示し、ｎは０〜１０の整数を示す。尚、２つのＲ^aは、それぞれ同一であってもよく異なっていてもよい。また、Ｒ^b及びｍが複数ある場合は、それぞれ同一であってもよく異なっていてもよい） The present invention also provides a method for manufacturing a light transmission type module, which includes the steps of forming a dam using the following dam material and filling the formed dam with the following fill material.
Dam material: 95 to 15% by weight of the compound (A) represented by the following formula (a), 3 to 83% by weight of the polymerization initiator (B) and the inorganic filler (C) Fill material: 99.99 to 50% by weight of the compound (A) represented by a) and a polymerization initiator (B)

(In the formula, R ^a represents a reactive functional group. R ^b represents a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, or an optionally protected group with a protecting group. A hydroxyalkyl group, an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protecting group; .R ^c indicating the optionally protected acyl group .m which represents single bond or a linking group represents an integer of 0 to 4, n is an integer of 0. the two R ^a is Each may be the same or different, and when there are a plurality of R ^b and m, they may be the same or different)

  The present invention also provides a method for producing the light transmissive module, wherein the viscosity of the dam material is 10 to 1000 Pa · s (25 ° C., shear rate: 20 (1 / s)).

  Since the light transmission module of the present invention uses the dam material and the fill material, the dam formed by the dam material can block the leakage of the fill material, and the fill material fills the space around the element. The element can be completely sealed. Furthermore, the dam material can form a cured product having both low outgas and low moisture permeability characteristics, and the fill material can form a cured product having both high refractive index and low outgas characteristics. Can do. Therefore, the amount of moisture and outgas in the device can be kept low enough for a long period of time without impeding light transmission, preventing deterioration of the device, excellent light extraction efficiency, long life and reliability A high light transmission module can be provided.

It is the schematic which shows an example of the manufacturing method of the light transmission type module of this invention. It is the schematic which shows another example of the manufacturing method of the light transmission type module of this invention.

[Dam material]
The dam material of the present invention contains at least the compound (A) represented by the formula (a), the polymerization initiator (B), and the inorganic filler (C).

(Compound (A))
The compound (A) of the present invention is a curable compound represented by the above formula (a). Two R ^a in the formula (a) are the same or different and represent a reactive functional group (polymerizable functional group), for example, vinyl group, allyl group, acryloyl group, methacryloyl group, epoxy group, glycidyl group. And oxetanyl group. In the present invention, among these, a group selected from a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group is preferable.

R ^b in the above formula (a) is a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group that may be protected with a protecting group, a hydroxyalkyl group that may be protected with a protecting group, or a protecting group. May be protected with an amino group which may be protected with, a carboxyl group which may be protected with a protective group, a sulfo group which may be protected with a protective group, a nitro group, a cyano group, or a protective group An acyl group is shown. Moreover, when m is an integer of 2-4, 2-4 ^Rb couple | bonded with the same aromatic ring may couple | bond together and may form the ring with the carbon atom which comprises an aromatic ring. Further, the plurality of R ^b in the formula (a) may be the same or different.

Examples of the halogen atom for R ^b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group in R ^b include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, hexyl group, heptyl group, octyl group, and nonyl group. And a C _1-10 (preferably C _1-5 ) alkyl group such as a decyl group. Examples of the haloalkyl group for R ^b include C _1-10 (preferably C _1-5 ) haloalkyl groups such as a chloromethyl group, a trifluoromethyl group, a trifluoroethyl group, and a pentafluoroethyl group. it can. Examples of the aryl group for R ^b include a phenyl group and a naphthyl group. The aromatic ring of the aryl group includes, for example, a halogen atom such as a fluorine atom, a C _1-4 alkyl group such as a methyl group, a C _1-5 haloalkyl group such as a trifluoromethyl group, a hydroxyl group, and a methoxy group. A C _1-4 alkoxy group, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group such as a methoxycarbonyl group, and a substituent such as an acyl group such as a nitro group, a cyano group, and an acetyl group may be included.

Examples of the hydroxyalkyl group for R ^b include C _1-10 (preferably C _1-5 ) in which at least one hydrogen atom of the C _1-10 alkyl group such as hydroxymethyl group is substituted with a hydroxyl group. A hydroxyalkyl group etc. can be mentioned. The protecting group for hydroxyl group and the protecting group for hydroxyalkyl group in R ^b are those commonly used in the field of organic synthesis [for example, alkyl groups (for example, C _1-4 alkyl such as methyl group, t-butyl group, etc.). Alkenyl group (for example, allyl group); cycloalkyl group (for example, cyclohexyl group); aryl group (for example, 2,4-dinitrophenyl group); aralkyl group (for example, benzyl group); Substituted methyl group (eg, methoxymethyl group, methylthiomethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl group, etc.), tetrahydropyrani Hydroxyl groups, tetrahydrofuranyl groups, 1-hydroxyalkyl groups (for example, 1-hydroxyethyl group, etc.) Groups and acetal or hemiacetal group capable of forming group; an acyl group (e.g., formyl group, acetyl group, a propionyl group, a butyryl group, an isobutyryl group, C _1-6 aliphatic acyl group such as pivaloyl group; acetoacetyl group; An aromatic acyl group such as a benzoyl group); an alkoxycarbonyl group (eg, a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); an aralkyloxycarbonyl group; a substituted or unsubstituted carbamoyl group; a substituted silyl group (eg, Dimethyl hydrocarbon group (for example, methylene group, ethylidene group, isopropylidene group, cyclohexane) which may have a substituent when there are two or more hydroxyl groups or hydroxymethyl groups in the molecule Pentylidene group, cyclohexylidene group, benzylidene group, etc.)] it can.

