JP2011148878A - Light-resistant sealing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for sealing an optical element, excellent in light resistance. <P>SOLUTION: This sealing resin composition of the optical element is provided by containing a curable main agent containing a fluorinated multi-functional epoxy resin and/or a fluorinated multi-functional epoxy (meth)acrylate resin, and a curing agent for curing the resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a light-resistant sealing resin composition containing an epoxy group-containing fluororesin that is useful as a seal or a material for various optical materials and has excellent light resistance, particularly resistance to ultraviolet rays.

  Conventionally, non-fluorine-based epoxy resins have been frequently used as sealants for optical elements (Patent Document 1).

  In addition, curable resin compositions using a fluorine-containing compound having an epoxy group are also known (Patent Documents 2 and 3), and are useful as adhesives for optical component materials, optical element / device components, and the like. Yes.

JP 2009-114390 A Japanese Patent Publication No. 08-030028 JP 09-309943 A

  However, non-fluorine type epoxy resins have insufficient light resistance to light such as ultraviolet rays, are severely deteriorated, and are required to be improved in terms of durability.

  The curable compositions disclosed in Patent Documents 2 and 3 are merely suggested for use as an adhesive and as a raw material for optical materials.

  When the sealant is used for packaging (encapsulation) or mounting of an optical functional element such as a light emitting element such as a light emitting diode (LED), an EL element, or a nonlinear optical element, deterioration due to light from the light emitting element is a particular problem. This contributes to shortening the service life.

  The objective of this invention is providing the resin composition for sealing excellent in light resistance.

  The present invention relates to a curable main agent (A) containing a fluorinated polyfunctional epoxy resin and / or a fluorinated polyfunctional epoxy (meth) acrylate resin, and a curing agent (B) for curing the resin. The present invention relates to a sealing resin composition for optical elements.

［式中、Ｒｆは、

｛式中、
Ａは式：

（式中、Ｒｆ¹は炭素数１〜１０のパーフルオロアルキル基；Ｒｆ²は炭素数１〜１２のパーフルオロアルキル基；ｐは０〜３の整数；ｑは０〜３の整数；ｒは０または１；ｓは０〜５の整数；ｔは０〜５の整数）で示される含フッ素有機基；
ＢはＡと同じかまたは水素原子、炭素数１〜８のアルキル基、もしくは炭素数１〜８のフルオロアルキル基；
Ｚは水素原子または炭素数１〜１８のフルオロアルキル基；
Ｍは、

（式中、Ｒは同じかまたは異なり、炭素数１〜５のアルキル基、ＯＨ、ＣＨ₃、ＮＨ₂、ハロゲン原子、炭素数１〜２０のフルオロアルキル基；ｌ₁、ｌ₂およびｌ₃はいずれも０または１〜１０の整数で置換基Ｒの個数を表す）で示される環式脂肪族炭化水素基；
ｘ１およびｘ２は１〜３６の整数｝で示される環式脂肪族炭化水素基；ｎ１〜ｎ４は０または任意の正の数］で示されるフッ素化された多官能エポキシ樹脂よりなる群から選ばれる少なくとも１種、および／または式（Ｖ）〜（VI）：

［式中、Ｒｆは上記と同じ；Ｙは水素原子またはＣＨ₃；ｎ５およびｎ６は０または任意の正の数］で示されるフッ素化された多官能エポキシ（メタ）アクリレート樹脂よりなる群から選ばれる少なくとも１種を含むものが好ましい。 As the curable main agent (A), the main agent (A) is represented by the formulas (I) to (IV):

[Wherein Rf is

{Where,
A is the formula:

(Wherein Rf ¹ is a C 1-10 perfluoroalkyl group; Rf ² is a C 1-12 perfluoroalkyl group; p is an integer of 0-3; q is an integer of 0-3; 0 or 1; s is an integer of 0 to 5; t is an integer of 0 to 5);
B is the same as A or a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a fluoroalkyl group having 1 to 8 carbon atoms;
Z is a hydrogen atom or a C1-C18 fluoroalkyl group;
M is

(Wherein R is the same or different, an alkyl group having 1 to 5 carbon atoms, OH, CH ₃ , NH ₂ , a halogen atom, a fluoroalkyl group having 1 to 20 carbon atoms; l ₁ , l ₂ and l ₃ are Each represents an integer of 0 or an integer of 1 to 10 representing the number of substituents R);
x1 and x2 are a cyclic aliphatic hydrocarbon group represented by an integer of 1 to 36; n1 to n4 are 0 or any positive number] and are selected from the group consisting of fluorinated polyfunctional epoxy resins represented by At least one and / or formulas (V) to (VI):

[Wherein Rf is the same as above; Y is a hydrogen atom or CH ₃ ; n5 and n6 are 0 or any positive number] and is selected from the group consisting of fluorinated polyfunctional epoxy (meth) acrylate resins Those containing at least one selected from the above are preferable.

（ｘ３は１〜６の整数）
であることが好ましく、なかでも

であることが好ましい。 Rf is

(X3 is an integer from 1 to 6)
It is preferable that

It is preferable that

  The encapsulating resin composition of the present invention is particularly suitable for encapsulating a light emitting element having a main emission peak at a wavelength of 350 to 500 nm, and is particularly suitable for encapsulating a light emitting diode (LED).

  Since the sealing resin composition of the present invention has excellent light resistance, for example, a package (encapsulation) or mounting of an optical functional element such as a light emitting element such as a light emitting diode (LED), an EL element, or a nonlinear optical element. When it is used, the durability is improved and the life of the optical functional element can be extended.

