JP5149126B2 - Curable composition for semiconductor encapsulation - Google Patents

Description

  The present invention relates to a curable composition for encapsulating a semiconductor suitably used for encapsulating a light-emitting element used for a display, a backlight light source, illumination, a traffic light, and various indicators, and a light-emitting element sealed using the same. It relates to a lamp that stops.

  Epoxy compounds are cured with various curing agents to give cured products with excellent mechanical properties, moisture resistance, electrical properties, etc., so sealing materials, molding materials, and casting materials for electrical / electronic / optical components It is used in a wide range of fields such as laminated materials, composite materials, adhesives, and powder coatings. Among the above fields, particularly in the field of sealing light emitting elements, high performance with respect to heat resistance and the like has been demanded from the viewpoint of life.

  A light emitting element including an optical semiconductor such as a light emitting diode (LED) is usually sealed with a sealing material because its light emission characteristics are rapidly deteriorated due to moisture in the atmosphere or floating dust when directly in contact with the atmosphere. It has a structure. As a resin constituting a sealing material for sealing such a light emitting element, an epoxy resin such as a bisphenol type epoxy resin or an alicyclic epoxy resin is used because of its high adhesive strength and excellent mechanical durability. (For example, refer to Patent Document 1).

  By the way, in recent years, LEDs have come to be used for applications that require high brightness, such as automotive headlights and lighting, and as a result, heat generated during lighting is used as a sealing material for sealing light emitting elements. In addition to high heat resistance that can withstand an increase in the amount of light, high light resistance that prevents light deterioration associated with higher brightness has been required. However, it is difficult to say that a conventional sealing material made of an epoxy resin has sufficient heat resistance and light resistance, and may not be applicable to applications requiring high brightness such as automotive headlights and lighting. There is a problem.

  In addition, a sealing material made of a conventional epoxy resin has advantages such as high adhesion and low moisture permeability, but has a problem that light resistance to short wavelength light is low and coloring occurs due to light deterioration. is there.

  On the other hand, instead of an epoxy resin, a method is known in which a silicone resin having a high transmittance for light having a short wavelength in the blue to ultraviolet region is used as a sealing material for sealing a light emitting element of an LED (for example, Patent Document 2). reference).

  However, since the silicone resin is generally soft and has surface tackiness, foreign substances are likely to adhere to the surface of the light emitting element, and the light emitting surface may be damaged during sealing. On the other hand, a silicone resin with an increased crosslink density is inferior in mechanical strength of a cured product and has a problem that adhesion to a housing material or the like enclosing a light emitting element becomes insufficient.

  Further, for example, Patent Document 3 discloses a thermosetting composition for sealing a light-emitting element, in which a modified polysiloxane having two or more epoxy groups in one molecule and, if necessary, an epoxy resin are blended. . The thermosetting composition for sealing a light-emitting element disclosed in Patent Document 3 can improve adhesion by blending an epoxy resin. However, the composition containing the modified polysiloxane and the epoxy resin is not compatible with the two components, and sufficient transparency cannot be obtained. The problems such as inferiority are largely left.

Further, for example, Patent Document 4 discloses a thermosetting resin composition in which an imide skeleton having an epoxy group is incorporated into a silicone resin for the purpose of improving heat resistance. However, the composition is easily colored. The compatibility with other resins and the adhesion to the light emitting element are poor, and the heat resistance performance of the skeleton itself cannot be extracted.

Therefore, as a resin that can be used for sealing semiconductors, particularly optical semiconductors (light emitting elements), it has excellent transparency (translucency), heat resistance, light resistance and adhesion, and crack resistance. Things are sought.
JP 2003-277473 A JP 2002-314142 A JP 2004-289102 A JP 2008-13544 A

  In view of the above-mentioned present situation, the present invention has excellent transparency (translucency), excellent heat resistance, light resistance (UV), and adhesion to a housing material, and has rapid solder reflow processes, thermal cycles, and the like. A curable composition for encapsulating a semiconductor, and a lamp using the same, in which a cured product is obtained in which cracks and delamination from an adherend are hardly generated even under various heat changes and a problem such as yellowing does not occur under use conditions. The purpose is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found the present invention. That is, the present invention has the following embodiments [1] to [7].

[1] A curable composition for encapsulating a semiconductor comprising the following components (A) and (B):
(A) Epoxy group-containing organosiloxane compound represented by the following general formula (1), (2) or (3) (B) 5- or 6-membered acid anhydride

（上記式（１）〜（３）中、R¹は水素原子またはメチル基であり、R²は水素原子、メチル基またはフェニル基であり、R³は水素原子またはメチル基であり、R⁴、R⁵は独立に置換もしくは非置換の炭素数１〜１０の一価炭化水素基であり、R⁶、R⁷は独立に置換もしくは非置換の炭素数１〜１０の一価炭化水素基または下記一般式（４）で表される一価炭化水素基であり、R⁸は水素原子、メチル基、エチル基またはフェニル基であり、ｎ、ｑは１以上の整数であり、ｐは0以上の整数であり、ｍは３から６までの整数である。）；

(In the above formulas (1) to (3), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a methyl group or a phenyl group, R ³ is a hydrogen atom or a methyl group, and R ⁴ , R ⁵ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁶ and R ⁷ are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms or It is a monovalent hydrocarbon group represented by the following general formula (4), R ⁸ is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, n and q are integers of 1 or more, and p is 0 or more. And m is an integer from 3 to 6.);

（上記式（４）において、R¹は水素原子またはメチル基であり、R²は水素原子、メチル基またはフェニル基であり、R³は水素原子またはメチル基であり、＊は結合手を示す。）。

(In the above formula (4), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a methyl group or a phenyl group, R ³ is a hydrogen atom or a methyl group, and * represents a bond. .)