Examples of the protecting group for the amino group in R ^b include protecting groups commonly used in the field of organic synthesis (eg, alkyl groups, aralkyl groups, acyl groups, alkoxycarbonyl groups and the like exemplified as the protecting groups for the hydroxyl group). Can do.

Examples of the protecting group for carboxyl group and sulfo group for R ^b include protecting groups commonly used in the field of organic synthesis [eg, alkoxy groups (eg, C _1-6 alkoxy such as methoxy group, ethoxy group, butoxy group, etc.). Group, etc.), cycloalkyloxy group, aryloxy group, aralkyloxy group, trialkylsilyloxy group, optionally substituted amino group, hydrazino group, alkoxycarbonylhydrazino group, aralkylcarbonylhydrazino group, etc. ] Can be mentioned.

Examples of the acyl group in R ^b include C _1-6 aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, and pivaloyl group; aromatic acyl groups such as acetoacetyl group and benzoyl group Groups and the like. As the protecting group for the acyl group, a protecting group commonly used in the field of organic synthesis can be used. Examples of the form in which the acyl group is protected include acetal (including hemiacetal).

When two or more R ^b are bonded per aromatic ring (that is, when m in the formula (a) is 2 to 4), two or more R ^b are bonded to each other to form the formula ( Examples of the ring formed together with the carbon atoms constituting the aromatic ring in a) include, for example, a 5-membered alicyclic carbocycle, a 6-membered alicyclic carbocycle, and two or more alicyclic carbocycles (monocyclic). And alicyclic carbocyclic rings such as condensed rings; lactone rings such as 5-membered lactone rings and 6-membered lactone rings.

R ^c in the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond ( -CONH-), carbonate bond (-OCOO-), and a group in which a plurality of these are linked. The linking group may have a substituent such as a hydroxyl group or a carboxyl group, and examples of such a linking group include a divalent hydrocarbon group having one or more hydroxyl groups.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. can be mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group. And divalent cycloalkylene groups (including cycloalkylidene groups) such as a silylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.

  M in the above formula (a) is the same or different and represents an integer of 0 to 4. N (the number of repeating structural units in parentheses to which n is attached) represents an integer of 0 to 10.

  Although the weight average molecular weight of a compound (A) is not specifically limited, 300-10000 are preferable at the point which is excellent in the solubility with respect to a compound (B), Most preferably, it is 300-1000, Most preferably, it is 300-500.

（式中、Ｒ^a、Ｒ^b、ｍは、前記に同じ） In the above formula (a), n is preferably 0 to 3 and particularly preferably 0 in that the viscosity of the dam material can be adjusted in a wide range. That is, as the compound (A), a compound represented by the following formula (a ′) is particularly preferable.

(Wherein R ^a , R ^b and m are the same as above)

Examples of the compound (A) in the present invention include compounds represented by the following formulas. In the following formula, R is a hydrogen atom or a methyl group.

Compound (A) can be produced by a known or conventional method. For example, a compound in which R ^a in formula (a) is a hydrogen atom (for example, 4,4′-thiobisbenzenethiol, etc.) is used as a raw material, and in the presence of a base, vinyl halide, allyl halide, ( Examples thereof include a method of reacting a halide of meth) acrylic acid, epihalohydrin and the like. In addition, a compound in which R ^a in formula (a) is a vinyl group is obtained by combining a compound in which R ^a in formula (a) is a hydrogen atom (for example, 4,4′-thiobisbenzenethiol etc.) with dihaloethane. It can also be produced by a reaction followed by dehydrohalogenation.

  A compound (A) can be used individually by 1 type or in combination of 2 or more types. The content (blending amount) of the compound (A) in the total amount (100% by weight) of the dam material of the present invention is 95 to 15% by weight, preferably 85 to 17% by weight, particularly preferably 80 to 18% by weight, Preferably it is 75 to 20 weight%, and it is preferable to adjust suitably according to the shape of the inorganic filler (C) to be used. For example, when a spherical inorganic filler is used, the content (blending amount) of the compound (A) in the total amount (100% by weight) of the dam material of the present invention is preferably 15 to 70% by weight, and particularly preferably 17%. -60% by weight, most preferably 20-50% by weight. When a plate-like inorganic filler is used, the content (blending amount) of the compound (A) in the total amount (100% by weight) of the dam material of the present invention is preferably 40 to 95% by weight, particularly preferably 50 to 85%. % By weight, most preferably 55-70% by weight. When the compound (A) is contained in the above range, a cured product with little outgas and high gas barrier properties can be obtained.

  The compound (A) has an action of trapping cations and suppressing the progress of cationic polymerization. Therefore, when the dam material of the present invention contains a photocationic polymerization initiator as the polymerization initiator (B), it is not completely cured only by generating cations by light irradiation, and is subjected to heat treatment after light irradiation and trapped. By releasing the formed cations, curing can proceed and complete curing can be achieved. Therefore, if you want to cure in one step, you can quickly cure by applying light irradiation using a photo radical polymerization initiator, if you want to cure stepwise, use a photo cationic polymerization initiator It can be cured in a stepwise manner by combining light irradiation and heat treatment in the order of light irradiation-heat treatment.