It is a graph which shows the change of the transmittance | permeability of the hardened | cured material after exposure of the predetermined amount measured in Example 16. FIG.

  The light-resistant sealing resin composition of the present invention comprises a curable main agent (A) containing a fluorinated polyfunctional epoxy resin and / or a fluorinated polyfunctional epoxy (meth) acrylate resin, and the resin. A curing agent (B) for curing is included.

  Hereinafter, each component will be described.

(A) Curing agent containing fluorinated polyfunctional epoxy resin and / or fluorinated polyfunctional epoxy (meth) acrylate resin Fluorinated polyfunctional epoxy resin and / or fluorinated polyfunctional epoxy As the (meth) acrylate resin, for example, a bisphenol compound, a benzene compound, a diphenyl ether compound, a cyclohexane compound, a glycol compound, a fluorinated compound of a vinyl ether compound is used, and a polyfunctional epoxy resin having a chemical structure with fluorine, If it is a polyfunctional epoxy (meth) acrylate resin, it will not specifically limit.

  Among them, the fluorinated polyfunctional epoxy resins represented by the above formulas (I) to (IV), the fluorinated polyfunctional epoxy (meth) acrylate resins represented by the formulas (V) to (VI), Besides being excellent in light resistance, it is preferable from the viewpoint of refractive index and heat resistance.

（式中、Ｒｆ、Ｙ、ｎ１〜ｎ６は前記と同じ）

(Wherein Rf, Y and n1 to n6 are the same as above)

｛式中、
Ａは式：

（式中、Ｒｆ¹は炭素数１〜１０のパーフルオロアルキル基；Ｒｆ²は炭素数１〜１２のパーフルオロアルキル基；ｐは０〜３の整数；ｑは０〜３の整数；ｒは０または１；ｓは０〜５の整数；ｔは０〜５の整数）で示される含フッ素有機基；
ＢはＡと同じかまたは水素原子、炭素数１〜８のアルキル基、もしくは炭素数１〜８のフルオロアルキル基；
Ｚは水素原子または炭素数１〜１８のフルオロアルキル基｝
であるものが好ましく、特に、つぎの化合物が好適である。 Among the compounds represented by formula (I), Rf is

{Where,
A is the formula:

(Wherein Rf ¹ is a C 1-10 perfluoroalkyl group; Rf ² is a C 1-12 perfluoroalkyl group; p is an integer of 0-3; q is an integer of 0-3; 0 or 1; s is an integer of 0 to 5; t is an integer of 0 to 5);
B is the same as A or a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a fluoroalkyl group having 1 to 8 carbon atoms;
Z is a hydrogen atom or a C1-C18 fluoroalkyl group}
In particular, the following compounds are preferred.

（式中、ｎ７〜ｎ１３は０もしくは任意の正の数）

(Where n7 to n13 are 0 or any positive number)

（ｘ４およびｘ５は１〜８の整数）
であるものが好ましく、特に、つぎの化合物が好適である。 Among the compounds represented by formula (II), Rf is

(X4 and x5 are integers of 1 to 8)
In particular, the following compounds are preferred.

（ｘ６は１〜６の整数）

(X6 is an integer from 1 to 6)

｛式中、
Ａは式：

（式中、Ｒｆ¹は炭素数１〜１０のパーフルオロアルキル基；Ｒｆ²は炭素数１〜１２のパーフルオロアルキル基；ｐは０〜３の整数；ｑは０〜３の整数；ｒは０または１；ｓは０〜５の整数；ｔは０〜５の整数）で示される含フッ素有機基；
ＢはＡと同じかまたは水素原子、炭素数１〜８のアルキル基、もしくは炭素数１〜８のフルオロアルキル基；
Ｚは水素原子または炭素数１〜１８のフルオロアルキル基｝
であるものが好ましく、特に、つぎの化合物が好適である。 Among the compounds represented by formula (III), Rf is

{Where,
A is the formula:

(Wherein Rf ¹ is a C 1-10 perfluoroalkyl group; Rf ² is a C 1-12 perfluoroalkyl group; p is an integer of 0-3; q is an integer of 0-3; 0 or 1; s is an integer of 0 to 5; t is an integer of 0 to 5);
B is the same as A or a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a fluoroalkyl group having 1 to 8 carbon atoms;
Z is a hydrogen atom or a C1-C18 fluoroalkyl group}
In particular, the following compounds are preferred.

（ｎ１４〜ｎ１８は０または任意の正の数）

(N14 to n18 are 0 or any positive number)

（ｘ６およびｘ７は１〜６の整数）
であるものが好ましく、特に、つぎの化合物が好適である。 Among the compounds represented by formula (IV), Rf is

(X6 and x7 are integers of 1 to 6)
In particular, the following compounds are preferred.

（ｘ８は１〜６の整数）

(X8 is an integer from 1 to 6)

  “Epoxy (meth) acrylate” in the fluorinated polyfunctional epoxy (meth) acrylate resin represented by the formula (V) or (VI) is a polyfunctional epoxy compound (for example, glycidyl ethers) (meth) acrylic acid. It means a hydroxy (meth) acrylate having a plurality of (meth) acryloyl groups produced by reacting with, i.e., forming hydroxy acrylate.

