JP2007291272A - Composition for sealing material, and optical device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for sealing materials that is transparent, exhibits excellent light resistance and permits thick film formation, and an optical device. <P>SOLUTION: The composition for sealing materials comprises a silsesquioxane compound having a silsesquioxane structure and containing no reactive groups other than a silanol group, where the silsesquioxane structure comprises an ethyl-silsesquioxane structure. The optical device is equipped with an optical element mounted on a substrate and a sealing material obtained by curing the composition for sealing materials that covers the optical element. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composition for an encapsulant and an optical device, and particularly relates to a composition for an encapsulant and an optical device that are transparent and excellent in light resistance.

  In recent years, optical elements that emit light having a short wavelength of 400 nm or less, such as light emitting diodes (LEDs) and semiconductor lasers (LDs), have been developed and used in the fields of information communication, information recording, and displays. Yes. Such an optical element is used by being mounted on a substrate or the like and sealed with a sealing material. Conventionally, a transparent epoxy resin has been used as a sealing material for optical elements such as LEDs. This transparent epoxy resin has poor light resistance and has a problem of yellowing with time due to visible light or ultraviolet rays.

Japanese Patent Laid-Open No. 2004-359933 discloses that a material made of silsesquioxane, which is a network-type oligomer containing silicon, is used as a sealing material for such an optical element (Patent Document 1). . Since a sealing material using a material made of silsesquioxane is superior in light resistance to a sealing material using a transparent epoxy resin, it is expected as a material for a sealing material of an optical element.
JP 2004-359933 A

  However, even a conventional sealing material using a material made of silsesquioxane is insufficient in light resistance, and a sealing material that exhibits further excellent light resistance is desired. Furthermore, it is also desired that a molded body having no cracks can be obtained even if it is molded into a thick film.

  This invention is made | formed in view of this point, and it aims at providing the composition for sealing materials and optical device which are transparent, excellent in light resistance, and in which thick film shaping | molding is possible.

  The composition for a sealing material of the present invention is a composition for a sealing material containing a silsesquioxane compound having a silsesquioxane structure and having only a silanol group as a reactive group. The oxane structure includes an ethylsilsesquioxane structure.

  According to this configuration, since the reactive group of the silsesquioxane compound is only a silanol group, it is possible to prevent other reactive groups from affecting the light resistance due to decomposition during the curing. For this reason, the sealing material very excellent in light resistance can be obtained. Moreover, since the composition for sealing materials of this invention contains silsesquioxane, it is transparent as a sealing material after hardening. Moreover, since the silsesquioxane structure includes an ethyl silsesquioxane structure, the moldability of the composition for a sealing material is improved, and a thick film molded body can be obtained.

  In the composition for sealing materials of this invention, it is preferable that the said silsesquioxane compound contains about 10 mol% or more of ethyl silsesquioxane structures.

  The optical device of the present invention comprises an optical element mounted on a substrate, and a sealing material that is coated on the optical element and that cures the composition for sealing material. .

  The composition for a sealing material of the present invention includes a silsesquioxane compound having a silsesquioxane structure and a reactive group having only a silanol group, and the silsesquioxane structure is Since the reactive group containing an ethylsilsesquioxane structure contains a silsesquioxane compound having only a silanol group, it is transparent, excellent in light resistance, and excellent in moldability.

  In the composition for a sealing material containing a silsesquioxane compound, the present inventors pay attention to the relationship between a reactive group and light resistance, and when the reactive group is only a silanol group, the sealing material The present invention has been found to be excellent in light resistance, and has been found to be excellent in moldability by including an ethylsilsesquioxane structure in the silsesquioxane structure.

  That is, the gist of the present invention includes a silsesquioxane compound having a silsesquioxane structure and a reactive group having only a silanol group, wherein the silsesquioxane structure is an ethyl silsesquioxane structure. By including an oxane structure, it is transparent, is excellent in light resistance, and implement | achieves the composition for sealing materials excellent in the moldability.

Hereinafter, embodiments of the present invention will be described in detail.
The composition for a sealing material of the present invention contains a silsesquioxane compound whose reactive group is only a silanol group. In addition, the composition for sealing materials of this invention should just contain the silsesquioxane compound whose reactive group is only a silanol group, and the reactive group has a silsesquioxane compound which is only a silanol group. If it contains, the silsesquioxane compound which has reactive groups other than a silanol group may be contained.

Here, the silsesquioxane compound means a compound containing at least an RSiO _3/2 silsesquioxane structure (R is the same as R ₁ described later). As such a silsesquioxane compound, a compound having a ladder-like silsesquioxane structure as shown in FIG. 1 (a), a compound having a cage-like silsesquioxane structure as shown in FIG. 1 (b). And compounds having an amorphous silsesquioxane structure as shown in FIG. 1 (c), and mixtures thereof. As the silsesquioxane compound, it is preferable that a relatively large amount of the cage silsesquioxane compound is contained in consideration of the high glass transition temperature.

  The silsesquioxane structures may be directly bonded to each other or may be bonded via any atom or functional group, for example, an oxygen atom or an organic group. Examples of the organic group include a hydrocarbon group, an oxyalkylene group, a siloxane group, a polymer thereof, and a structure combining them.

  As content of the silsesquioxane in the silsesquioxane compound of this invention, 20 to 100 weight% is preferable and 40 to 100 weight% is more preferable.

  In the present invention, the silsesquioxane structure includes an ethyl silsesquioxane structure. Thus, by including an ethyl silsesquioxane structure, the moldability of the composition for a sealing material can be improved, and a thick film molded body having a thickness of about 1 mm to 2 mm can be obtained. Become. In this case, the silsesquioxane compound is an all-silsesquioxane compound in consideration of the cured state of the composition for encapsulating materials (there is no crack, and there is no stickiness when the cured molded body is touched). The ethyl silsesquioxane structure is preferably contained in an amount of about 10 mol% or more, more preferably about 25 mol% or more, and further preferably 50 mol% or more based on the sun structure.