(Polymerization initiator (B))
As the polymerization initiator (B) constituting the dam material of the present invention, a well-known and usual polymerization initiator can be used. In the present invention, it is preferable to use a photopolymerization initiator. The photopolymerization initiator includes a photocationic polymerization initiator and a photoradical polymerization initiator. When it is desired to cure the dam material of the present invention in one step (only by light irradiation), it is preferable to use a radical photopolymerization initiator as the polymerization initiator, and when it is desired to cure the dam material of the present invention stepwise. It is preferable to use a photocationic polymerization initiator. In addition, a polymerization initiator (B) can be used individually by 1 type or in combination of 2 or more types.

(Photocationic polymerization initiator)
The cationic photopolymerization initiator is a compound that generates a cationic species by light irradiation and initiates the curing reaction of the cationically polymerizable compound, and includes a cationic part that absorbs light and an anion part that is a source of acid generation.

  Examples of the photocationic polymerization initiator of the present invention include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, and bromine salt compounds. A compound etc. can be mentioned.

  Among these, the use of a sulfonium salt compound is preferable in that a cured product having excellent curability can be formed. Examples of the cation part of the sulfonium salt compound include arylsulfonium ions (particularly, triarylsulfonium ions) such as triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and tri-p-tolylsulfonium ion. Can be mentioned.

Examples of the anion part of the cationic photopolymerization initiator include BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , [(Rf) _n PF _6−n ] ⁻ (Rf: 80% of hydrogen atoms) The above is an alkyl group substituted with a fluorine atom, n: an integer of 1 to 5, AsF ₆ ⁻ , SbF ₆ ⁻ , pentafluorohydroxyantimonate, and the like.

  Examples of the photocationic polymerization initiator of the present invention include 4- (4-biphenylthio) phenyl-4-biphenylphenylsulfonium tetrakis (pentafluorophenyl) borate and diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluoro). Phenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4- (4-biphenylthio) phenyl-4-biphenylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, trade name “Cyracure UVI-” 6970 "," Syracure UVI-6974 "," Syracure UVI-6990 "," Syracure UVI-950 "(manufactured by Union Carbide, USA)," Irgacure 25 " “0”, “Irgacure 261”, “Irgacure 264” (manufactured by Ciba Specialty Chemicals), “SP-150”, “SP-151”, “SP-170”, “Optomer SP-171” (and above) , Manufactured by ADEKA Corporation), "CG-24-61" (manufactured by Ciba Specialty Chemicals), "DAICAT II" (manufactured by Daicel Corporation), "UVAC1590", "UVAC1591" (above, Daicel Ornex) "CI-2064", "CI-2439", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI" -2758 "," CIT-1682 "(manufactured by Nippon Soda Co., Ltd.)," PI-2074 "(Rhodia, pentafluorophenyl volley) Toluylcumyl iodonium salt), “FFC509” (manufactured by 3M), “BBI-102”, “BBI-101”, “BBI-103”, “MPI-103”, “TPS-103”, “MDS-103” ”,“ DTS-103 ”,“ NAT-103 ”,“ NDS-103 ”(manufactured by Midori Chemical Co., Ltd.),“ CD-1010 ”,“ CD-1011 ”,“ CD-1012 ”(US, Sartomer Co., Ltd.), "CPI-100P", "CPI-101A", "CPI-200K" (above, San Apro Co., Ltd.) and other commercial products can be used.

  The cationic photopolymerization initiator can be used singly or in combination of two or more, and the amount used (blending amount) is 0.01 to 15% by weight in the total amount of dam material (100% by weight). More preferably, it is 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight, and most preferably 0.1 to 3% by weight.

(Curing accelerator)
The dam material of the present invention may contain a curing accelerator. The curing accelerator is a compound having a function of accelerating the curing rate when the polymerizable compound in the dam material of the present invention is cured by the photocationic polymerization initiator. For example, 1,8-diazabicyclo [5.4 0.0] undecene-7 (DBU), and salts thereof (eg, phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt); 1,5-diazabicyclo [4.3.0 Nonene-5 (DBN) and its salts (eg, phosphonium salts, sulfonium salts, quaternary ammonium salts, iodonium salts); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, Tertiary amines such as N-dimethylcyclohexylamine; 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazoles such as midazole; phosphines such as phosphate ester and triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organometallic salts such as tin octylate and zinc octylate; metal chelates be able to. These can be used alone or in combination of two or more.

  Moreover, as said hardening accelerator, brand name "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X", "12XD" (development product) (above) , San Apro Co., Ltd.), "TPP-K", "TPP-MK" (above, manufactured by Hokuko Chemical Co., Ltd.), "PX-4ET" (manufactured by Nippon Chemical Industry Co., Ltd.) It can also be used.

  As content of the said hardening accelerator, about 0.01-5 weight% of the dam material whole quantity (100 weight%) of this invention is preferable, More preferably, it is 0.02-3 weight%, Especially preferably, it is 0.05. -3 wt%, most preferably 0.1-2.5 wt%. When the curing accelerator is contained in the above range, a curing acceleration effect can be exhibited without causing coloring in the cured product.