  [2] The curable composition for semiconductor encapsulation according to [1], wherein the acid anhydride (B) is a compound represented by the following general formula (5) or (6):

（上記式中R⁹ 、R¹⁰、R¹¹、R¹²はそれぞれ独立に水素原子、塩素原子または置換もしくは非置換の炭素数１〜４の一価炭化水素基であり、R¹³、R¹⁴は独立に水素原子、塩素原子または置換もしくは非置換の炭素数１もしくは２の一価炭化水素基である。）。

(In the above formulas, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a chlorine atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ¹³ and R ¹⁴ are Independently a hydrogen atom, a chlorine atom, or a substituted or unsubstituted monovalent hydrocarbon group having 1 or 2 carbon atoms.

  [3] The semiconductor encapsulation according to [1] or [2], further comprising an epoxy compound having two or more epoxy groups and having an aromatic ring or an alicyclic skeleton, and a curing accelerator. Curable composition.

  [4] The functional group ratio (epoxy group / acid anhydride group) of the epoxy group and the acid anhydride group in the curable composition for semiconductor is 0.6 to 2.0 [1] Thru | or the curable composition for semiconductor sealing in any one of [3].

  [5] Hydrosilyl an organohydrosiloxane compound represented by the following general formula (7), (8) or (9) and a compound containing an epoxy group and an alkenyl group represented by the following general formula (10) The method for producing a curable composition for encapsulating a semiconductor according to any one of [1] to [4], which comprises a step of producing an epoxy group-containing organosiloxane compound by performing a chemical reaction.

（上記式（７）〜（９）中、R⁴、R⁵は独立に置換もしくは非置換の炭素数１〜１０の一価炭化水素基であり、R⁶、R⁷は独立に水素原子または置換もしくは非置換の炭素数１〜１０の一価炭化水素基であり、R⁸は水素原子、メチル基、エチル基またはフェニル基であり、ｎ、ｑは１以上の整数であり、ｐは0以上の整数であり、ｍは３から６までの整数である
。）；

(In the above formulas (7) to (9), R ⁴ and R ⁵ are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ⁶ and R ⁷ are independently hydrogen atoms or A substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁸ is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, n and q are integers of 1 or more, and p is 0 And m is an integer from 3 to 6.);

（上記式（１０）中、R¹は水素原子またはメチル基であり、R²は水素原子、メチル基またはフェニル基であり、R³は水素原子またはメチル基である。）。

(In the above formula (10), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a methyl group or a phenyl group, and R ³ is a hydrogen atom or a methyl group).

  [6] A lamp comprising a substrate, an electrode disposed on the substrate, a light emitting element electrically connected to the electrode, and a sealing material for sealing the light emitting element, the sealing A lamp, wherein the material is a cured product of the curable composition for semiconductor encapsulation according to any one of [1] to [4].

  [7] The lamp according to [6], wherein a phosphor is dispersed in the sealing material.

The hardened | cured material of the curable composition for semiconductor sealing of this invention is excellent in translucency and light resistance (UV) property, and is suitable for sealing uses, such as a light emitting element (LED). In addition, the cured product of the curable composition for semiconductor encapsulation of the present invention is excellent in insulation sealing properties, moisture absorption resistance, and adhesion, so that it is not only a light emitting element but also other electric / electronic / optical components. It is useful in a wide range of fields such as sealing materials, molding materials, casting materials, laminated materials, composite materials, adhesives, and powder coatings.

  Hereinafter, the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications are possible.

[Curable composition for semiconductor encapsulation of the present invention]
The curable composition for semiconductor encapsulation of the present invention (hereinafter also simply referred to as curable composition) is (A) an epoxy group-containing organosiloxane compound represented by the following general formula (1), (2) or (3) And (B) a 5-membered or 6-membered acid anhydride.

上記式（１）〜（３）において、R¹は水素原子またはメチル基であり、R²は水素原子、メチル基またはフェニル基であり、R³は水素原子またはメチル基であり、R⁴、R⁵は独立に置換もしくは非置換の炭素数１〜１０の一価炭化水素基であり、R⁶、R⁷は独立に置換もしくは非置換の炭素数１〜１０の一価炭化水素基または下記一般式（４）で表される一価炭化水素基であり、R⁸は水素原子、メチル基、エチル基またはフェニル基であり、ｎ、ｑは１以上の整数であり、ｐは0以上の整数であり、ｍは３から６までの整数である。

In the above formulas (1) to (3), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a methyl group or a phenyl group, R ³ is a hydrogen atom or a methyl group, R ⁴ , R ⁵ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁶ and R ⁷ are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms or It is a monovalent hydrocarbon group represented by the general formula (4), R ⁸ is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, n and q are integers of 1 or more, and p is 0 or more. M is an integer from 3 to 6.

上記式（４）において、R¹は水素原子またはメチル基であり、R²は水素原子、メチル基またはフェニル基であり、R³は水素原子またはメチル基であり、＊は結合手を示す。

In the above formula (4), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a methyl group or a phenyl group, R ³ is a hydrogen atom or a methyl group, and * represents a bond.

  Examples of the substituent in the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and isobutyl. Group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, benzyl group, 2-phenylethyl group, 3-phenylpropyl group, phenyl group, p- Examples thereof include t-butylphenyl group, p-tolyl group, o-tolyl group, 1-naphthyl group and 2-naphthyl group.

Preferred substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms as R ⁴ and R ⁵ are a methyl group, an ethyl group, an n-propyl group, and a phenyl group.
Preferred substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms as R ⁶ and R ⁷ are a methyl group, an ethyl group, and a phenyl group.