｛式中、
Ａは式：

（式中、Ｒｆ¹は炭素数１〜１０のパーフルオロアルキル基；Ｒｆ²は炭素数１〜１２のパーフルオロアルキル基；ｐは０〜３の整数；ｑは０〜３の整数；ｒは０または１；ｓは０〜５の整数；ｔは０〜５の整数）で示される含フッ素有機基；
ＢはＡと同じかまたは水素原子、炭素数１〜８のアルキル基、もしくは炭素数１〜８のフルオロアルキル基；
Ｚは水素原子または炭素数１〜１８のフルオロアルキル基｝
であり、ＹがＨであるものが好ましく、特に、つぎの化合物が好適である。 As the fluorinated polyfunctional epoxy (meth) acrylate resin of the formula (V), among others, Rf is

{Where,
A is the formula:

(Wherein Rf ¹ is a C 1-10 perfluoroalkyl group; Rf ² is a C 1-12 perfluoroalkyl group; p is an integer of 0-3; q is an integer of 0-3; 0 or 1; s is an integer of 0 to 5; t is an integer of 0 to 5);
B is the same as A or a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a fluoroalkyl group having 1 to 8 carbon atoms;
Z is a hydrogen atom or a C1-C18 fluoroalkyl group}
Wherein Y is H, and the following compounds are particularly preferable.

（ｎ１９は０または任意の正の数）

（ｎ２０は０または任意の正の数）

（ｎ２１は０または任意の正の数）

（ｎ２２は０または任意の正の数）

（ｎ２３は０または任意の正の数）

(N19 is 0 or any positive number)

(N20 is 0 or any positive number)

(N21 is 0 or any positive number)

(N22 is 0 or any positive number)

(N23 is 0 or any positive number)

（ｘ９およびｘ１０は１〜８の整数）
であり、ＹがＨであるものが好ましく、特に、つぎの化合物が好適である。 As the fluorinated polyfunctional epoxy (meth) acrylate resin represented by the formula (VI), among them, Rf is

(X9 and x10 are integers of 1 to 8)
Wherein Y is H, and the following compounds are particularly preferable.

（ｘ１１は１〜６の整数）

(X11 is an integer from 1 to 6)

  Among the compounds (I) to (VI), the compounds of formulas (I), (III) and (V), particularly the following compounds, are particularly excellent in the required properties of the sealant, such as heat resistance and transparency, and light resistance. Those are preferred.

（ｎ７は０または任意の正の数）

（ｎ１６は０または任意の正の数）

（ｎ１９は０または任意の正の数）

(N7 is 0 or any positive number)

(N16 is 0 or any positive number)

(N19 is 0 or any positive number)

  The main agent containing a fluorinated polyfunctional epoxy resin and / or a fluorinated polyfunctional epoxy (meth) acrylate resin in the present invention is a fluorinated polyfunctional epoxy resin or a fluorinated epoxy resin as at least one component. As long as the polyfunctional epoxy (meth) acrylate resin is included, it may be composed of one or more of a fluorinated polyfunctional epoxy resin and a fluorinated polyfunctional epoxy (meth) acrylate resin. Other than these fluorinated polyfunctional epoxy resins and fluorinated polyfunctional epoxy (meth) acrylate resins for refractive index adjustment, curability adjustment, resin composition mutual compatibility adjustment, etc. Other epoxy compounds and (meth) acrylate compounds may be used in combination.

  Specific examples of such a compound to be used in combination will be described below separately for the case of using a fluorinated polyfunctional epoxy resin as the main agent and the case of using a fluorinated polyfunctional epoxy (meth) acrylate resin.

（ｎ２４〜ｎ２６は０または任意の正の数）

のほかに、ノボラツクエポキシ、ｏ−クレゾールノボラツクエポキシ、エポキシ化ポリブタジエンなどの非フッ素系多官能エポキシ樹脂があげられる。 (When using fluorinated polyfunctional epoxy resin)
Examples of other epoxy compounds used by mixing with the fluorinated polyfunctional epoxy resins represented by the formulas (I) to (IV) in the light-resistant sealing resin composition of the present invention include the following structures: Epoxy resin represented by the formula:

(N24 to n26 are 0 or any positive number)

In addition to these, non-fluorinated polyfunctional epoxy resins such as novolak epoxy, o-cresol novolak epoxy, and epoxidized polybutadiene can be used.

  Further, non-fluorinated polyfunctional epoxy compounds as shown in the following structural formula can also be used.

（ｘ１２は１〜４０の整数）

(X12 is an integer from 1 to 40)

  For the purpose of reducing the viscosity of the composition, as a diluent, in addition to alkyl monoglycidyl ether having 2 to 25 carbon atoms such as butyl glycidyl ether and 2-ethylhexyl glycidyl ether, butanediol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, neopentyl glycol diglycidyl ether, dodecanediol diglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, phenyl glycidyl ether, resorcin diglycidyl ether, p-tert-butyl Phenyl glycidyl ether, allyl glycidyl ether, tetrafluoropropyl glycidyl ether, octafluoropentyl glycidyl Ethers, dodecafluoro octyl diglycidyl ether, styrene oxide, limonene diepoxide, limonene monoxide, alpha-pinene epoxide, beta-pinene epoxide, cyclohexene epoxide, cyclooctene epoxide, and vinyl cyclohexene dioxide and the like. In addition, a compound represented by the following structural formula can also be used as a diluent.

（ＱはＨ、Ｃｌ、Ｂｒ、炭素数１〜１８のアルキル基、または炭素数１〜１８のフルオロアルキル基）、

（ＹはＨまたはＣＨ₃）

(Q is H, Cl, Br, an alkyl group having 1 to 18 carbon atoms, or a fluoroalkyl group having 1 to 18 carbon atoms),

(Y is H or CH ₃ )

(When using fluorinated polyfunctional epoxy (meth) acrylate resin)
In the light-resistant sealing resin composition of the present invention, as a (meth) acrylate compound used by mixing with a fluorinated polyfunctional epoxy (meth) acrylate resin represented by formulas (V) to (VI) Can include a fluorine-based or non-fluorinated monofunctional (meth) acrylate compound, a non-fluorinated bifunctional (meth) acrylate compound, a tri- or higher functional non-fluorinated polyfunctional (meth) acrylate compound, and the like. .