(Photo radical polymerization initiator)
Examples of the photo radical polymerization initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, Orthobenzoyl methyl benzoate, ethyl 4-dimethylaminobenzoate (Nippon Kayaku Co., Ltd., trade name “Kayacure EPA”, etc.), 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name) “Kayacure DETX”, etc.), 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Gaigi Co., Ltd., trade name “Irgacure 907”, etc.), 2-dimethylamino -2 2-Amino-2-benzoyl-1-phenylalkane compounds such as (4-morpholino) benzoyl-1-phenylpropane, tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1- Aminobenzene derivatives such as phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2 ′ -Imidazole compounds such as biimidazole (trade name "B-CIM" manufactured by Hodogaya Chemical Co., Ltd.), 2,6-bis (trichloromethyl) -4- (4-methoxynaphthalen-1-yl)- Halomethylated triazine compounds such as 1,3,5-triazine, 2-trichloromethyl-5- (2-benzofuran-2-yl-ethenyl)- , It may be mentioned 3,4-oxadiazol-halomethyl oxadiazole compounds such like. These can be used alone or in combination of two or more. Examples of the photo radical polymerization initiator include a combination of an imidazole compound and an aminobenzene derivative, a 2-amino-2-benzoyl-1-phenylalkane compound, a halomethylated triazine compound, a halomethyl oxa compound from the viewpoints of sensitivity and chemical resistance. Diazole compounds are preferred. Moreover, a photosensitizer can be added to the dam material of the present invention as necessary.

  The above radical photopolymerization initiators can be used alone or in combination of two or more, and the amount used (blending amount) is 0.01 of the total amount (100% by weight) of the dam material of the present invention. -5 wt% is preferred, more preferably 0.1-3 wt%.

(Inorganic filler (C))
As the inorganic filler (C), it is preferable to use a filler that does not block visible light. Examples of the raw material for the inorganic filler (C) include silica (nanosilica etc.), alumina, mica, synthetic mica, talc, calcium oxide, calcium carbonate, zirconium oxide (nanozirconia etc.), titanium oxide (nanotitania etc.), titanium. Barium acid, calcined kaolin, bentonite, diatomaceous earth, boron nitride, aluminum nitride, silicon carbide, zinc oxide, cerium oxide, cesium oxide, magnesium oxide, glass beads, glass fiber, graphite, carbon nanotube, calcium hydroxide, magnesium hydroxide, Examples thereof include aluminum hydroxide and cellulose. These can be used alone or in combination of two or more.

The said inorganic filler (C) can be manufactured by well-known methods, such as the flame hydrolysis method described in the international publication 96/31572, a flame thermal decomposition method, a plasma method, for example. In the present invention, it is preferable to use stabilized nano-dispersed sols of colloidal inorganic particles. For example, silica sol manufactured by BAYER, SnO ₂ sol manufactured by Goldschmidt, TiO ₂ sol manufactured by MERCK Commercially available products such as SiO ₂ , ZrO ₂ , Al ₂ O ₃ and Sb ₂ O ₃ sols manufactured by Nissan Chemicals, Aerosil dispersions manufactured by DEGUSSA, and the like can be suitably used.

  Further, the inorganic filler (C) may be one whose viscosity behavior is changed by modifying its surface. The surface modification of the inorganic filler (C) can be performed using a known surface modifier. As such a surface modifier, for example, a compound capable of interacting with a functional group present on the surface of the inorganic filler (C) such as a covalent bond or complex formation can be used. Examples of such surface modifiers include carboxyl groups, (primary, secondary, and tertiary) amino groups, quaternary ammonium groups, carbonyl groups, glycidyl groups, vinyl groups, ( A compound having a functional group such as a (meth) acryloxy group or a mercapto group can be used. As such a surface modifier, it is usually a liquid under standard temperature and pressure conditions, and a low molecular weight molecule having a carbon number in the molecule of 15 or less (more preferably 10 or less, more preferably 8 or less). Surface modifiers composed of organic compounds are preferred. The molecular weight of the low molecular weight organic compound is not particularly limited, but is preferably 500 or less, more preferably 350 or less, and still more preferably 200 or less.

Examples of the surface modifier include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic acid, succinic acid, glutaric acid, oxalic acid and maleic acid. C _1-12 saturated or unsaturated mono- and polycarboxylic acids (preferably monocarboxylic acids) such as acid and fumaric acid; and esters thereof (preferably C _1-4 alkyl esters such as methyl methacrylate); Amides; β-dicarbonyl compounds such as acetylacetone, 2,4-hexanedione, 3,5-heptanedione, acetoacetic acid, C _1-4 alkylacetoacetic acids, silylating agents (eg, vinyltrimethoxysilane) and Examples include silane coupling agents (for example, vinyltrimethoxysilane).

  The shape of the inorganic filler (C) may be, for example, a perfect sphere, a substantially true sphere, a plate shape (square plate shape, disk shape), a prismatic shape, a cylindrical shape, etc. Are preferably used.

  The average particle diameter of the inorganic filler (C) is, for example, about 0.01 nm to 100 μm. In addition, the average particle diameter in this invention is a value calculated | required by the laser diffraction type particle diameter distribution measuring method etc.