Moreover, although n is an integer greater than or equal to 1, Preferably it is an integer of 1-50, More preferably, it is an integer of 1-5.
Although q is an integer greater than or equal to 1, Preferably it is an integer of 1-30, More preferably, it is an integer of 2-10.

Although p is an integer greater than or equal to 0, Preferably it is an integer of 0-200, More preferably, it is an integer of 1-100.
m is an integer from 3 to 6, but is preferably an integer from 4 to 5.

<Epoxy group-containing organosiloxane compound (A) and production method thereof>
The epoxy group-containing organosiloxane compound (A) represented by the general formula (1), (2) or (3) is an organohydrosiloxane represented by the general formula (7), (8) or (9), respectively. It can be obtained by a hydrosilylation reaction between a compound and a compound containing an epoxy group and an alkenyl group represented by the following general formula (10).

上記式（７）〜（９）において、R⁴、R⁵は独立に置換もしくは非置換の炭素数１〜１０の一価炭化水素基であり、R⁶、R⁷は独立に水素原子または置換もしくは非置換の炭素数１〜１０の一価炭化水素基であり、R⁸は水素原子、メチル基、エチル基またはフェニル基であり、ｎ、ｑは１以上の整数であり、ｐは0以上の整数であり、ｍは３から６までの整数で
ある。

In the above formulas (7) to (9), R ⁴ and R ⁵ are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ⁶ and R ⁷ are independently hydrogen atoms or substituted. Or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁸ is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, n and q are integers of 1 or more, and p is 0 or more. M is an integer from 3 to 6.

In the above formula (10), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a methyl group or a phenyl group, and R ³ is a hydrogen atom or a methyl group.
Examples of substituents in the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferred substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms as R ^{4 to} R ⁷ are those described above. This is the same as described for the compounds of the general formulas (1) to (3) and the monovalent hydrocarbon group represented by the general formula (4).

  Also for m, n, p, and q, preferable numerical values are the same as those described for the compounds of the general formulas (1) to (3).

  Examples of the organohydrosiloxane compound represented by the general formula (7), (8), or (9) include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraethyldisiloxane. Siloxane, 1,1,3,3-tetraphenyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, hydrogenated polydimethylsiloxane at both ends, methylhydrogenpolysiloxane, methylhydrogensiloxane -Linear siloxane compounds such as dimethylsiloxane copolymer; 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraethylcyclotetrasiloxane, 1,3,5,7-tetraphenylcyclotetra Siloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-pen And cyclic siloxane compounds such as phenyl cyclopentasiloxane and the like. The organohydrosiloxane compound may be a mixture of two or more or may be used alone.

  Specifically, as the compound represented by the general formula (10), a reaction product of butadiene and (meth) acrylic acid, crotonic acid, or cinnamic acid is used as a precursor, and regioselective after (meth) allyl esterification. The monoepoxy compound obtained by performing an epoxidation reaction can be mentioned. Examples of such monoepoxy compounds include 3,4-epoxycyclohexane-1-carboxylic acid (meth) allyl ester, 3,4-epoxycyclohexane-1-methyl-1-carboxylic acid (meth) allyl ester, 3,4 -Epoxycyclohexane-6-methyl-1-carboxylic acid (meth) allyl ester, 3,4-epoxycyclohexane-6-phenyl-1-carboxylic acid (meth) allyl ester and the like.

In the hydrosilylation reaction between the organohydrosiloxane compound represented by the general formula (7), (8) or (9) and the compound containing an epoxy group and an alkenyl group represented by the general formula (10), the general formula ( 7) The ratio of the SiH group of the compound represented by (8) or (9) and the alkenyl group of the compound represented by the general formula (10), that is, the ratio of the number of alkenyl groups to SiH groups (alkenyl Group / SiH group) is usually 0.8 or more, preferably 0.98 to 1.5. When this ratio is less than 0.8, other side reactions due to the remaining SiH tend to occur. In addition, when an excessive amount of alkenyl group is used, that is, when the ratio is too large, a large amount of a compound containing an epoxy group and an alkenyl group remains, and an extra operation such as distillation purification is required. There is.

  In addition, an addition reaction catalyst such as a platinum-based catalyst is used in the hydrosilylation reaction. Examples of the catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, a reaction product of chloroplatinic acid and a vinyl group-containing siloxane, and the like. There are platinum-based catalysts. Although there is no restriction | limiting in particular in these catalyst addition amount, 0.0001-0.5 mass% of the mass of a reaction substrate may be sufficient as platinum metal.

  This reaction is usually carried out in the range of room temperature to 200 ° C, but heating to 50 ° C or higher is preferable because the reaction proceeds faster. On the other hand, when the temperature is higher than 150 ° C., side reactions increase, so it is preferable to perform the reaction at 150 ° C. or lower. Although reaction time is not specifically limited, 1 to 20 hours are preferable.

The reaction is carried out in a solvent as necessary. Solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane and octane, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and isobutyl acetate, diisopropyl ether, 1 An ether solvent such as 1,4-dioxane, an alcohol solvent such as isopropanol, or a mixed solvent thereof can be used. The reaction atmosphere may be either air or inert gas, but is preferably inert gas for safety.

  After completion of the hydrosilylation reaction, the reaction mixture is treated by a general method such as water washing or activated carbon treatment to remove the addition reaction catalyst. When a solvent is used, the epoxy group-containing organosiloxane compound (A) is obtained by distilling off under heating and / or reduced pressure.

  In the reaction product after the reaction, an excessively used epoxy monomer (compound represented by the general formula (10)) and a side reaction product remain, so that the shrinkage rate of the curable composition of the present invention and the In order to improve the mechanical properties of the cured product of the composition, it is an effective technique to distill out residual monomers, low boiling point impurities, and low molecular weight oligomers using a thin film evaporator or molecular distillation apparatus.