  In addition, the silsesquioxane compound may include a phenyl silsesquioxane structure. The silsesquioxane compound has a phenyl silsesquioxane structure and an ethyl group in consideration of the cured state of the composition for a sealing material (there is no crack, and the cured molded body is brought into a non-sticky state). The combined silsesquioxane structure is preferably contained in an amount of about 10 mol% or more, more preferably about 25 mol% or more, and further preferably 50 mol% or more.

  When the silsesquioxane compound contains a phenyl silsesquioxane structure and an ethyl silsesquioxane structure, the content ratio is determined by the solubility in a solvent and the cured state of the composition for a sealing material (there is no crack and the composition is cured). In view of the fact that the molded product is not sticky when touched), the molar ratio (phenylsilsesquioxane structure: ethylsilsesquioxane structure) is preferably 100: 0 to 5:95, 75:25 to 25:75 is more preferable.

  In addition, when using the composition for sealing materials of this invention as a sealing material of LED, since the wavelength of LED is about 350 nm and absorption of a phenyl group is 300 nm or less, a phenyl group is deteriorated with the light of LED. There is no fear. However, if the conjugation of the phenyl group extends to other functional groups or a dimer is formed between the phenyl groups, the absorption wavelength becomes longer, and the phenyl group may be degraded by the light of the LED. For this reason, as for the amount of phenylsilsesquioxane structure contained in the silsesquioxane compound and the presence state of the phenylsilsesquioxane structure in the compound, the conjugation of the phenyl group does not extend to other functional groups, It is preferable to determine appropriately so as not to form a dimer between phenyl groups.

  The cage silsesquioxane compound in the composition for a sealing material of the present invention is (1) an unpolymerized cage silsesquioxane (structure of n = 0 in the following chemical formula 1); (2) polymerized. Partially cleaved cage silsesquioxane (structure of k = 0 in the following chemical formula 9); (3) cage silsesquioxane polymer obtained by polymerizing a plurality of cage silsesquioxanes; (4) Partially cleaved cage silsesquioxane polymer obtained by polymerizing a plurality of partially cleaved cage silsesquioxanes; (5) Co-weight of caged silsesquioxane and partially cleaved cage silsesquioxanes Includes coalescence.

式（１）において、ｍは６から１４の整数であり、ｎは０以上ｍ以下の整数である。Ｒ₁は水酸基、シラノール基を含有する一価の有機基、非反応性の一価の有機基から選ばれ、Ｒ₁はすべて同一でも異なっていても良い。 A specific structure of the cage silsesquioxane having a closed siloxane structure is represented by the following formula (1).

In Formula (1), m is an integer of 6 to 14, and n is an integer of 0 or more and m or less. R ₁ is selected from a hydroxyl group, a monovalent organic group containing a silanol group, and a non-reactive monovalent organic group, and R ₁ may be the same or different.

  Examples of the non-reactive monovalent organic group include a substituted or unsubstituted hydrocarbon group, a silicon atom-containing group, and a group obtained by combining them. Examples of the monovalent organic group containing a silanol group include a group obtained by modifying a part of the non-reactive monovalent organic group into a silanol group.

  Examples of the hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, butyl (n-butyl, i-butyl, t-butyl, sec-butyl), pentyl (n-pentyl, i-pentyl, Neopentyl, cyclopentyl, etc.), hexyl (n-hexyl, i-hexyl, cyclohexyl etc.), heptyl (n-heptyl, i-heptyl etc.), octyl (n-octyl, i-octyl, t-octyl etc.), nonyl ( acyclic such as n-nonyl, i-nonyl, etc., decyl (n-decyl, i-decyl etc.), undecyl (n-undecyl, i-undecyl etc.), dodecyl (n-dodecyl, i-dodecyl etc.) Or cyclic aliphatic hydrocarbon group; aralkyl such as benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl Le group; a phenyl group, an aryl group such as tolyl or xylyl group.

  A hydrogen atom or a part of the main chain skeleton of the hydrocarbon group may be partially substituted with a substituent such as an ether bond, an ester group (bond), a carbonyl group, or a fluorine atom.

  The total number of carbon atoms including the substituent in the substituted or unsubstituted hydrocarbon group is usually 20 or less, but is not limited thereto. Considering heat resistance and the like, the total number of carbon atoms is preferably 16 or less, more preferably 6 or less.

  Examples of the silicon-containing group include groups having structures represented by the following formulas (2) and (3). The number of silicon atoms in the silicon atom-containing group is usually 1 to 10, preferably 1 to 6, and more preferably 1 to 3, but is not limited thereto.

式（２）において、ｎ'は、通常１〜１０の整数であり、好ましくは１〜６の整数、より好ましくは１〜３の整数であるが、これに限定されるものではない。式（２）において、置換基Ｒ₂，Ｒ₃，Ｒ₄は、ヒドロキシル基、又は炭素数１〜１０個、好ましくは炭素数１〜６個の有機基である。

In Formula (2), n 'is an integer of 1-10 normally, Preferably it is an integer of 1-6, More preferably, it is an integer of 1-3, However, It is not limited to this. In the formula (2), the substituents R ₂ , R ₃ and R ₄ are a hydroxyl group or an organic group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

Examples of the organic group having 1 to 10 carbon atoms include various substituted or unsubstituted hydrocarbon groups. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group. An aromatic hydrocarbon group such as a phenyl group, a benzyl group, or a phenethyl group; a fluorine-containing alkyl group such as CF ₃ CH ₂ CH ₂ —, and the like.