  Examples of non-fluorine monofunctional (meth) acrylate compounds include methyl (meth) acrylate, acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and cyclohexane-1,4-dimethanol. Mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, p-cumylphenoxyethyl ( (Meth) acrylate, isobornyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di Black pentenyl oxyethyl (meth) acrylate, o- phenylphenol polyethoxy (meth) acrylate.

（式中、Ｚ₁はＨ、Ｆ、ＣＨ₃；ｋは１〜６の整数；ｍ１は１〜２９の整数；ｍ２は０〜５０の整数；Ｙ₁はＨまたはＦ；Ｒ^1e、Ｒ^2e、Ｒ^3eは同じかまたは異なり、Ｈ、炭素数１〜２９のエーテル結合を含んでいてもよいアルキル基または炭素数１〜２９のエーテル結合を含んでいてもよい含フッ素アルキル基。ただし、Ｒ^1e、Ｒ^2e、Ｒ^3eのいずれかにフッ素原子を含む）
などがあげられる。 As fluorine-based monofunctional (meth) acrylate compounds,

Wherein Z ₁ is H, F, CH ₃ ; k is an integer of 1-6; m1 is an integer of 1-29; m2 is an integer of 0-50; Y ₁ is H or F; R ^1e , R ^2e , R ^3e may be the same or different, and H, an alkyl group that may contain an ether bond having 1 to 29 carbon atoms or a fluorine-containing alkyl group that may contain an ether bond having 1 to 29 carbon atoms, provided that R ^1e , R ^2e , or R ^3e contains a fluorine atom)
Etc.

などがあげられる。 More specifically,

Etc.

  Non-fluorinated bifunctional (meth) acrylate monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, Tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) Examples include acrylates.

  Non-fluorinated trifunctional or higher polyfunctional (meth) acrylate compounds include tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth). ) Acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol hydroxybivalate (for example, manufactured by Nippon Kayaku Co., Ltd.) , KAYARAD HX-220, HX-620, etc.), trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, ditrimethylolpropane Examples thereof include tetra (meth) acrylate.

  Non-fluorinated (meth) acrylate oligomers can also be used in combination. Specifically, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and the like can be given.

  Examples of non-fluorinated urethane (meth) acrylates include diol compounds (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1 , 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1, 5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypro Or a reaction product of these diol compounds with a dibasic acid or an anhydride thereof (for example, succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid, or an anhydride thereof). Certain polyester diols and organic polyisocyanates (for example, chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone) Diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, water Cyclic saturated hydrocarbon isocyanates such as xylene diisocyanate and hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate, Examples thereof include a reaction product obtained by reacting 6-isopropyl-1,3-phenyl diisocyanate, aromatic polyisocyanate such as 1,5-naphthalene diisocyanate) and then adding a hydroxyl group-containing (meth) acrylate.

  Non-fluorine type epoxy (meth) acrylate is a reaction product of epoxy resin and (meth) acrylic acid, etc., and as epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, Examples thereof include terminal glycidyl ether and fluorene epoxy resin of a propylene oxide adduct of bisphenol A.

  Examples of the non-fluorinated polyester (meth) acrylate include a reaction product of polyester diol which is a reaction product of the above diol compound and the above dibasic acid or its anhydride, and (meth) acrylic acid. .

  Furthermore, you may use the above epoxy compound and (meth) acrylate compound as an oligomer as it is, or mixed with another component. In general, in the production of a curable epoxy resin or an epoxy (meth) acrylate resin, the product is divided into a monomer, a quantifier, an oligomer, and a solid polymer depending on its boiling point. These products have different viscosities, and can be used properly depending on the use as an adhesive or the like. Also in this invention, the usage of the fluorinated polyfunctional epoxy resin and the fluorinated polyfunctional epoxy (meth) acrylate resin constituting the main agent is the same.

  The light-resistant sealing resin composition of the present invention can further contain a curing agent (B) for curing the main resin, an antioxidant, a UV absorber, and the like.

  When the fluorinated polyfunctional epoxy resin is the main agent (A), the curing agent (B) is one or two selected from the group consisting of an acid anhydride, a modified acid anhydride, and a cationic polymerization initiator. More than seeds are used.

  As the cationic polymerization initiator, so-called onium salts and metallocene complexes are preferably used. As the onium salt, ammonium salt, diazonium salt, iodonium salt, sulfonium salt, phosphonium salt, selenium salt, arsonium salt and the like are used. These curing agents may be monomeric, quantified, oligomeric, or polymeric chemical structures. The chemical structure of each curing agent is not particularly limited, but generally known compounds known to be effective for curing epoxy resins can be arbitrarily selected and used. For example, “organic materials for imaging” (organic The onium salts and metallocene complexes described in the Electronics Materials Study Group, July 8, 1993, published by Bunshin Publishing) can be used. For example, each compound represented by the following formula and derivatives thereof can be mentioned. Although the density | concentration of a hardening | curing agent changes with activity and reactivity of the hardening | curing agent to be used, it is normally used by the density | concentration of 10 mass parts or less with respect to 100 mass parts of resin compositions. More preferably, 5 parts by mass or less is sufficient, and particularly highly reactive ones are used at 1 part by mass or less.