  The above thin film evaporation apparatus is an apparatus that, after completion of the hydrosilylation reaction, forms a reaction mixture after distilling off the solvent if necessary, and evaporates it under vacuum at a lower temperature without affecting the heat. A falling film type thin film evaporator, a stirring type thin film evaporator, a centrifugal thin film evaporator and the like are known. Generally, this apparatus is operated at a pressure of 0.01 kPa to 10 kPa and a temperature of 50 ° C to 250 ° C.

  The above-mentioned molecular distillation apparatus is designed to keep the liquid film of the reaction liquid on the evaporation surface as thin as possible so that the extremely low vacuum is maintained and extremely quiet evaporation occurs from the evaporation surface, and the distance between the evaporation surface and the condensation surface is the average of the molecules. It is a device that keeps the temperature difference between the evaporation surface and the condensing surface to be as small as possible, and suppresses the return of molecules to the condensing surface as much as possible. Pot molecular distillation device, falling film type A molecular distillation apparatus, a centrifugal molecular distillation apparatus, an experimental centrifugal molecular distillation apparatus, and the like are known. In general, this apparatus is operated at a pressure of 2 kPa or less, usually 0.0001 to 1 kPa, a temperature of 50 ° C. to 250 ° C., and a molecular weight close to 1,000 can be evaporated.

In this way, the epoxy group-containing organosiloxane compound (A) represented by the general formula (1), (2), or (3) can be obtained.
The ratio of the epoxy group-containing siloxane unit in the total siloxane units of the epoxy group-containing organosiloxane compound (A) contained in the curable composition for semiconductor encapsulation of the present invention is 2 to 100%. If it is less than 2%, the curability of the curable composition, the heat resistance of the cured product of the composition, and the adhesion to the LED element or the package material (substrate, lead frame, reflector, etc.) on which the LED element is mounted may be reduced. is there. In addition, when it exceeds 80%, heat-resistant yellowing may deteriorate. Therefore, when importance is attached to this characteristic, the proportion of the epoxy group-containing siloxane unit is preferably 2 to 80%, more preferably 5 to 80%.

  In addition, since the total number of siloxane units in the general formulas (1), (2), and (3) is n + 1, p + q + 2, and m, respectively, the ratio of the epoxy group-containing siloxane units in the total siloxane units is (2 / n + 1). %, (Q / p + q + 2)%, 100%. The values of n, p, and q can be obtained by analysis such as NMR.

Also, after completion of the hydrosilylation reaction, the epoxy equivalent of the reaction mixture and the isolated product is also important. If reaction runaway occurs during hydrosilylation, the hydrosilyl group of the compound represented by the general formula (7), (8) or (9) reacts with the epoxy group of the compound represented by the general formula (10) as a side reaction. In some cases, the epoxy group may be ring-opened, and water is unintentionally mixed into the reaction apparatus or the purification apparatus. As a result, the epoxy group is hydrolyzed and converted into a diol, or a diol produced by this side reaction. When the hydroxyl group inside further reacts with another epoxy group, the epoxy equivalent increases. The measurement of the epoxy equivalent is also important in checking that such an unintended reaction has not occurred, and the epoxy equivalent of the reaction mixture or product is checked, and the value is more than twice the theoretical value. It is better to make sure that it is not.

  The curable composition of the present invention may contain any one of the compounds represented by the general formula (1), (2) or (3) as the epoxy group-containing organosiloxane compound (A) alone. It can also contain multiple types.

<5- or 6-membered acid anhydride (B)>
Examples of the 5-membered or 6-membered ring acid anhydride (B) include derivatives of succinic anhydride, maleic anhydride or glutaric anhydride. Specifically, succinic anhydride, dodecenyl succinic anhydride, maleic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-norbornene -2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride, etc. Examples thereof include alicyclic acid anhydrides, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and other aromatic acid anhydrides, 2,4-diethylglutaric anhydride, and the like.

  In addition, acid dianhydrides such as methylcyclohexene tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydro trimellitate can also be used.

  Among them, the alicyclic acid anhydrides represented by the following general formula (5) or (6) have a 5-membered ring in the acid anhydride portion and are unsaturated like phthalic anhydride or maleic anhydride. Since it does not contain a bond, it is particularly preferable from the viewpoint of the curing rate of the curable composition of the present invention.

上記式中R⁹、R¹⁰、R¹¹、R¹²はそれぞれ独立に水素原子、塩素原子または置換もしくは非
置換の炭素数１〜４の一価炭化水素基であり、R¹³、R¹⁴は独立に水素原子、塩素原子または置換もしくは非置換の炭素数１もしくは２の一価炭化水素基である。

In the above formula, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a chlorine atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ¹³ and R ¹⁴ are independently Are a hydrogen atom, a chlorine atom, or a substituted or unsubstituted monovalent hydrocarbon group having 1 or 2 carbon atoms.

  Examples of the substituent in the substituted or unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, Examples thereof include t-butyl group and 2-methyl-1-propenyl group.

Moreover, a methyl group or an isobutyl group is preferable as a substituted or unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms.
On the other hand, examples of the substituent in the substituted or unsubstituted monovalent hydrocarbon group having 1 or 2 carbon atoms include a methyl group and an ethyl group.

A preferred substituted or unsubstituted monovalent hydrocarbon group having 1 or 2 carbon atoms as R ¹³ and R ¹⁴ is a methyl group.
Specific examples of the compound represented by the general formula (5) or (6) include methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-norbornane-2. , 3-dicarboxylic anhydride.