  The content (blending amount) of the inorganic filler (C) is 3 to 83% by weight of the total amount (100% by weight) of the dam material, preferably 15 to 83% by weight, particularly preferably 25 to 80% by weight. , Depending on the shape. For example, when the shape of the inorganic filler is spherical, the content (mixing amount) of the inorganic filler (C) is preferably 30 to 83% by weight, particularly preferably the total amount of the dam material (100% by weight). It is 40 to 83% by weight, most preferably 50 to 80% by weight. Moreover, when the shape of the inorganic filler is plate-like, the content (mixing amount) of the inorganic filler (C) is preferably 5 to 60% by weight, particularly preferably the total amount of dam material (100% by weight). 15 to 50% by weight, most preferably 25 to 45% by weight. When the inorganic filler (C) is contained in the above range, it is possible to form a dam having an appropriate viscosity and preventing the following fill material from leaking, and having excellent low moisture permeability. When there is too much content of an inorganic filler (C), there exists a tendency for a viscosity to become high too much and to become difficult to apply | coat. On the other hand, when there are too few inorganic fillers (C), there exists a tendency for the characteristic of low moisture permeability to become difficult to be acquired. Moreover, there exists a tendency for a viscosity to become low and to raise | generate liquid dripping easily.

(Spacer filler)
In addition, a spherical spacer filler may be added to the dam material of the present invention in order to easily control the thickness of the dam formed.

  Examples of the raw material for the spacer filler include plastics such as acrylic polymer, styrene- (meth) acrylic acid copolymer, and divinylbenzene polymer.

  The average particle diameter of the spacer filler is, for example, about 500 nm to 100 μm, and can be appropriately adjusted according to the desired film thickness of the dam.

  The content (mixing amount) of the spacer filler is 0.01 to 10% by weight of the total amount (100% by weight) of the dam material, preferably 0.1 to 5% by weight, particularly preferably 0.3 to 3% by weight. It is.

(Other additives)
The dam material of the present invention is, for example, a polymerization inhibitor, a silane coupling agent, an organic filler, an antioxidant, a light stabilizer, a plasticizer, a leveling agent, an antifoaming agent, a pigment, an organic solvent, and an ultraviolet ray as necessary. Conventional additives such as an absorbent, an ion adsorbent, a pigment, a phosphor, and a release agent may be contained. Moreover, although the dam material of this invention may contain other polymeric compounds (for example, an acryl-type compound, an olefin type compound, etc.) other than the said compound (A), the total polymerization property contained in a dam material is included. The proportion of the compound (A) in the compound is, for example, 70% by weight or more, preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more.

  The dam material of the present invention comprises a compound (A), a polymerization initiator (B), an inorganic filler (C), and other additives as required, a revolving type stirring deaerator, a homogenizer, and a planetary mixer. It can be produced by uniformly mixing using a generally known mixing device such as a three-roll mill or a bead mill. Each component may be mixed simultaneously or sequentially.

  The viscosity (25 ° C., shear rate: 20 (1 / s)) of the dam material of the present invention thus obtained is, for example, 10 to 1000 Pa · s, preferably 20 to 500 Pa · s, particularly preferably 40 to 300 Pa. -S. Therefore, the dam which can prevent the leakage of the fill material can be formed by applying.

[Fill material]
The fill material of the present invention contains at least the compound (A) represented by the formula (a) and the polymerization initiator (B).

  Examples of the compound (A) include the same examples as the compound (A) used in the dam material. A compound (A) can be used individually by 1 type or in combination of 2 or more types. The content (blending amount) of the compound (A) in the total amount (100% by weight) of the fill material of the present invention is 99.99 to 50% by weight, preferably 99.9 to 60% by weight, particularly preferably 99.7. -70 wt%, most preferably 99.5-75 wt%. Since the fill material containing the compound (A) in the above range has high fluidity and excellent filling properties, the element can be protected from moisture, and when cured, it has a high refractive index and excellent light transmittance. Further, a cured product with less outgas is obtained.

  Examples of the polymerization initiator (B) include the same examples as the polymerization initiator (B) used in the dam material. A polymerization initiator (B) can be used individually by 1 type or in combination of 2 or more types. When a photocationic polymerization initiator is used as the polymerization initiator (B), its use amount (blending amount) is preferably from 0.01 to 15% by weight, more preferably from 0.1 to 15% by weight based on the total amount of the filler material (100% by weight). It is 01 to 10% by weight, particularly preferably 0.05 to 5% by weight, and most preferably 0.1 to 3% by weight. When a curing accelerator is used, the amount used is preferably about 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, particularly preferably 0.2% of the total amount of the filler material (100% by weight). -3% by weight, most preferably 0.25-2.5% by weight. When using a radical photopolymerization initiator, its use amount (blending amount) is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total amount (100% by weight) of the fill material. .

  In addition to the compound (A) and the polymerization initiator (B), the fill material of the present invention may contain other components as necessary. Examples of other components include inorganic filler (C) used in the dam material and other additives. The content of these other components is 40% by weight or less, preferably 30% by weight or less, based on the total amount (100% by weight) of the fill material. If the content of other components exceeds the above range, the refractive index of the resulting cured product tends to decrease, and the light transmittance tends to decrease. The fill material of the present invention may contain other polymerizable compounds (for example, an acrylic compound, an olefin compound, etc.) in addition to the compound (A). The proportion of the compound (A) in the compound is, for example, 70% by weight or more, preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more. If the content of other polymerizable compounds exceeds the above range, the refractive index of the resulting cured product tends to decrease, and the light transmittance tends to decrease.

  The fill material of the present invention comprises a compound (A), a polymerization initiator (B), and other additives as necessary, a self-revolving stirring deaerator, a homogenizer, a planetary mixer, a three roll mill, a bead mill, etc. Can be produced by uniformly mixing using the generally known mixing equipment. Each component may be mixed simultaneously or sequentially.