Specific examples of the silicon atom-containing group represented by the formula (2) include trimethylsiloxy group (Me ₃ Si-), dimethylphenylsiloxy group (Me ₂ PhSiO-), diphenylmethylsiloxy group, phenethyldimethylsiloxy group. , dimethyl -n- hexyl siloxy group, dimethyl cyclohexyl siloxy group, dimethyl octyl siloxy _{group, (CH 3) 3 SiO [} Si (CH 3) 2 O] q - (q = 1~9), 2- phenyl-2, 4,4,4-tetramethyldisiloxy group (OSiPhMeOSiMe ₃ ), 4,4-diphenyl-2,2,4-trimethyldisiloxy (OSiMe ₂ OSiMePh ₂ ), 2,4-diphenyl-2,4,4- And trimethyldisiloxy (OSiPhMeOSiPhMe ₂ ).

式（３）において、Ｒ_aは炭素数１〜１０個の２価の炭化水素基であり、炭素数は、好ましくは２〜６個であり、より好ましくは２又は３個である。Ｒ_aの具体例としては、−ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂−、−（ＣＨ₂）_p−（ｐ＝４〜１０）などのアルキレン基が挙げられる。

In the formula (3), R _a is _a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 or 3 carbon atoms. Specific examples of R _a include alkylene groups such as —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, and — (CH ₂ ) _p — (p = 4 to 10).

R _2, R _3, R _4, R _5, R ₆ in the formula (3) is the same as R _2, R _3, R ₄ in the formula (2). n ″ is 0 or an integer of 1 to 9, preferably 0 or an integer of 1 to 5, particularly preferably 0, 1 or 2.

As a specific example of the cage silsesquioxane described above, a structure like Formula (4) represented by m = 6 in Formula (1), and represented by m = 8 in Formula (1) A structure like Formula (5), a structure like Formula (6) represented by m = 10 in Formula (1), and a formula (7) like m = 12 in Formula (1) A structure, a structure like Formula (8) represented by m = 14 in Formula (1), etc. are mentioned. However, the formula (4) R in - (8) represents a bond of similar or other cage-like silsesquioxane or partial cleavage type cage-like silsesquioxane Sanhe and R ₁ in formula (1), of the R N (that is, 1 or more and m or less) represents a bond to another (partially cleaved) cage silsesquioxane.

  The partially cleaved cage silsesquioxane refers to a structure in which a part of the silicon-oxygen bond of the cage silsesquioxane structure is cleaved or a structure in which a part of the cage silsesquioxane structure is eliminated. . A specific structure is represented by the following formula (9).

式（９）において、６≦ｌ＋ｊ≦４０、ｌ≧１、ｊ≧４である。式（９）においてＲ₁は、式（１）におけるＲ₁と同様であり、すべて同一の構造でも、互いに異なっていても良い。

In Expression (9), 6 ≦ l + j ≦ 40, l ≧ 1, and j ≧ 4. In formula (9), R ₁ is the same as R ₁ in formula (1), and they may all be the same structure or different from each other.

As a specific example of such a partially cleaved cage silsesquioxane, a structure such as formula (10) represented by j = 4 and l = 3 in formula (9), formula (9) Examples include structures such as formula (11) and formula (12) represented by j = 6 and l = 2. However, in the formula (10) ~ (12), R is the same as R ₁ of formula (1), X is R ₁ the same or another cage-like silsesquioxane or parts of the general formula (1) Represents a bond to a cleaved cage silsesquioxane. K of X (that is, 0 or more and 3 or less) represents a bond to another cage-like silsesquioxane or a partially cleaved cage-like silsesquioxane.

  Next, a (partially cleaved) cage silsesquioxane polymer obtained by polymerizing a plurality of (partially cleaved) cage silsesquioxanes will be described. The (partially cleaved) cage silsesquioxane polymer may be bonded in a linear, branched or three-dimensional network. Silsesquioxanes (ie, cage silsesquioxanes, partially cleaved cage silsesquioxanes, cage silsesquioxanes and partially cleaved cage silsesquioxanes) are directly bonded. It may be bonded via any atom or functional group, for example, an oxygen atom or an organic group. Examples of the organic group include a hydrocarbon group, an oxyalkylene group, a siloxane group, a polymer thereof, and a structure combining them.

Examples of the hydrocarbon group and the polymer thereof include — (CH ₂ ) _s —, an alkylene group represented by (s is a natural number), an aromatic hydrocarbon group, and the like. S in — (CH ₂ ) _s — is preferably from 1 to 100, more preferably from 1 to 20. Specifically, the alkylene group includes a methylene group, an ethylene group, a polyethylene structure, and the aromatic hydrocarbon group includes a phenylene group.

Examples of the oxyalkylene group and its polymer-(R'O) _t- (t is a natural number) include oxymethylene group, oxyethylene group, oxypropylene group, polyoxymethylene, polyoxyethylene, polyoxypropylene and the like. It is done. The t is preferably 1 or more and 100 or less, and more preferably 1 or more and 20 or less.

ここで、Ｒ₂，Ｒ₃は式（２）におけるＲ₂，Ｒ₃と同じである。ｎ'''は自然数である。 As said siloxane group and its polymer, the structure represented by following formula (13) is mentioned, for example.

Wherein, R _2, R ₃ are the same as R _2, R ₃ in the formula (2). n ″ ′ is a natural number.

  In the above hydrocarbon group, oxyalkylene group, siloxane group and polymers thereof, a hydrogen atom or a part of the skeleton may be partially substituted with an organic group. In consideration of moldability and the like, it is preferable that a siloxane group is contained in an organic group that bonds silsesquioxanes.

  The number average molecular weight of the (partially cleaved) cage silsesquioxane polymer is preferably 500 or more and 400,000 or less, more preferably 500 or more and 50,000 or less.

  When the cage silsesquioxane polymer and the partially cleaved cage silsesquioxane polymer are copolymerized, in the binding sequence of the cage silsesquioxane and the partially cleaved cage silsesquioxane, Both may be combined alternately or in a random order. Moreover, you may couple | bond with a fixed regularity.