  Although the compounding quantity of the said acid anhydride (B) is not specifically limited, The functional group ratio (epoxy group / acid anhydride group) with the epoxy group in the curable composition for semiconductor encapsulation is preferably 0.6 to An amount of 2.0, more preferably 0.8 to 1.5 is preferred.

  In addition, the epoxy group in the said functional group ratio is an epoxy group of the epoxy group containing organosiloxane compound (A) contained in the curable composition of this invention, and other than the compound (A) contained as needed below. Refers to the total number of epoxy groups in the epoxy compound. The acid anhydride group in the functional group ratio refers to the total number of acid anhydride groups derived from the acid anhydride (B).

The curable composition for semiconductor encapsulation of the present invention can contain an epoxy compound other than the epoxy group-containing organosiloxane compound (A) as necessary. Such an epoxy compound is not particularly limited as long as it is compatible with the epoxy group-containing organosiloxane compound (A). Specifically, dicyclopentadiene oxide, limonene dioxide, 4-vinylcyclohexene dioxide, (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, di (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexyl) methyl alcohol, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene 1,2-di (3,4-epoxycyclohexane) Carboxylic acid) ester, 3,4-epoxycyclohexanecarboxylic acid allyl, phenylglycidyl ether, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-, m-, p Cresol novolac type epoxy resin, phenol novolak type epoxy resins, polyglycidyl ethers of polyhydric alcohols can be exemplified.

  Among these, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate having two or more epoxy groups and having an aromatic ring or alicyclic skeleton, bisphenol A type epoxy resin, bisphenol F type epoxy resin preferable.

  These may be used alone or in combination of two or more. The content of these epoxy compounds in the curable composition of the present invention is usually 10 to 300 parts by mass, preferably 50 to 200 parts by mass with respect to 100 parts by mass of the epoxy group-containing organosiloxane compound (A). is there.

  The curable composition of the present invention preferably further contains a curing accelerator from the viewpoint of improving the curing rate of the composition. The curing accelerator is not particularly limited, and examples thereof include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; tertiary such as 1,8-diazabicyclo (5,4,0) undecene-7 Amines and salts thereof; Phosphines such as triphenylphosphine and tricyclohexylphosphine; Phosphonium salts such as triphenylphosphonium bromide; Tins such as aminotriazoles, tin octylate and dibutyltin dilaurate, and zincs such as zinc octylate And metal catalysts such as acetylacetonate such as aluminum, chromium, cobalt and zirconium. These hardening accelerators may be used independently and may use 2 or more types together.

  Although the compounding quantity of the said hardening accelerator is not specifically limited, It is 0.01-5 mass parts normally with respect to 100 mass parts of curable compositions. If the amount is less than 0.01 parts by mass, the effect of adding the above-mentioned curing accelerator tends to be not obtained. And light resistance may deteriorate. A more preferable range is 0.05 to 1.5 parts by mass.

  The “curable composition” of “100 parts by mass of the curable composition” as used herein refers to the epoxy group-containing organosiloxane compound (A) and the 5- or 6-membered acid anhydride (B). It refers to an epoxy compound other than the epoxy group-containing organosiloxane compound (A) added as necessary. That is, “100 parts by mass of the cured composition” means that the total amount of these is 100 parts by mass. The following “100 parts by mass of curable composition” has the same meaning.

The curable composition for semiconductor encapsulation of the present invention may contain a coupling agent for imparting adhesion. The coupling agent is not particularly limited. For example, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N- Examples include silane coupling agents such as phenyl-3-aminopropyltrimethoxysilane. These coupling agents may be used independently and 2 or more types may be used together.

  The blending ratio of the coupling agent is usually 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable composition. If the amount is less than 0.1 parts by mass, the effect of the coupling agent may not be sufficiently exhibited. If the amount exceeds 5 parts by mass, the excess coupling agent volatilizes, and the curable composition of the present invention is cured. May cause film loss.

Moreover, the curable composition for semiconductor encapsulation of the present invention may contain an antioxidant in order to improve the heat resistance of the cured product of the composition. The antioxidant is not particularly limited. For example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 4,4 '-Butylidenebis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) Phenolic antioxidants such as triphenyl phosphite, tridecyl phosphite, nonyl diphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene, 9,10-dihydro- Phosphorous antioxidants such as 9-oxa-10-phosphaphenanthrene-10-oxide, dilauryl-3,3′-thiodipropionate, ditridecyl-3,3 '-Thiodipropionate, [4,4'-thiobis (3-methyl-6-tert-butylphenyl)]-bis (
Sulfur-based antioxidants such as alkylthiopropionate) and other antioxidants include metal-based antioxidants such as fullerene, iron, zinc and nickel. These antioxidants may be used alone or in combination of two or more.

  The mixing ratio of the antioxidant is usually 0.001 to 2 parts by mass with respect to 100 parts by mass of the curable composition. When the amount is less than 0.001 part by mass, the effect of blending the antioxidant may not be sufficiently exhibited. When the amount exceeds 2 parts by mass, the antioxidant volatilizes and cures the curable composition of the present invention. In some cases, the film may be reduced, or the cured product may become brittle.

  Further, the curable composition of the present invention may contain fine silica powder, a high molecular weight silicone resin and the like in order to adjust the viscosity. In particular, the silica fine powder not only has a thickening action but also acts as a thixotropic agent, and therefore is an optional component in the fluidity control of the curable composition of the present invention and the curable composition of the present invention described later. It is more preferable because it also has an effect of preventing phosphor sedimentation.