で表される陰イオンを示す。ｎは１〜１０，０００である。 In the above structural formula, unless otherwise specified, R and R _{1 to} R ₄ represent H, an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, or a phenyl group, and may be the same or different from each other. It may be. X ⁻ represents a halogen ion, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CF ₃ COO ⁻ , HSiF ₆ ⁻ , HSO ₄ ⁻ , SCN ⁻ , CH ₃ SO ₄ ⁻ Or the following formula:

An anion represented by n is 1 to 10,000.

  Moreover, an acid anhydride and a modified product of an acid anhydride can also be used as the curing agent (B).

  The acid anhydride as the curing agent (B) in the light-resistant sealing resin composition of the present invention is preferably an acid anhydride having no carbon-carbon double bond in the molecule. Examples thereof include hydrophthalic acid, methylhexahydrophthalic anhydride, hydrogenated nadic anhydride, hydrogenated methyl nadic anhydride, hydrogenated trialkylhexahydrophthalic anhydride, and 2,4-diethylglutaric anhydride. These may be used alone or in combination of two or more. Among these, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride are particularly preferable in that they have excellent heat resistance and a colorless cured product can be obtained.

  When only the acid anhydride is used as the curing agent (B), the blending ratio of the acid anhydride varies depending on the epoxy equivalent of all the epoxy resin components of the light-resistant sealing resin composition, but preferably 100 parts by mass of all the epoxy resin components In contrast, it is blended within the range of 40 to 200 parts by mass.

  The modified acid anhydride as the curing agent (B) in the light-resistant sealing resin composition of the present invention is the above-mentioned acid anhydride, preferably hexahydrophthalic anhydride, anhydrous methylhexahydrophthalic acid is glycol. Etc.

  Examples of glycols that can be used for modification include glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol; two or more of these Copolymer polyether glycols of glycol and / or polyether glycol can be used. These may be used alone or in combination of two or more.

  The amount of modification is preferably 0.4 mol or less of glycol with respect to 1 mol of acid anhydride. When the amount of modification increases, the viscosity of the composition increases, workability deteriorates, the reactivity with the epoxy resin decreases, the curing slows down, and the productivity when sealing the device is deteriorated. This is not preferable because

  When only the modified acid anhydride is used as the curing agent (B), the blending ratio of the modified acid anhydride varies depending on the epoxy equivalent of all the epoxy resin components of the light-resistant sealing resin composition, but preferably all It mix | blends within the range of 40-200 mass parts with respect to 100 mass parts of epoxy resin components.

  When using an acid anhydride and / or a modified acid anhydride as the curing agent (B), the light-resistant sealing resin composition of the present invention contains an epoxy resin and an acid anhydride and / or a modified product thereof. For the purpose of accelerating the curing reaction, a curing accelerator can be used.

  Examples of curing accelerators include tertiary amines and salts thereof; imidazoles and salts thereof; organic phosphine compounds; organic acid metal salts such as zinc octylate and tin octylate. Particularly preferred curing accelerators are Organic phosphine compounds.

  The blending ratio of the curing accelerator is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the acid anhydride and / or modified product blended as the curing agent. If it is out of the above range, the balance between heat resistance and moisture resistance of the cured epoxy resin tends to deteriorate.

  When the fluorinated polyfunctional epoxy (meth) acrylate resin is a curable main agent (A), a thermal radical polymerizable initiator and a photo radical polymerizable initiator are preferably used as the curing agent (B). It is done.

  Specific examples of the thermal radical polymerizable initiator include diisopropyl peroxydicarbonate, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butylperoxy-2-ethylhexanoate, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butyl hydroperoxide, t-butylperoxyneodikenate, t-butylper Organic peroxides such as oxybenzoate and cumene hydroperoxide; azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobisdiethylvaleronitrile are exemplified, but are particularly limited. It is not a thing.

  Examples of the photo radical polymerizable initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy- 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) Acetophenones such as phenyl] -2-morpholinopropan-1-one; acetylphenones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone Thraquinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide be able to.

  Preferred are acetophenones, and more preferred are 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone.

  In addition, in the resin composition of this invention, a radical initiator may be used independently and may be used in mixture of multiple types. Further, a thermal radical initiator and a photo radical initiator may be combined. The mixing ratio of the radical initiator is usually 0.001 to 50 parts by mass, preferably 0.005 to 40 parts by mass with respect to 100 parts by mass of the light-resistant sealing resin composition.

  It is preferable to add an antioxidant to the light-resistant sealing resin composition of the present invention to prevent oxidative deterioration during heating and to produce a cured product with little coloring.

  As the antioxidant, phenol-based, sulfur-based, and phosphorus-based antioxidants can be used. Specific examples include the following antioxidants.

(Phenolic antioxidant)
Monophenols; 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate, etc.

  Bisphenols; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-) 6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4) -Hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, etc.

  Polymeric phenols; 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3' -Bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, etc.

(Sulfur-based antioxidant)
Dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, etc.

(Phosphorus antioxidant)
Phosphites; triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, Cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butyl) -4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc.

  Oxaphosphaphenanthrene oxides; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

  These antioxidants may be used singly or in combination of two or more, but may be used in a combination of phenol / sulfur or a combination of phenol / phosphorus. Particularly preferred.

  The blending ratio of these antioxidants is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total epoxy resin component or the total epoxy (meth) acrylate resin component of the light-resistant sealing resin composition of the present invention. Is preferred. When the blending amount of the antioxidant is too small, it is not possible to obtain a sufficient addition effect, and when it is too large, the physical properties after curing, particularly the UV degradation resistance, tend to be lowered.

  The light-resistant sealing resin composition of the present invention can also be blended with an ultraviolet absorber to further improve the light resistance.

  As the UV absorber, a general UV absorber for plastics can be used, and examples thereof include the following.