  The ratio of the cage silsesquioxane and the partially cleaved cage silsesquioxane is a molar ratio of (cage silsesquioxane) :( partially cleaved cage silsesquioxane) = 1: 99 to 95. : 5, more preferably 5:95 to 30:70.

The silsesquioxane compound described above, that is, the silsesquioxane compound in which the reactive group is only a silanol group, is prepared by, for example, treating a trialkoxysilane compound having no reactive group other than an alkoxy group in the presence of an acid or a base. It can obtain by making it react on these conditions. The alkoxy group is hydrolyzed / condensed to produce a silsesquioxane skeleton and a silanol group. Further, since the trialkoxysilane has no reactive group other than the alkoxyl group, the product obtained by hydrolysis / condensation has no reactive group other than the silanol group. Examples of trialkoxysilane compounds having no reactive group other than alkoxy groups include methyltrialkoxysilane, ethyltrialkoxysilane, isobutyltrialkoxysilane, cyclopentyltrialkoxysilane and the like. Examples of the acid and base include hydrochloric acid, lithium hydroxide, sodium hydroxide, and tetramethylammonium hydroxide. The predetermined condition is, for example, room temperature stirring. The structure of the silsesquioxane compound can be confirmed by using ¹ H-NMR and ²⁹ Si-NMR.

  Since the composition for sealing materials of this invention contains the silsesquioxane compound whose reactive group is only a silanol group, it is excellent in light resistance and excellent in adhesiveness with a base material. Regarding light resistance, the reactive group is only a silanol group, and other functional groups do not contribute to the reaction at the time of curing, so that the bond generated at the time of curing is a siloxane group with high light resistance. Conceivable. Moreover, about adhesiveness, it is thought that it is based on the interaction between a silanol group and the hydroxyl group which exists in the base-material surface.

  In the composition for sealing materials of this invention, the compound which has a functional group which can react with a silanol group other than the silsesquioxane compound may be contained. By including such a compound, the compound reacts with the silsesquioxane compound and is cured in the curing process of the composition for encapsulant. Moreover, the elasticity modulus of hardened | cured material can be controlled by adjusting content of such a compound. Examples of such a compound include a compound containing two or more SiH and / or SiOH and a cyclic polyfunctional compound. Examples of the skeleton of the compound containing two or more SiH and / or SiOH include siloxane, alkylene, oxyalkylene, polymers thereof, and a combination of them. The skeleton of the cyclic polyfunctional compound includes a cycloalkane structure such as cyclobutane, cyclopentane, and cyclohexane; a cyclosiloxane structure such as tetracyclosiloxane; an aromatic ring structure such as benzene, and the functional group is SiH or SiOH. Some are listed. Among these, the skeleton of the cyclic polyfunctional compound is preferably a cycloalkane structure or a cyclosiloxane structure. In particular, the cyclic polyfunctional compound is preferably a polyfunctional vinylcycloalkane (for example, polyfunctional vinylcyclohexane) or a polyfunctional cyclosiloxane.

  Examples of the method for curing the composition for sealing material of the present invention include thermal curing, curing with actinic rays, and curing by a combination thereof.

  In the thermosetting condition of the composition for sealing material of the present invention, the curing temperature is preferably room temperature or higher and 200 ° C. or lower in consideration of the light resistance of the optical element. In the curing of the encapsulant composition, for example, the encapsulant composition is poured into a mold and temporarily cured, and then the temporarily cured product is removed from the mold and the temporarily cured product is cured to obtain a molded body. In addition, the method of obtaining a molded object from the composition for sealing materials is not limited to this, It can carry out by changing variously.

  When the composition for a sealing material of the present invention is cured with actinic rays, a photoacid generator or a photobase generator may be added as a compound that accelerates curing. Examples of the photoacid generator include onium salts and sulfonic acid derivatives, and aromatic onium salts are particularly effective. Examples of the photobase generator include benzyl carbamate compounds, benzoin carbamate compounds, o-carbamoylhydroxyamines, o-carbamoyl oximes, aromatic sulfonamides, N- (2-arylethenyl) amides, aryl azides , N-arylformamides, acyloxyimino compounds, and N-substituted-4- (orthonitrophenyl) dihydropyridines.

  The curing mode of the composition for sealing material of the present invention is as follows: 1) reaction between silanol-type silsesquioxanes, 2) reaction between silsesquioxanes and SiH-based additives, 3) silsesquioxanes and silanols. Reaction with system additives, and the like. In the curing of 1), it is presumed that silanols are cured by dehydration condensation. In the curing of 2), it is estimated that silsesquioxane silanol and additive SiH are condensed by dehydrogenation, or SiH is transformed into silanol and then dehydrated and condensed with silsesquioxane silanol. (The arrow on the right side in FIG. 2). In the curing of 3), it is presumed that silanol of silsesquioxane and silanol of additive are dehydrated and condensed to cure (left arrow in FIG. 2).

  The composition for a sealing material of the present invention may contain other additives such as a surfactant and a silane coupling agent in an amount that does not depart from the scope of the present invention.

Since the composition for sealing materials of the present invention contains highly reactive silanol groups, it is preferably stored in a refrigerator. In this case, the following points should be noted.
1) Container Since the reaction by the silanol group is a dehydration reaction, it is important to keep the water concentration in the encapsulant composition constant in order to keep the encapsulant composition stable. Therefore, in general, it is preferable to store in a glass container or a metal container having low water permeability. Since these containers have a large amount of adsorbed water, it is preferable to sufficiently remove the adsorbed water when these containers are used. For example, a resin with little adsorbed water is coated on the inner surface of a glass container.