The average particle diameter of the silica fine powder is not particularly limited, but a preferable upper limit is 100 nm. When it exceeds 100 nm, the transparency of the curable composition of the present invention may be lowered.
The silica fine powder preferably has a BET specific surface area in the range of 30 to 500 m ² / g in view of performance. If it is less than 30 m ² / g, the thickening effect and the thixotropic effect may be insufficient, and if it exceeds 500 m ² / g, the silica fine powder tends to be agglomerated and difficult to disperse. .

Examples of such silica fine powder include Aerosil 50 (specific surface area: 50 m ² / g), Aerosil 90 (specific surface area: 90 m ² / g), Aerosil 130 (specific surface area: 130 m ² / g), Aerosil 200 ( Specific surface area: 200 m ² / g), Ae
rosil 300 (specific surface area: 300 m ² / g), Aerosil 380 (specific surface area:
380 m ² / g), Aerosil OX50 (specific surface area: 50 m ² / g), Aerosi
l TT600 (specific surface area: 200 m ² / g), Aerosil R972 (specific surface area: 1
10 m ² / g), Aerosil R974 (specific surface area: 170 m ² / g), Aerosi
l R202 (specific surface area: 100 m ² / g), Aerosil R812 (specific surface area: 26
0 m ² / g), Aerosil R812S (specific surface area: 220 m ² / g), Aerosi
l R805 (specific surface area: 150 m ² / g), RY200 (specific surface area: 100 m ² / g),
RX200 (specific surface area: 140 m ² / g) (all manufactured by Nippon Aerosil Co., Ltd.) and the like.

  The curable composition of the present invention may contain an antifoaming agent, a colorant, a phosphor, a modifying agent, a leveling agent, a light diffusing agent, a thermally conductive filler, a flame retardant, and the like as necessary.

  The curable composition of the present invention can be thermally cured. The conditions for thermosetting are usually heating at 40 to 300 ° C. for 0.5 to 48 hours. This heating may be performed in a plurality of times. In particular, when emphasizing coloring, it is not preferable to cure at an excessively high temperature. Initially, curing proceeds gradually at a low temperature of 80 ° C. or lower, and the temperature rises as the curing proceeds, but the final curing temperature is 200 ° C. Hereinafter, it is better to keep the temperature below 160 ° C.

  The cured product obtained by curing the curable composition for encapsulating a semiconductor according to the present invention containing each of these components has an excellent balance between gas barrier properties and heat-resistant yellowing. Specifically, it is suitable for sealing applications of light emitting elements.

As a semiconductor device obtained when the cured product of the curable composition of the present invention is used as a sealing material for a light emitting element, for example, a lamp can be mentioned.
The lamp has, for example, a substrate, an electrode disposed on the substrate, a light emitting element electrically connected to the electrode, and a sealing material for sealing the light emitting element. It is. The sealing material is a cured product of the curable composition of the present invention. In such a lamp, various known substrates, electrodes, and light emitting elements can be used without limitation. In addition, the lamp can be manufactured by a known method including a method of electrically connecting the electrode and the light emitting element. In the lamp of the present invention, electrodes can be arranged on the lead frame, and the lead frame itself can be used as a substrate.

Further, for the purpose of obtaining light closer to white light, a phosphor that emits light when excited by light emitted from the light emitting element may be dispersed in the sealing material. Specific examples of such a phosphor include the following.
_{(1) (RE 1-x} Sm x) 3 (Al y Ga 1-y) 5 O 12: Ce
However, 0 ≦ x <1, 0 ≦ y ≦ 1, and RE is at least one selected from Y and Gd.
(2) (Y _1-pqr Gd _p Ce _q Sm _r ) ₃ (Al _1-s Ga _S ) ₅ O ₁₂
However, 0 ≦ p ≦ 0.8, 0.003 ≦ q ≦ 0.2, 0.0003 ≦ r ≦ 0.08, 0 ≦ s ≦ 1).
(3) Ca ₁₀ (PO ₄ ) ₆ FCl: Sb, Mn
(4) M ₅ (PO ₄ ) ₃ Cl: Eu (where M is at least one selected from Sr, Ca, Ba, Mg)
(5) BaMg ₂ Al ₁₆ O ₂₇ : Eu
(6) BaMg ₂ Al ₁₆ O ₂₇ : Eu, Mn
(7) 3.5MgO.0.5MgF ₂ .GeO ₂ : Mn
(8) Y ₂ O ₂ S: Eu
(9) Mg ₆ As ₂ O ₁₁ : Mn
(10) Sr ₄ Al ₁₄ O ₂₅ : Eu
(11) (Zn, Cd) S: Cu
(12) SrAl ₂ O ₄ : Eu
(13) Ca ₁₀ (PO ₄ ) ₆ ClBr: Mn, Eu
(14) Zn ₂ GeO ₄ : Mn
(15) Gd ₂ O ₂ : Eu
(16) La ₂ O ₂ S: Eu.

  In order to disperse such a phosphor in the sealing material, for example, the phosphor is vigorously stirred and dispersed in the curable composition with a homogenizer, a planetary mixer, or the like, and then removed with a rotation / revolution hybrid mixer or the like. Just foam.

  Throughout the specification, the epoxy equivalent of the epoxy group-containing organosiloxane compound (A) is measured by the following method. The measurement principle is to determine the amount of hydrochloric acid reacted by reacting hydrochloric acid with an epoxy group and titrating the amount of remaining hydrochloric acid with an alkali to determine the amount of epoxy present in the epoxy group-containing organosiloxane compound (A). It is to calculate.