  The viscosity (25 ° C., shear rate: 20 (1 / s)) of the fill material of the present invention thus obtained is, for example, 0.01 to 20 Pa · s, preferably 0.015 to 5 Pa · s, particularly preferably. Is 0.020 to 1 Pa · s. Therefore, it is excellent in discharge property and filling property, and can be suitably used as an element sealing material.

  In addition, since the fill material of the present invention contains the compound (A) having a cation trapping action, it is preferable to perform light irradiation using a photo radical polymerization initiator when curing in one stage is desired, When two-stage curing is desired, it is preferable to use a photocationic polymerization initiator as the polymerization initiator (B) and perform light irradiation and heat treatment in this order. Since it has the property that curing is completed by applying heat treatment after light irradiation without being completely cured only by light irradiation, it is bonded to the element while maintaining the adhesiveness after light irradiation, and then heated. A method of completing the curing can be employed, whereby the element can be sealed while being protected from light degradation.

[Method of manufacturing light-transmissive module]
The manufacturing method of the light transmission type module of this invention includes the process of forming a dam using the said dam material, filling the said fill material in the formed dam, and hardening a dam material and a fill material.

  Examples of the light transmission type module of the present invention include an organic EL module (top emission method, bottom emission method), a solar cell module, a liquid crystal module, and the like.

More specifically, the light transmission type module of the present invention can be manufactured by the following method 1 or 2 (see FIGS. 1 and 2).
<Method 1>
Step 1: Place the element on the substrate Step 2: Form a dam using dam material around the element Step 3: Fill the dam with a fill material Step 4: Lay the lid (lid), Harden dam and fill materials

<Method 2>
Process 1 ′: Forming a dam using a dam material on a lid (lid) Process 2 ′: Filling a dam with a fill material Process 3 ′: Installing an element on a substrate, inverting and bonding the process 4 ': Harden dam material and fill material

  It is preferable to use a moisture-proof base material as the substrate and lid (lid), for example, glass substrate such as soda glass and non-alkali glass; metal substrate such as stainless steel and aluminum; polyethylene trifluoride, polytrifluoride Polyfluorinated ethylene polymers such as ethylene chloride (PCTFE), polyvinylidene fluoride (PVDF), copolymers of PCTFE and PVDF, copolymers of PVDF and polyfluoroethylene chloride, polyimide, polycarbonate, dicyclopentadiene, etc. And cycloolefin resins, polyesters such as polyethylene terephthalate, and resin substrates such as polyethylene and polystyrene.

  In the case of an organic EL module, the element includes a laminate of an anode / light emitting layer / anode. If necessary, a passivation film such as a SiN film may be provided.

  The dam can be formed, for example, by applying a dam material on a substrate or a lid (lid). The dam formation range is not particularly limited as long as the purpose of protecting the element from moisture can be achieved.

  Filling with the fill material can be performed, for example, by discharging into the dam using a dispenser or the like. The filling amount of the fill material is not particularly limited as long as the element can be protected from moisture and the light extraction efficiency can be improved.

The dam material and the fill material can be cured by (1) light irradiation alone or (2) light irradiation and heat treatment in this order. (1) In the case where only light irradiation is performed, and a coating film having a thickness of 100 μm, it is preferable to irradiate light of 500 mJ / cm ² or more with a mercury lamp or the like. (2) In the case of performing light irradiation and heat treatment, the light irradiation is preferably performed by irradiating light of 1000 mJ / cm ² or more with a mercury lamp or the like. More preferably, it is preferably heated at 60 to 120 ° C., more preferably 80 to 110 ° C. for 10 to 200 minutes (more preferably 30 to 120 minutes). Since the dam material and the fill material of the present invention contain the compound (A) having a cation trapping action, they can be cured in one stage or in two stages. When it is desired to cure in one stage, it can be carried out by using a photo radical polymerization initiator as the polymerization initiator (B). When it is desired to cure in two stages, the polymerization initiator (B ) As a photocationic polymerization initiator, and can be performed by applying light irradiation and heat treatment in this order, and at the stage of light irradiation, the progress of curing is suppressed to the extent that adhesion is maintained, Then, hardening can be completed by performing heat processing.

  Therefore, a photocationic polymerization initiator is used as the polymerization initiator (B) for the dam material and the fill material, and after filling the inside of the dam with the fill material in the above method 2 (step 2 '), first, light irradiation is performed, and then The dam material and the fill material can be cured (process 4 ') by heating after placing the element on the substrate, bonding the inverted ones (process 3'), and easily deteriorated by ultraviolet irradiation The element can be sealed while preventing the element from deteriorating at the stage of curing the dam material and the fill material.

  The light transmittance (wavelength: 450 nm) of the cured product (thickness: 10 μm) of the fill material of the present invention is, for example, 90% or more, preferably 93% or more.

  Moreover, the refractive index (at 23 degreeC) with respect to the light of wavelength 528nm of the hardened | cured material of the fill material of this invention is 1.6 or more, for example, Preferably it is 1.63-1.75, Most preferably, it is 1.65-1. .74. In addition, the refractive index of hardened | cured material can be measured by the method based on JISK7142, or the method using a prism coupler, for example.