  In addition, after filling and sealing the sealing material composition in a resin container with little adsorbed water, for example, a polyolefin resin such as PE (polyethylene) or PP (polypropylene), the entire resin container For example, it is preferable to completely seal with an aluminum laminate film. Aluminum laminate film can prevent moisture permeation, so that the moisture adhering to and adsorbing to the container during refrigerated storage and refrigerated transportation of a composition for sealing materials containing a highly reactive compound having a silanol group. Etc. can be excluded. Thereby, the storage stability equivalent to the glass container and metal container which resin-coated the inner surface is securable. Since the resin container is preferably made of a material with little adsorbed water, in addition to the olefin resin, PFA (tetrafluoroethylene / perfluoroalkoxyethylene copolymer), PTFE (polytetrafluoroethylene), TFE (tetrafluoroethylene). ), ETFE (tetrafluoroethylene / ethylene copolymer), FLPE (fluorine-processed high-density polyethylene), and the like can be used. Therefore, a form in which a container made of a polyolefin resin such as PE or PP is filled and sealed with a composition for a sealing material, and then the entire resin container is directly packaged with an aluminum laminate film is most preferable in practice.

2) Others In order to obtain reproducibility such as adhesion between the cured product of the encapsulant composition and the substrate and transparency of the cured product of the encapsulant composition, the adsorbed water of the substrate is used. It is preferable that the composition is sufficiently removed and the base material is coated with the encapsulant composition and cured in a dry environment. Generally, in order to remove adsorbed water from the base material, it is effective to heat the base material to around 200 ° C. In particular, heating in a vacuum is more effective. In addition, as a heating method, there are a method of simply heating in an oven, a method of irradiating heat rays with a powerful lamp such as a halogen lamp, and removing moisture adsorbed on the surface of the substrate and the surrounding material. Can be mentioned.

  When the above-described composition for a sealing material according to the present invention is used for sealing an optical device such as a light emitting diode, a semiconductor laser, or a photodiode, an optical element that is a material to be sealed is mounted on the substrate. The composition for sealing material is supplied so that the optical element is covered, and then the composition for sealing material is cured. Here, as a method of supplying the composition for encapsulant so that the optical element is coated, the viscosity of the composition for encapsulant is adjusted to a predetermined viscosity as necessary, and the composition is placed on the optical element. Examples thereof include a method (potting) for curing the composition for encapsulant by discharging, a method for curing the composition for encapsulant using a predetermined mold after ejection to an optical element, and the like. The conditions for supplying the encapsulant composition are appropriately set in consideration of the type, viscosity, etc. of the organosilicon compound and cyclic compound in the encapsulant composition.

Next, examples performed for clarifying the effects of the present invention will be described.
In this example, Varian Unity 400 is used for NMR spectrum measurement.
For measurement of molecular weight using a spectrometer, GPC (Gel Filtration Chromatography) “High Performance Liquid Chromatography System manufactured by JASCO Corporation” was equipped with “SEC Column (KF-805L) manufactured by Showa Denko KK”. A device was used.

  In this example, the main reagents used were ethyltrimethoxysilane (manufactured by Chisso), 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso), and ricacid MH-700 (new Nippon Rika Co., Ltd.). Made).

Further, in this example, an apparatus having the configuration shown in FIG. 3 was used for light resistance evaluation. That is, in this apparatus, the UV filter 3 is disposed above the glass substrate 1 as a mounting table with a predetermined interval (about 5 mm), and the lamp is disposed above the UV filter 3 with a predetermined interval (about 5 mm). The evaluation sample 2 is placed on the glass substrate 1 and the evaluation sample 2 is irradiated with light from the lamp 4 through the UV filter 3 for evaluation. The light source of the lamp 4 was an ultra-high pressure mercury lamp UVF352S (manufactured by Mitsunaga Electric Co., Ltd.), and the evaluation conditions were an illuminance of 5000 mW / cm ² , a temperature of 100 ° C., and an irradiation time of 24 hours.

Example 1
Synthesis of ethyl silsesquioxane A A 2 L three-neck flask equipped with a reflux tube with a ball, a stir bar, and a thermometer was purged with nitrogen and under a nitrogen stream. To this, 57.6 g of 1N aqueous sodium hydroxide solution and 800 mL of tetrahydrofuran were added, and 240 g (1.6 mol) of ethyltrimethoxysilane was added at room temperature while stirring with mechanical stirring (600 rpm). Next, the reaction system was heated to 60 ° C. using an oil bath with a thermostat and reacted for 6 days. After the reaction, 17.6 dilute hydrochloric acid (57.6 g) was added for neutralization, and then the low boiling point portion was distilled off by a rotary evaporator. Next, 600 mL of diethyl ether was added for extraction, and the aqueous phase was discarded. Then, the organic phase was washed twice with 150 mL of saturated brine, then 60 g of anhydrous magnesium sulfate was added, and the mixture was allowed to stand at room temperature for 15 hours for dehydration. . Insoluble matters such as salts were removed by filtration, and the low boiling point portion was distilled off under reduced pressure to obtain ethyl silsesquioxane A, which is a silsesquioxane compound of Example 1, as a pale yellow opaque high-viscosity liquid compound.

The yield of ethyl silsesquioxane A was 99.5 g (1.23 mol, 76.8%), and the molecular weight was as shown in Table 1 below. In Table 1, Mw is a weight average molecular weight, Mn is a number average molecular weight, and P indicates dispersion. In ethyl silsesquioxane A, since two components of a high molecular weight part and a low molecular weight part were observed in GPC, the area ratio (abundance ratio) between the high molecular weight part and the low molecular weight part determined from the molecular weight shown in Table 1 Also corresponded). ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) was set to −66 ppm (T3 component) and −56 ppm (T2 component). From the measurement results of ²⁹ Si-NMR, it was found that the ratio of the T2 component containing a silanol group (SiOH) was 8 mol%. Table 1 also shows T2 / T3 = 8/92. Here, T2 represents a structure in which two of three oxygen atoms bonded to a silicon atom are bonded to an adjacent silicon atom and the remaining one is silanol. T3 represents a structure in which three of the three oxygen atoms bonded to the silicon atom are bonded to the adjacent silicon atom. Therefore, the value of T2 / T3 corresponds to the amount of silanol, and the larger the amount of T2 / T3, the larger the amount of silanol.