A sample of 2 to 4 mmol equivalent in which the amount of epoxy groups is less than the amount of hydrochloric acid used for measurement is accurately weighed and placed in a 200 ml stoppered Erlenmeyer flask, and 0.2 M hydrochloric acid-dioxane solution is placed in this container. 25 mL is added and dissolved using a whole pipette and left at room temperature for 30 minutes. Next, add 10 ml of methyl cellosolve while washing the stopper and inner wall of the Erlenmeyer flask, add 4 to 6 drops of 0.1% cresol red-ethanol solution as an indicator, and stir well until the sample is uniform. This is titrated with a 0.1 M potassium hydroxide-ethanol solution, and the end point of neutralization is taken when the blue-violet indicator continues for 30 seconds. The value obtained from the result using the following calculation formula is defined as the epoxy equivalent of the epoxy group-containing organosiloxane compound (A).
Epoxy equivalent (g / eq.) = (10,000 × S) / [(BA) × f]
S: Sample collection amount (g)
A: Amount of 0.1 M potassium hydroxide-ethanol solution used (ml)
B: Amount of 0.1 M potassium hydroxide-ethanol solution used in the blank test (ml)
f: Factor of 0.1M potassium hydroxide-ethanol solution

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Synthesis Example 1]
A 2 L three-necked flask equipped with a thermometer, a dropping funnel, a stirrer, and a Dimroth condenser was installed in an oil bath, and 3,4-epoxycyclohexane-1-carboxylic acid (meth) allyl ester 456.56 (g ), Toluene 314.90 (g), and Pt-VTS (platinum divinyltetramethyldisiloxane complex) catalyst (platinum equivalent 3% isopropyl alcohol solution) 0.0607 (g).

Stirring was started and the internal temperature was adjusted to 40 (° C.). 1,1,3,3-Tetramethyldisiloxane 168.58 (g) was added dropwise over 10 hours while adjusting the internal temperature so as not to exceed 42 ° C. After completion of dropping, the mixture was aged at 40 ° C. for a whole day and night.

  After completion of aging, toluene used as a solvent was distilled off using a rotary evaporator to obtain a crude product 612.34 (g). The product was purified using a molecular distillation apparatus (MS-FL special model, manufactured by Daishin Kogyo Co., Ltd.) to obtain the product 597.28 (g). The epoxy equivalent of the product was 251.4.

The structure of the product was confirmed using NMR and IR. ¹ H-NMR chart, ¹³ C-NMR chart and IR chart are shown in FIGS. 1, 2 and 3, respectively.
As a result of analyzing each observed NMR spectrum, a peak attributed to alicyclic epoxy was observed at 2 (ppm) in the ¹ H-NMR observation result, and similarly from the measurement result of ¹³ C-NMR, 50 ( In the vicinity of ppm), a clear peak derived from the epoxy of epoxycyclohexane was observed.

The results of IR analysis, absorption derived from the alicyclic epoxy 1172Cm ^-1, absorption derived from ester carbonyl 1732 cm ^-1, and characteristic absorption derived from Si-O to 1057cm ^-1 were observed.
From the above analysis results, it was confirmed that the product obtained here was the target compound represented by the following structure.

[Synthesis Example 2]
A 1 L three-necked flask equipped with a thermometer, a dropping funnel, a stirrer, and a Dimroth condenser was installed in an oil bath, and 3,4-epoxycyclohexane-1-carboxylic acid (meth) allyl ester 155.78 (g ), Toluene 108.32 (g), and Pt-VTS (platinum divinyltetramethyldisiloxane complex) catalyst (platinum equivalent 3% isopropyl alcohol solution) 0.0260 (g).

Stirring was started and the internal temperature was adjusted to 60 (° C.). 1,3,5,7-tetramethylcyclotetrasiloxane 51.42 (g) was added dropwise over 5 hours while adjusting the internal temperature so as not to exceed 61 ° C. After completion of the dropwise addition, the mixture was aged at 60 ° C. all day and night, and it was confirmed by GC analysis that the peak of the raw material 1,3,5,7-tetramethylcyclotetrasiloxane had disappeared.

  After completion of aging, toluene used as a solvent was distilled off using a rotary evaporator to obtain a crude product 207.19 (g). The product was purified using a molecular distillation apparatus (MS-FL special model, manufactured by Daishin Kogyo Co., Ltd.) to obtain product 150.10 (g). The epoxy equivalent of the product was 245.5.

The structure of the product was confirmed using NMR and IR. ^{The 1} H-NMR chart, ¹³ C-NMR chart and IR chart are shown in FIGS. 4, 5 and 6, respectively.
As a result of analyzing each observed NMR spectrum, a peak attributed to alicyclic epoxy was observed at 2 (ppm) in the ¹ H-NMR observation result, and similarly from the measurement result of ¹³ C-NMR, 50 ( In the vicinity of ppm), a clear peak derived from the epoxy of epoxycyclohexane was observed.

The results of IR analysis, absorption derived from the alicyclic epoxy 1172Cm ^-1, absorption derived from ester carbonyl 1732 cm ^-1, and characteristic absorption derived from Si-O to 1057cm ^-1 were observed.
From the above analysis results, it was confirmed that the product obtained here was the target compound represented by the following structure.

[Synthesis Example 3]
A 1 L three-necked flask equipped with a thermometer, a dropping funnel, a stirrer, and a Dimroth condenser was installed in an oil bath, and in a nitrogen atmosphere, 3,4-epoxycyclohexane-1-carboxylic acid (meth) allyl ester 213.95 (g ), Toluene 150.32 (g), and Pt-VTS catalyst (3% isopropyl alcohol solution in terms of platinum) 0.0315 (g).

  Stirring was started and the internal temperature was adjusted to 40 (° C.). 1,1,3,3,5,5-Hexamethyltrisiloxane 121.17 (g) was added dropwise over 6 hours while appropriately adjusting the internal temperature to be in the range of 40 ° C to 43 ° C. After completion of dropping, the mixture was aged at 40 ° C. for a whole day and night.