  Salicylic acids such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy Benzophenones such as -4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5 ′; -Di tert- Tilphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert- Butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-amylphenyl) benzotriazole, 2-{(2′-hydroxy-3 ′, 3 ″, 4 ″) Benzotriazoles such as 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl} benzotriazole; bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{ 5- bis (1,1-dimethylethyl) -4-hydroxyphenyl} hindered amines such as methyl] butyl malonate

  The blending ratio of these ultraviolet absorbers is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total epoxy resin component or the total epoxy (meth) acrylate resin component of the light-resistant sealing resin composition of the present invention. Is preferred. If the blending amount of the UV absorber is too small, a sufficient addition effect cannot be obtained, and if it is too large, the physical properties after curing, particularly heat resistance, tend to be lowered.

  In the light-resistant sealing resin composition of the present invention, in addition to the above components, other additives can be appropriately blended as necessary to the extent that the characteristics of the light-resistant sealing resin composition of the present invention are not impaired. .

  Examples of other additives include the following.

(I) Powdery reinforcing agents and fillers, for example, metal oxides such as aluminum oxide and magnesium oxide; silicon compounds such as fine powder silica, fused silica and crystalline silica; transparent fillers such as glass beads; metals such as aluminum hydroxide Other examples include hydroxides; kaolin, mica, quartz powder, graphite, molybdenum disulfide, and the like.

  These reinforcing agents and fillers are blended within a range that does not impair the transparency of the light-resistant sealing resin composition of the present invention, and are usually added to 100 parts by mass of the main component (A) of the light-resistant sealing resin composition of the present invention. On the other hand, 100 parts by mass or less is appropriate.

(Ii) Colorant or pigment Examples include titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red, and organic dyes.

(Iii) Flame retardant For example, antimony trioxide, a bromine compound, a phosphorus compound, etc. can be illustrated.

  In addition, (iv) an ion adsorbent, (v) a coupling agent, and the like can be used.

  These components (ii) to (v) can be usually blended in an amount of 0.01 to 30 parts by mass with respect to 100 parts by mass of the main component (A) of the light-resistant sealing resin composition of the present invention.

  The light-resistant sealing resin composition of the present invention can further contain various curable monomers, oligomers, or synthetic resins for the purpose of improving the properties of the obtained cured product.

  Examples of such compounds and resins for improving properties include one or a combination of two or more of diols or triols, vinyl ethers, oxetane compounds, silicone resins and the like.

  The compounding ratio of these compounds and resins is in an amount that does not impair the original properties of the light-resistant sealing resin composition of the present invention, that is, 100 masses of the main component (A) of the light-resistant sealing resin composition of the present invention. 50 parts by mass or less is preferable with respect to parts.

  The encapsulating resin composition of the present invention is a composition used for encapsulating optical elements and the like.

  Examples of usage of the sealing resin composition include packages (encapsulation) of light functional elements such as light emitting elements such as light emitting diodes (LEDs), EL elements, and nonlinear optical elements, and light receiving elements such as CCD, CMOS, and PD. The implementation can be exemplified.

  The sealed optical element is used in various places, but non-limiting examples include backlights such as liquid crystal displays, photocouplers, high-mount stop lamps and meter panels, mobile phone backlights, Light sources such as lighting, various sensors, printers, copiers, vehicle measuring instrument light sources, signal lights, indicator lights, display devices, planar light source light sources, displays, light sources for remote control devices for various electrical products, decorations, various lights And light emitting elements such as switching elements; camera autofocus, light receiving elements for optical pickup for CD / DVD, and the like. In particular, a top-view type optical semiconductor element that directly takes out light from the light-emitting element is preferable.

  In particular, a cured product obtained by curing the resin composition for sealing an optical element of the present invention is excellent in heat resistance, light resistance, and transparency, and has low water absorption, so that the use environment (heat, light, Regardless of water), it exhibits performance as a sealing resin, so it is used for optical semiconductors such as LEDs, especially ultraviolet light emitting elements that emit light at a relatively short wavelength with a peak wavelength of 350 to 500 nm. It is useful as a sealing material for LED, blue-violet LED, blue LED, white LED or white LED for illumination.

Examples of such light-emitting elements include Group III of the periodic table formed by metal organic chemical vapor deposition (MOCVD), molecular beam crystal growth (MBE), and halide vapor deposition (HVPE). Nitride-based compound semiconductors are examples. The general formula is represented by Al _X Ga _Y In _1-XY N (0 ≦ X ≦ 1, 0 ≦ Y ≦ 1, 0 ≦ X + Y ≦ 1), and a so-called binary system of Al _X , GaN and InN, Al _X It includes so-called ternary systems of Ga _1-X N, Al _X In _1-X N, and Ga _X In _1-X N (where 0 ≦ X ≦ 1). Examples of the semiconductor structure include a homostructure having a MIS junction, a PIN junction, a pn junction, or the like, a heterostructure, or a double heterostructure. Various emission wavelengths can be selected depending on the material of the semiconductor layer and the degree of mixed crystal. In addition, a single quantum well structure or a multiple quantum well structure in which the semiconductor active layer is formed in a thin film in which a quantum effect is generated can be used.

  As a general method of sealing, a low-pressure transfer molding method can be mentioned, but sealing can also be performed by injection molding, compression molding, casting, potting, casting, screen printing or the like. Although the curing conditions at the time of molding and / or after molding vary depending on the type and amount of each component of the resin composition, the curing temperature is preferably 50 to 200 ° C. and the curing time is preferably 1 minute to 10 hours.