Next, 20 g of ethyl silsesquioxane A was dissolved in 80 parts of toluene, and this was added to 600 mL of acetonitrile with vigorous stirring and reprecipitated. The precipitate was separated by decantation and purified by drying under reduced pressure (ethylsilsesquioxane AP). This material was a colorless solid and the yield was 14.2 g. ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) was set to −66 ppm (T3 component) and −56 ppm (T2 component). From the ²⁹ Si-NMR measurement results, it was found that the ratio of the T2 component containing silanol groups (SiOH) was 6 mol%. Table 1 also shows T2 / T3 = 8/92.

(Example 2)
Synthesis of ethyl silsesquioxane B A 1 L three-necked flask equipped with a reflux tube with a ball, a stirring rod, and a thermometer was purged with nitrogen and under a nitrogen stream. To this, 38.9 g of a 1N aqueous sodium hydroxide solution and 300 mL of tetrahydrofuran were added, and 72 g (0.48 mol) of ethyltrimethoxysilane was added at room temperature while stirring with mechanical stirring (600 rpm). Next, the reaction system was heated to 60 ° C. using an oil bath with a thermostat and reacted for 24 hours. After the reaction, 18.9 dilute hydrochloric acid (38.9 g) was added for neutralization, and then the low boiling point portion was distilled off by a rotary evaporator. Next, 300 mL of diethyl ether was added for extraction, and the aqueous phase was discarded. The organic phase was washed twice with 75 mL of saturated brine, then 30 g of anhydrous magnesium sulfate was added, and the mixture was allowed to stand at room temperature for 15 hours for dehydration. did. Insoluble matter such as salt was removed by filtration, and the low boiling point portion was distilled off under reduced pressure to obtain ethyl silsesquioxane B, which is a silsesquioxane compound of Example 2, as a pale yellow opaque high-viscosity liquid compound.

The yield of ethyl silsesquioxane B was 32.2 g (0.408 moL, 84.9%), and the molecular weight was as shown in Table 1 below. The area ratio between the high molecular weight part and the low molecular weight part determined from the molecular weight shown in Table 1 is also shown. ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) was set to −66 ppm (T3 component) and −56 ppm (T2 component). From the ²⁹ Si-NMR measurement results, it was found that the ratio of T2 component containing silanol group (SiOH) was 17 mol%. T2 / T3 = 17/83 is also shown in Table 1.

Next, 20 g of ethyl silsesquioxane B was dissolved in 80 parts of toluene, and this was added to 600 mL of acetonitrile with vigorous stirring and reprecipitated. The precipitate was separated by decantation and purified by drying under reduced pressure (ethylsilsesquioxane BP). This material was a colorless solid and the yield was 13.8 g. ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) was set to −66 ppm (T3 component) and −56 ppm (T2 component). From the ²⁹ Si-NMR measurement results, it was found that the ratio of the T2 component containing silanol groups (SiOH) was 11 moL%. T1 / T3 = 11/89 is also shown in Table 1.

(Example 3)
Synthesis of ethyl silsesquioxane C A 1 L three-necked flask equipped with a reflux tube with a ball, a stirring rod, and a thermometer was purged with nitrogen and under a nitrogen stream. To this, 86.4 g of 1N aqueous sodium hydroxide solution and 300 mL of tetrahydrofuran were added, and 72 g (0.48 mol) of ethyltrimethoxysilane was added at room temperature while stirring with mechanical stirring (600 rpm). Next, the reaction system was heated to 60 ° C. using an oil bath with a thermostat and reacted for 24 hours. After the reaction, 86.4 g of 1N dilute hydrochloric acid was added for neutralization, and then the low boiling point portion was distilled off by a rotary evaporator. Part of the solution gelled during the distillation. The gel was removed by filtration, and 300 mL of diethyl ether was added to the solution for extraction and the aqueous phase was discarded. The organic phase was washed twice with 75 mL of saturated brine, and then 30 g of anhydrous magnesium sulfate was added for 15 hours at room temperature. And dehydrated. Insoluble matter such as salt was removed by filtration, and the low boiling point portion was distilled off by drying under reduced pressure to obtain ethyl silsesquioxane C, which is a silsesquioxane compound of Example 3, as a colorless opaque high-viscosity liquid compound.

The yield of ethyl silsesquioxane C was 16.6 g (0.210 moL, 43.8%), and the molecular weight was as shown in Table 1 below. The area ratio between the high molecular weight part and the low molecular weight part determined from the molecular weight shown in Table 1 is also shown. ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) was set to −66 ppm (T3 component) and −56 ppm (T2 component). From the ²⁹ Si-NMR measurement results, it was found that the ratio of the T2 component containing silanol groups (SiOH) was 23 mol%. T2 / T3 = 23/77 is also shown in Table 1.

Example 4
Synthesis of ethyl silsesquioxane D A 1 L three-necked flask equipped with a reflux tube with a ball, a stir bar, and a thermometer was purged with nitrogen under a nitrogen stream. To this was added 13.0 g of 1N aqueous sodium hydroxide solution and 600 mL of tetrahydrofuran, and 36 g (0.24 mol) of ethyltrimethoxysilane was added at room temperature while stirring by mechanical stirring (600 rpm). Next, the reaction system was heated to 60 ° C. using an oil bath with a thermostat and reacted for 24 hours. After the reaction, 13.0 g of 1N dilute hydrochloric acid was added for neutralization, and then the low boiling point portion was distilled off by a rotary evaporator. 80 mL of diethyl ether was added thereto for extraction, and the aqueous phase was discarded. The organic phase was washed twice with 30 mL of saturated saline, then 20 g of anhydrous magnesium sulfate was added, and the mixture was allowed to stand at room temperature for 15 hours for dehydration. did. Insoluble matter such as salt was removed by filtration, and the low boiling point portion was distilled off by drying under reduced pressure to obtain ethyl silsesquioxane D, which is a silsesquioxane compound of Example 4, as a colorless and opaque high-viscosity liquid compound.