The cured product of the dam material of the present invention is excellent in moisture resistance and has a water vapor permeability of 40 g / m ² · day · atm or less, preferably 35 to 5 g / m ² · day · atm, particularly preferably 20 to 5 g / m. ² · day · atm. The moisture permeability of the cured product can be calculated by measuring the moisture permeability of the cured product adjusted to a thickness of 100 μm according to JIS L1099 and JIS Z0208 under the conditions of 60 ° C. and 90% RH. .

  Furthermore, the outgas amount of the cured product (60 mg) of the dam material of the present invention is about 1000 ppm or less (preferably 1 to 100 ppm), and the outgas amount of the cured material (60 mg) of the present invention is about 300 ppm or less (preferably 1 to 100 ppm). 50 ppm) and exhibits low outgassing properties. The outgas amount can be measured by the head space GC / MS.

  The cured product of the fill material of the present invention is excellent in transparency and moisture resistance as described above, and has low outgassing properties and a high refractive index. Moreover, the dam material and the fill material of the present invention are excellent in curability and can be cured in one or two stages depending on the application. Therefore, when the cured product of the dam material and the fill material of the present invention is used as a sealing material for the element, the deterioration of the element in the process of curing the dam material and the fill material, and the cured product of the dam material and the fill material (sealing material ) Without causing deterioration due to outgas, and without inhibiting light transmission (when the light transmissive module of the present invention is an organic EL module, without inhibiting transmission of light emitted from the light emitting layer) It has excellent light extraction efficiency), can prevent moisture from entering into the device, and can provide a long-life and highly reliable light transmission module.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
Rotating 99 parts by weight of BSV (bis (4-vinylthiophenyl) sulfide) and 1 part by weight of 4- (4-biphenylthio) phenyl-4-biphenylphenylsulfonium tetrakis (pentafluorophenyl) borate as a polymerization initiator It was put into a revolution mixer (trade name “Awatori Neritaro ARE-310”, manufactured by Shinky Co., Ltd.) and stirred to obtain a fill material (1).
Further, 24 parts by weight of BSV (bis (4-vinylthiophenyl) sulfide), 1 part by weight of 4- (4-biphenylthio) phenyl-4-biphenylphenylsulfonium tetrakis (pentafluorophenyl) borate as a polymerization initiator, and inorganic 75 parts by weight of a spherical surface-modified silica filler as a filler is put into a rotation / revolution mixer (trade name “Awatori Nertaro ARE-310”, manufactured by Shinky Co., Ltd.) and stirred, and a dam material ( 1) was obtained.

On the glass substrate, the obtained dam material (1) was used at 25 ° C. and a discharge pressure of 0.3 MPa using a dispenser device (Robot SM200DS manufactured by Musashi Engineering, dispenser ML-5000XII, precision nozzle HN-0.2N). A 5 cm square dam was formed by discharging.
The obtained fill material (1) was discharged into the dam at 25 ° C. and a discharge pressure of 0.05 MPa using the dispenser device.

Then, UV light was irradiated with a 200 W / cm conveyor type high-pressure mercury lamp (irradiation amount: 2000 mJ / cm ² ), bonded to a glass substrate on which ITO was vapor-deposited in a vacuum oven (5 torr or less), and heated at 100 ° C. for 1 hour. Thus, a cured product (1) was obtained.

Examples 2-3 and Comparative Examples 1-3
As shown in the following table, a cured product was produced in the same manner as in Example 1 except that the formulation of the dam material and the fill material was changed.

<Measurement of viscosity>
The viscosity at 25 ° C. of the dam material and the fill material obtained in Examples and Comparative Examples was measured using a rheometer (trade name “Physica MCR301”, manufactured by Anton Paar), and the shear rate was 20 (1 / The value at the time of s).

<Measurement of refractive index>
About the hardened | cured material (thickness: 10 micrometers) obtained by the Example and the comparative example, the refractive index of 528 nm light was measured at 23 degreeC using Metricon2010M.

<Water vapor permeability>
The moisture permeability of the dam material cured product obtained in the examples and comparative examples is the moisture permeability of the cured product (thickness 100 μm) at 60 ° C. and 90% according to JIS L 1099 and JIS Z 0208 (cup method). Measured under RH conditions.

<Transmissivity>
The transmittance of the cured cured material (thickness: 10 μm) obtained in the examples and comparative examples was measured using a spectrophotometer (trade name “UV-2450”, manufactured by Shimadzu Corporation). The transmittance of 450 nm light of the laminate is measured, and the transmittance of 450 nm light in the case of only a glass substrate is defined as 100%, and the transmittance (%) of 450 nm light of the cured material (thickness: 10 μm) is obtained. Asked.

<Outgas>
The outgas amount of the dam material cured product and the fill material cured product obtained in the examples and comparative examples was obtained by putting 60 mg of hexane (toluene 100 ppm) and 60 mg of the dam material cured product or the fill material cured product in a vial bottle, and irradiating with UV ( 2000 mJ / cm ² ) and then allowed to stand at 100 ° C. for 1 hour, a calibration curve was prepared using toluene as a standard substance, and the amount of outgas in the vial was measured. In addition, a brand name “HP-6890N” (manufactured by Hewlett-Packard) was used as a measuring instrument, and a brand name “DB-624” (manufactured by Agilent) was used as a column.