  When sealing the light emitting element using the sealant of the present invention, other sealants may be used in combination. In this case, after sealing the light emitting element with the sealing agent of the present invention, the periphery thereof may be sealed with the other sealing agent, and the light emitting element is sealed with the other sealing agent. Thereafter, the periphery thereof may be sealed with the sealant of the present invention.

  The other sealing agent is not particularly limited, and examples thereof include an epoxy resin, a silicone resin, an acrylic resin, a urea resin, an imide resin, and glass. Moreover, when a surface modifier is contained, a liquid can be applied to provide a protective layer on the surface.

  Moreover, since the sealing resin composition of this invention is excellent in light resistance and heat resistance, it is useful also as a sealing resin for solar cells, a sealing material, a sealing material. Since the sealing resin composition of the present invention has low water absorption, it is said that the solar cell is relatively weak against moisture, particularly organic solar cells such as dye-sensitized solar cells and organic thin film solar cells. It is also useful for batteries. These solar cells have high design properties, and transparent sealing materials and sealing material materials are required. Further, since it has high light resistance, it is also useful as a sealing material (or filler) for optical members such as lenses for deep ultraviolet microscopes. In these applications, high light resistance is required. In addition, it can also be used as a sealing member material for electronic semiconductors utilizing the heat resistance and low water absorption of the present invention, a water and moisture resistant adhesive, and a heat resistant sealing material for power devices such as SiC.

  EXAMPLES Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited only to these examples.

The test methods performed in this example are summarized.

(1) Refractive index (n)
A value measured with an Abbe refractometer at 25 ° C. using sodium D-line as a light source is adopted.

(2) Water absorption rate The water absorption rate is determined by a method based on JIS K 6911 except that a test piece having a disk size of 10 mmφ × 1 mm is used.

(3) Transmittance The transmittance at 405 nm of a 1 mm thick sheet is measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.).

(4) Fluorine content 10 mg of the sample is burned by the oxygen flask combustion method, the decomposition gas is absorbed in 20 ml of deionized water, and the fluorine ion concentration in the absorption liquid is determined by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion). ) To obtain (mass%).

(5) Thermal decomposition temperature (Td)
Using a thermogravimeter (TGA-50 manufactured by Shimadzu Corporation), measurement is performed under the conditions of an air atmosphere at a rate of temperature increase of 10 ° C./min, and evaluation is performed at a temperature of 1% mass loss.

(6) Light resistance Using a UV-LED device (ZUV-C10 manufactured by OMRON Corporation), after irradiating a sheet of 1 mm thickness with UV light of 365 nm for 120 minutes, the transmittance of light of 405 nm is measured spectrophotometrically. Measurement is performed using a meter (U-4100 manufactured by Hitachi, Ltd.).

(7) Heat resistance After leaving a cured product having a thickness of 1 mm in an oven at 150 ° C. for 500 hours, the transmittance at 500 nm is measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.).

Example 1
Add 2 g of CHEp as a fluorinated polyfunctional epoxy resin, 1.15 g of HN-5500 manufactured by Hitachi Chemical Co., Ltd. as an acid anhydride, and 0.09 g of U-CAT18X manufactured by San Apro Co., Ltd. as an epoxy curing catalyst. The whole was kept at 60 ° C. to prepare a uniform curable composition.

  The composition was then degassed under vacuum and reduced pressure, poured into a predetermined mold, and heated in a thermostatic bath at 90 ° C. for 2 hours and further at 130 ° C. for 3 hours to obtain a cured product.

  Various physical properties of the obtained cured product were measured. The results are shown in Table 1.

Examples 2-10
A composition was prepared using the components shown in Table 1 in the same manner as in Example 1, and then thermally cured in the same manner as in Example 1 to obtain a cured product.

  Various physical properties of the obtained cured product were measured. The results are shown in Table 1.

Comparative Examples 1-2
A composition was prepared using the components shown in Table 1 in the same manner as in Example 1, and then thermally cured in the same manner as in Example 1 to obtain a cured product.

  Various physical properties of the obtained cured product were measured. The results are shown in Table 1.

  The components used in Examples 1 to 10 and Comparative Examples 1 and 2 shown in Table 1 are as follows.

ＤＦＥｐ：

ＣＨＥｐ：

ＢｚＥＰ：

ＤＰＥｐ：

ＣＨＣＯｐ：

Ｒｆｎ＝２Ｅｐ：

(Fluorinated polyfunctional epoxy resin)
AFEp:

DFEp:

CHEp:

BzEP:

DPEp:

CHCOp:

Rfn = 2Ep:

ＸＹ−８０００（（株）ジャパンエポキシレジン製）：

(Non-fluorinated polyfunctional epoxy resin)
Aep:

XY-8000 (manufactured by Japan Epoxy Resin Co., Ltd.):

エポライト１５００ＮＰ（共栄社化学（株）製）：

セロキサイド２０２１Ｐ（ダイセル化学（株）製）：

(Diluent)
Epolite 1600 (manufactured by Kyoeisha Chemical Co., Ltd.):

Epolite 1500NP (manufactured by Kyoeisha Chemical Co., Ltd.):

Celoxide 2021P (manufactured by Daicel Chemical Industries):

(Curing agent: acid anhydride)
HN-5500 (manufactured by Hitachi Chemical Co., Ltd.)

(Curing accelerator)
U-CAT18X (Epoxy resin curing accelerator manufactured by San Apro Co., Ltd.)

Example 11
Add 1 g of CHEp as the fluorinated polyfunctional epoxy resin, 1 g of Epolite 1600 (manufactured by Kyoeisha Chemical Co., Ltd.) as the polyfunctional epoxy, and 0.085 g of CPI-100 from San Apro Co., Ltd. as the photocationic polymerization initiator. The whole was kept at 60 ° C. to prepare a uniform curable composition.