The yield of ethyl silsesquioxane D was 15.2 g (0.192 moL, 80.2%), and the molecular weight was as shown in Table 1 below. The area ratio between the high molecular weight part and the low molecular weight part determined from the molecular weight shown in Table 1 is also shown. ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) was set to −66 ppm (T3 component) and −56 ppm (T2 component). From the measurement results of ²⁹ Si-NMR, it was found that the ratio of the T2 component containing a silanol group (SiOH) was 12 mol%. T2 / T3 = 12/88 is also shown in Table 1.

(Example 5)
-Synthesis of ethyl silsesquioxane E A 1 L three-necked flask equipped with a reflux tube with a ball, a stirring rod, and a thermometer was purged with nitrogen and under a nitrogen stream. 19.4 g of 1N aqueous sodium hydroxide solution and 600 mL of tetrahydrofuran were added thereto, and 36 g (0.24 mol) of ethyltrimethoxysilane was added at room temperature while stirring (600 rpm) with mechanical stirring. Next, the reaction system was heated to 60 ° C. using an oil bath with a thermostat and reacted for 24 hours. After the reaction, 19.4 g of 1N dilute hydrochloric acid was added for neutralization, and then the low boiling point portion was distilled off by a rotary evaporator. 80 mL of diethyl ether was added thereto for extraction, and the aqueous phase was discarded. The organic phase was washed twice with 30 mL of saturated saline, then 20 g of anhydrous magnesium sulfate was added, and the mixture was allowed to stand at room temperature for 15 hours for dehydration. did. Insoluble matter such as salt was removed by filtration, and the low boiling point portion was distilled off by drying under reduced pressure to obtain ethyl silsesquioxane E, which is a silsesquioxane compound of Example 5, as a colorless opaque high-viscosity liquid compound.

The yield of ethyl silsesquioxane E was 14.8 g (0.187 mol, 78.1%), and the molecular weight was as shown in Table 1 below. The area ratio between the high molecular weight part and the low molecular weight part determined from the molecular weight shown in Table 1 is also shown. ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) was set to −66 ppm (T3 component) and −56 ppm (T2 component). From the ²⁹ Si-NMR measurement results, it was found that the ratio of the T2 component containing silanol groups (SiOH) was 10 mol%. T2 / T3 = 10/90 is also shown in Table 1.

(Example 6)
Synthesis of ethyl silsesquioxane F A 1 L three-necked flask equipped with a reflux tube with a ball, a stir bar, and a thermometer was purged with nitrogen and under a nitrogen stream. To this, 43.2 g of 1N aqueous sodium hydroxide solution and 600 mL of tetrahydrofuran were added, and 36 g (0.24 mol) of ethyltrimethoxysilane was added at room temperature while stirring with mechanical stirring (600 rpm). Next, the reaction system was heated to 60 ° C. using an oil bath with a thermostat and reacted for 24 hours. After the reaction, 43.2 g of 1N dilute hydrochloric acid was added for neutralization, and then the low boiling point portion was distilled off by a rotary evaporator. 80 mL of diethyl ether was added thereto for extraction, and the aqueous phase was discarded. The organic phase was washed twice with 30 mL of saturated saline, then 20 g of anhydrous magnesium sulfate was added, and the mixture was allowed to stand at room temperature for 15 hours for dehydration. did. Insoluble matter such as salt was removed by filtration, and the low boiling point portion was distilled off by drying under reduced pressure to obtain ethyl silsesquioxane F, which is a silsesquioxane compound of Example 6, as a colorless and opaque high-viscosity liquid compound.

The yield of ethyl silsesquioxane F was 16.2 g (0.205 moL, 85.4%), and the molecular weight was as shown in Table 1 below. The area ratio between the high molecular weight part and the low molecular weight part determined from the molecular weight shown in Table 1 is also shown. ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) was set to −66 ppm (T3 component) and −56 ppm (T2 component). From the ²⁹ Si-NMR measurement results, it was found that the ratio of the T2 component containing silanol groups (SiOH) was 27 mol%. T2 / T3 = 27/73 is also shown in Table 1.

Each of the compounds of Examples 1 to 6 was dried and then molded according to the following procedure.
First, a 25 μm thick polyimide film was hot-pressed at a temperature of 220 ° C. for 5 minutes using an aluminum mold previously provided with a recess having a diameter of 26 mm and a depth of 1 mm, whereby an inner diameter of 25 mm and a depth of about 1 mm. A mold for melt molding was prepared. Actual molding was performed using the mold and a hot press heater. Place a suitable amount of ethyl-substituted Tn precipitate on the mold, place it on a hot press heated to 200 ° C in advance, and surround the mold with an insulating wall made of aluminum foil (about 10 mm high). The upper heater of the hot press machine was lowered to a position where it touches the aluminum wall lightly and left as it was. This standing period is the molding time. Specific molding conditions were a temperature of 200 ° C. and a molding time of 20 hours. In the molding process, since there was foaming due to the condensation reaction of silanol groups, the heater was appropriately raised and the foam was crushed with a spatula or the like. After a predetermined molding time, the sample collected from the hot press was allowed to cool together with the mold, lowered to room temperature, and then removed from the mold to complete the molding. Thus, the colorless and transparent molded object of Example 1- Example 6 was produced.