The compounds used in Examples and Comparative Examples are as follows.
[Curable compound]
BSV: bis (4-vinylthiophenyl) sulfide, molecular weight: 302, manufactured by Sumitomo Seika Co., Ltd. YL-983U: 4- (glycidyloxy) phenyl [4- (glycidyloxy) phenyl] methane, Mitsui Chemicals, Inc. YD-8125: 4- (glycidyloxy) phenyl [4- (glycidyloxy) phenyl] dimethylmethane, Nippon Steel & Sumikin Chemical Co., Ltd. OPP-G: 2- (glycidyloxy) biphenyl, Sanko Co., Ltd. [polymerization] Initiator]
4- (4-biphenylthio) phenyl-4-biphenylphenylsulfonium tetrakis (pentafluorophenyl) borate (photocation polymerization initiator)
[Inorganic filler]
Surface-modified silica filler (true spherical shape): trade name “SE-2050GD” (average particle size: 0.6 μm, silica filler + dimethyldimethoxysilane, manufactured by Admatex Co., Ltd.)
Surface modified kaolin filler (plate-like): Trade name “Translink 77” (average particle size: 0.8 μm, calcined kaolin + vinyltrimethoxysilane, manufactured by BASF)
Surface modified talc filler (plate-like): talc (average particle size: 1 μm, trade name “D-1000”, manufactured by Nippon Talc Co., Ltd.) KBM-1003 (vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 3% by weight, kneaded using a rotating / revolving mixer (trade name “Awatori Nertaro ARE-310”, manufactured by Shinky Co., Ltd.), and then dried in a vacuum dryer at 100 ° C. for 5 hours. Obtained surface-modified plate-like talc [spacer filler]
L-11R: Plastic fine particles (acrylic polymer), average particle size: 10 μm, manufactured by Hayakawa Rubber Co., Ltd.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Cathode 3 Light emitting layer 4 Anode 5 Dam 6 Dispenser 7 Fill material 8 Lid (lid)

Claims (9)

A light transmission type module in which the periphery of an element is surrounded by a dam made of a cured material of the following dam material, and the elements in the dam are sealed with a cured material of the following fill material.
Dam material: 15 to 70% by weight of the compound (A) represented by the following formula (a), 25 to 60 % by weight of a polymerization initiator (B), and a plate-like inorganic filler (C) Fill material: 99.99 to 50% by weight of a compound (A) represented by the following formula (a) and a polymerization initiator (B)

(In the formula, R ^a represents a reactive functional group. R ^b represents a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, or an optionally protected group with a protecting group. A hydroxyalkyl group, an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protecting group; .R ^c indicating the optionally protected acyl group .m which represents single bond or a linking group represents an integer of 0 to 4, n is an integer of 0. the two R ^a is Each may be the same or different, and when there are a plurality of R ^b and m, they may be the same or different) The light transmission module according to claim 1, wherein the compound (A) is a compound represented by the following formula (a ′).

(Wherein R ^a , R ^b and m are the same as above)   The light transmission module according to claim 1, wherein the polymerization initiator (B) is a photopolymerization initiator.   The viscosity of the dam material is 10 to 1000 Pa · s (25 ° C., shear rate: 20 (1 / s)), and the viscosity of the fill material is 0.01 to 20 Pa · s (25 ° C., shear rate: 20 (1 / s)). The light transmission type module according to any one of claims 1 to 3.   The light transmittance (wavelength: 450 nm) of the cured product of the fill material (thickness: 10 μm) is 90% or more, and the refractive index (wavelength: 528 nm, at 23 ° C.) is 1.6 or more. 5. The light transmission type module according to any one of 4 above.   The light transmission module according to any one of claims 1 to 5, wherein the light transmission module is an organic electroluminescence module or a solar cell module. The manufacturing method of the light transmission type module which has the process of forming a dam using the following dam material and filling the following fill material in the formed dam.
Dam material: 15 to 70% by weight of the compound (A) represented by the following formula (a), 25 to 60 % by weight of a polymerization initiator (B), and a plate-like inorganic filler (C) Fill material: 99.99 to 50% by weight of a compound (A) represented by the following formula (a) and a polymerization initiator (B)

(In the formula, R ^a represents a reactive functional group. R ^b represents a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, or an optionally protected group with a protecting group. A hydroxyalkyl group, an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protecting group; .R ^c indicating the optionally protected acyl group .m which represents single bond or a linking group represents an integer of 0 to 4, n is an integer of 0. the two R ^a is Each may be the same or different, and when there are a plurality of R ^b and m, they may be the same or different) Form the dam using the following dam material, fill the formed dam with the following fill material, irradiate with light, and then cure the dam material and the fill material by heating after pasting the elements together A method for producing a light-transmissive module having a process.
Dam material: Fill material containing 95 to 15 wt% of compound (A) represented by the following formula (a ″), 3 to 83 wt% of photocationic polymerization initiator (B ′), and inorganic filler (C) : 99.99 to 50% by weight of the compound (A) represented by the following formula (a ″) and a cationic photopolymerization initiator (B ′)

(In the formula, R ^a represents a vinyl group or an allyl group. R ^b represents a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protective group, or a protective group. May be a hydroxyalkyl group, an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protected group .R ^c indicating the optionally protected acyl group group .m which represents single bond or a linking group represents an integer of 0 to 4, n is an integer of 0. the two R ^a May be the same or different, and when there are a plurality of R ^b and m, they may be the same or different.   The viscosity of the dam material is 10 to 1000 Pa · s (25 ° C., shear rate: 20 (1 / s)), and the viscosity of the fill material is 0.01 to 20 Pa · s (25 ° C., shear rate: 20 (1 / s)). The method for producing a light transmission type module according to claim 7 or 8.

Images