This composition is defoamed under vacuum and reduced pressure, then poured into a predetermined mold, sandwiched with a slide glass at the top and bottom, and irradiated with a total of 6 J / cm ² of UV light using a belt conveyor type UV exposure machine and cured. I got a thing.

  Various physical properties of the obtained cured product were measured. The results are shown in Table 2.

Examples 12-14
A composition was prepared using the components shown in Table 2 in the same manner as in Example 11, and then photocured in the same manner as in Example 11 to obtain a cured product.

  Various physical properties of the obtained cured product were measured. The results are shown in Table 2.

  In addition to the components described in Table 1, the following components were used in Table 2.

(Curing agent: Photocatalyst)
CPI-100P (Photocationic polymerization initiator manufactured by San Apro Co., Ltd.)

Example 15
1 g of CHEpA as a fluorinated polyfunctional epoxy (meth) acrylate resin, 1 g of 16HX as a non-fluorinated polyfunctional epoxy (meth) acrylate compound, 0.08 g of Dicure MBF manufactured by Ciba Specialty Chemicals as a photo radical polymerization initiator In addition, the whole was kept at 60 ° C. to prepare a uniform curable composition.

This composition is defoamed under vacuum and reduced pressure, poured into a predetermined mold, sandwiched with a slide glass, and irradiated with a total of 4 J / cm ² of UV light by a belt conveyor type UV exposure machine, and cured. I got a thing.

  Various physical properties of the obtained cured product were measured. The results are shown in Table 3.

Examples 16-23
A composition was prepared using the components shown in Table 3 in the same manner as in Example 15, and then photocured in the same manner as in Example 15 to obtain a cured product.

  Various physical properties of the obtained cured product were measured. The results are shown in Table 3.

Comparative Examples 3-4
A composition was prepared using the components shown in Table 3 in the same manner as in Example 15, and then photocured in the same manner as in Example 15 to obtain a cured product.

  Various physical properties of the obtained cured product were measured. The results are shown in Table 3.

  The components used in Examples 15 to 23 and Comparative Examples 3 to 4 shown in Table 3 are as follows.

ＡｆＥｐＭＡ：

ＣＨＥｐＡ：

ＢｚＥｐＭＡ：

ＤｐＥｐＡ：

Ｒｆｎ＝２ＥｐＡ：

(Fluorinated polyfunctional epoxy (meth) acrylate resin)
AFEpA:

AfEpMA:

CHEpA:

BzEpMA:

DpEpA:

Rfn = 2EpA:

(Non-fluorinated polyfunctional epoxy (meth) acrylate resin)
BisA-EpA:

(Non-fluorinated polyfunctional (meth) acrylate compounds)
16HX (1,6-hexanediol diacrylate):
_{CH 2 = CHCOO (CH 2)} 6 OCOCH = CH 2
TMPA (trimethylolpropane triacrylate):
_{H 5 C 2 -C (CH 2} OCOCH = CH 2) 3

(Fluorine-containing monofunctional (meth) acrylate compound)
8FA:
CH ₂ = CHCOOCH ₂ C ₄ F ₈ H

(Curing agent: Photocatalyst)
Darocur MBF (photo radical polymerization initiator manufactured by Ciba Specialty Chemicals)

Example 16
The resin compositions prepared in Example 1 and Comparative Example 2 were exposed using a belt conveyor type UV exposure machine, and the transmittance at 400 nm was measured for each cured product obtained after exposure for a predetermined amount.

  The transmittance of each cured product after exposure was determined as a relative value (%) with the initial transmittance being 100% and plotted on a graph. The results are shown in FIG.

  As is clear from FIG. 1, the cured product of this example showed high light resistance.

Claims (6)

Optical element comprising curable main agent (A) containing fluorinated polyfunctional epoxy resin and / or fluorinated polyfunctional epoxy (meth) acrylate resin, and curing agent (B) for curing the resin Sealing resin composition. The main agent (A) is represented by the formulas (I) to (IV):

[Wherein Rf is

{Where,
A is the formula:

(Wherein Rf ¹ is a C 1-10 perfluoroalkyl group; Rf ² is a C 1-12 perfluoroalkyl group; p is an integer of 0-3; q is an integer of 0-3; 0 or 1; s is an integer of 0 to 5; t is an integer of 0 to 5);
B is the same as A or a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a fluoroalkyl group having 1 to 8 carbon atoms;
Z is a hydrogen atom or a C1-C18 fluoroalkyl group;
M is

(Wherein R is the same or different, an alkyl group having 1 to 5 carbon atoms, OH, CH ₃ , NH ₂ , a halogen atom, a fluoroalkyl group having 1 to 20 carbon atoms; l ₁ , l ₂ and l ₃ are Any of 0 or an integer of 1 to 10 represents the number of substituents R);
x is an integer of 1 to 36}, at least one selected from the group consisting of fluorinated polyfunctional epoxy resins represented by n or 0 or any positive number], And / or formulas (V) to (VI):

[Wherein Rf is the same as above; Y is a hydrogen atom or CH ₃ ; n is 0 or any positive number] and is selected from the group consisting of fluorinated polyfunctional epoxy (meth) acrylate resins The resin composition for sealing of Claim 1 containing 1 type. Rf is

The sealing resin composition according to claim 2. Rf is

The sealing resin composition according to claim 2. The sealing resin composition according to claim 1, wherein the optical element is a light emitting element having a main light emission peak at a wavelength of 350 to 500 nm. The sealing resin composition according to claim 1, wherein the optical element is a light emitting diode (LED).

Images