(Example 7)
-Synthesis of phenylethylsilsesquioxane A 1 L three-necked flask equipped with a reflux tube with a ball, a stir bar, and a thermometer was purged with nitrogen under a nitrogen stream. To this, 51.8 g of 1N sodium hydroxide aqueous solution and 600 mL of tetrahydrofuran were added, and while stirring by mechanical stirring (600 rpm), 72.0 g (480 mmol) of ethyltrimethoxysilane and 95.0 g (480 mmol) of phenyltrimethoxysilane at room temperature. Was added. Next, the reaction system was heated to 60 ° C. using an oil bath with a thermostat and reacted for 24 hours. After the reaction, 51.8 g of 1N dilute hydrochloric acid was added for neutralization, and then the low boiling point portion was distilled off by a rotary evaporator. Next, 300 mL of diethyl ether was added for extraction, and the aqueous phase was discarded. The organic phase was washed twice with 50 mL of saturated brine, then 20 g of anhydrous magnesium sulfate was added, and the mixture was allowed to stand at room temperature for 6 hours or more. did. Insoluble matter such as salt was removed by filtration, and the low boiling point portion was distilled off by drying under reduced pressure to obtain 100 g of the silsesquioxane compound of Example 7.

¹ H-NMR (deuterated chloroform, tetramethylsilane internal standard) of this compound is 0.0 to 1.1 (bm, 4.9H), 6.6 to 8.0 (bm, 5.1), ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) was −80, −69, −65, and −56. From the measurement results of ²⁹ Si-NMR, it was found that the ratio of the T2 component containing a silanol group (SiOH) was 10 mol%.

  Take 2.0 g of the compound synthesized in this way, pour it into a mold with a depth of about 1 mm while heating at 60 ° C., defoam using an aspirator, and then cure by heating in an oven at 250 ° C. for 15 hours. Thus, a colorless and transparent molded article of Example 7 was produced.

(Comparative Example 1)
・ Synthesis of glycidyl-substituted Tn Into a 1 L three-necked flask equipped with a reflux tube with a ball, a stir bar, and a thermometer, 45 g of 1N aqueous sodium hydroxide solution and 500 ml of tetrahydrofuran were added and stirred with mechanical stirring (500 rpm). Then, 113.3 g (480 mmol) of 3-glycidoxypropyltrimethoxysilane was added at room temperature. Next, while stirring these mixtures, the mixture was heated to 60 ° C. using an oil bath with a thermostat and reacted for 3 hours. After the reaction, the reaction mixture was neutralized by adding 45 g of 1N dilute hydrochloric acid, and the low boiling point portion was distilled off by a rotary evaporator. Next, 150 ml of ethyl acetate was added for extraction, the aqueous phase was discarded, and the organic phase was washed twice with 100 ml of saturated brine, and then 20 g of anhydrous magnesium sulfate was added and allowed to stand at room temperature for 6 hours or more for dehydration. did. Insoluble matters such as salt were removed by filtration, and the low boiling point portion was distilled off by purification under reduced pressure, followed by purification to obtain a silsesquioxane compound of Comparative Example 1. This compound was a colorless and viscous solid, and the yield was 66.4 g and the yield was 83%.

¹ H-NMR (deuterated chloroform, tetramethylsilane internal standard) of this compound is 0.6 to 0.9 (m, 2H), 1.6 to 1.9 (m, 2H), 2.5 to 2. 7 (m, 1H), 2.7 to 2.9 (m, 1H), 3.1 to 3.2 (m, 1H), 3.3 to 3.4 (m, 1H), 3.4 to 3.6 (m, 2H), 3.7 to 4.1 (m, 1H), ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) is -68 (T3 component), -58 ( T2 component). From the ²⁹ Si-NMR measurement results, it was found that the ratio of the T2 component containing silanol groups (SiOH) was 17 mol%.

It can be seen that the epoxy group is bound by the three peaks of 2.5 to 2.7 ppm, 2.7 to 2.9 ppm, and 3.1 to 3.2 ppm of the ¹ H-NMR. Therefore, a reactive group other than a silanol group is bonded to this compound.

  2.0 g of the compound thus synthesized was mixed with 2.0 g of MH-700, poured into a mold, heated in an oven at 120 ° C. for 6 hours to be cured, and the molded article of Comparative Example 1 Was made.

  A light resistance test was performed on the molded bodies of Examples 1 to 7 and Comparative Example 1 thus obtained using the above-described apparatus. When taken out after 24 hours, it was found that the molded bodies of Examples 1 to 7 exhibited excellent light resistance without any change in the sample appearance before and after the test. On the other hand, regarding the molded body of Comparative Example 1, it was found that the light irradiation part was severely damaged and completely disintegrated. Moreover, about the molded object of Example 1- Example 7, it was confirmed that the crack has not generate | occur | produced by visual observation. Furthermore, it was confirmed that the surface of the molded body was not sticky by the finger. Thereby, it turned out that thick film shaping | molding is possible.

  The present invention is not limited to the embodiment described above, and can be implemented with various modifications. The numerical values and materials in the above embodiment are not limited to this, and can be changed as appropriate. In addition, various modifications can be made without departing from the scope of the present invention.

(A)-(c) is a figure which shows a silsesquioxane structure. It is a figure for demonstrating hardening of the composition for sealing materials of this invention. It is a figure which shows the apparatus for evaluating light resistance.

Explanation of symbols

1 Glass substrate 2 Evaluation sample 3 UV filter 4 Lamp

Claims (3)

  A composition for a sealing material having a silsesquioxane structure and having a silsesquioxane compound in which a reactive group is only a silanol group, wherein the silsesquioxane structure is an ethyl silsesquioxane structure The composition for sealing materials characterized by including.   The composition for sealing material according to claim 1, wherein the silsesquioxane compound contains an ethyl silsesquioxane structure in an amount of about 10 mol% or more.   An optical element mounted on a substrate; and a sealing material coated on the optical element and formed by curing the composition for sealing material according to claim 1 or 2. Optical device to do.

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