After completion of ripening, the crude product obtained by distilling off toluene using a rotary evaporator was purified using a molecular distillation apparatus (MS-FL special model, manufactured by Otsuka Industries Co., Ltd.). A product 268.10 (g) having the following structure was obtained.

[Synthesis Example 4]
A 1000 mL three-necked flask equipped with a thermometer, a dropping funnel, a stirrer, and a Dimroth condenser was installed in an oil bath, and 3,4-epoxycyclohexane-1-carboxylic acid (meth) allyl ester 150.12 (g ), Toluene 200.59 (g), and Pt-VTS catalyst (platinum equivalent 3% isopropyl alcohol solution) 0.0217 (g) were charged.

Stirring was started and the internal temperature was adjusted to 60 (° C.). 1,3,5,7,9-pentamethylcyclopentasiloxane 48.27 (g) was added dropwise over 2 hours while adjusting the internal temperature so as not to exceed 61 ° C. After completion of dropping, the mixture was aged at 60 ° C. for a whole day and night.

  After completion of the aging, the crude product obtained by distilling off toluene was purified using a molecular distillation apparatus (MS-FL special model, manufactured by Daishin Kogyo Co., Ltd.), and the product 170.58 (shown by the following structure) g) was obtained.

[Example 1]
27.6 g of the compound synthesized in Synthesis Example 1 and HN-5500E (manufactured by Shin Nippon Rika Co., Ltd., 7: 3 mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride) 16.8 g (epoxy group /
Acid anhydride group ≒ 1.1) and U-CAT5003 (San Apro Co., Ltd.) tetra-substituted phosphonium
Bromide (structure not disclosed)) 0.22g was mixed well, degassed, and then TPX (poly-4-methylpentene-1) resin petri dish was used for 60 ℃ -30min, 100 ℃ -2hr, 150 ℃ Mold curing was performed by cast polymerization over -2 hr.

[Example 2]
Instead of the compound synthesized in Synthesis Example 1, the compound synthesized in Synthesis Example 2 was used in combination with the functional group ratio of Example 1 (epoxy group / acid anhydride group≈1.1) 27.0 g. Molding hardening was performed by the same operation as in Example 1.

[Comparative Example 1]
Instead of the compound synthesized in Synthesis Example 1, 1,3-bis (3-glycidyloxypropyl) -1,1,3,3-
Mold curing was carried out in the same manner as in Example 1 except that 19.9 g of tetramethyldisiloxane was used in combination with the functional group ratio of Example 1 (epoxy group / acid anhydride group≈1.1). It was.

[Comparative Example 2]
Instead of the compound synthesized in Synthesis Example 1, hydrogenated bisphenol-A type liquid epoxy resin (
jER-YX-8000 (manufactured by Japan Epoxy Resins Co., Ltd.) was used in the same manner as in Example except that 22.2 g (epoxy group / acid anhydride group≈1.1) was used in combination with the functional group ratio of Example 1 Mold hardening was performed by the same operation as 1.

[Comparative Example 3]
In place of the compound synthesized in Synthesis Example 1, an alicyclic epoxy resin (Celoxide 2021P, manufactured by Daicel Chemical Industries, Ltd.) is used in a functional group ratio (epoxy group / acid anhydride group≈1.1) 14.3 g Except for the use, molding and curing were performed in the same manner as in Example 1.

  The following measurements were performed using the cured plates obtained in Examples 1 and 2 and Comparative Examples 1 to 3.

<Measurement of color difference>
Using a colorimetric color difference meter (Nippon Denshoku Industries Co., Ltd., ZE-2000), a 50 mm square sample with a thickness of 3 mm was used under the following measurement conditions. Conversion to numerical values of each color system was performed by the colorimetric color difference meter main body, and data of the color system was obtained.

Measurement mode: Transmission Number of measurements: n = 3
Output data: L (lightness), a (redness), b (yellowness).

<Measurement of light transmittance>
Using a turbidimeter (Nippon Denshoku Industries Co., Ltd., NDH2000), using a sample of 50 mm square and 3 mm thickness, haze value, total light transmittance (Tt), diffuse transmittance (Dfs), parallel light transmittance (Pt) was determined.

<Measurement of volumetric shrinkage>
The density before and after curing of the curable composition was measured to calculate the volume shrinkage. The liquid before curing was measured with a vibration type digital density meter DM-4500 (manufactured by Anton Paar Co., Ltd.).
The cured product was measured by Archimedes method.

<Measurement of bending strength>
In accordance with JIS-K6911, measurement was performed using a strip-shaped sample (width 10 mm × length 100 mm × thickness 3 mm) (unit: MPa).

<UV resistance test>
According to JIS-K5400, UV irradiation was performed at 60 ° C using a mercury lamp type fading test machine No.518 (manufactured by Yasuda Seiki Co., Ltd., 365nm, 400W high pressure mercury lamp). ΔE was calculated from the values a, b.

  The obtained results are summarized in Table 1.

実施例１，２は比較例１〜３と同等の光線透過率を有し、かつ黄色度を表すｂ値およびΔＥ値が比較例１〜３に比べて小さい。これより本発明の硬化性組成物の硬化物は黄味が小さくかつ耐光（ＵＶ）性が良好であり、光学特性に優れていることがわかる。また、実施例１，２は比較例１〜３に比べて硬化収縮率が小さく、機械的特性も良好である。したがって、本発明の硬化性組成物は半導体封止用、殊に光半導体封止用として有用である。

Examples 1 and 2 have light transmittance equivalent to that of Comparative Examples 1 to 3, and the b value and ΔE value representing yellowness are smaller than those of Comparative Examples 1 to 3. From this, it can be seen that the cured product of the curable composition of the present invention has small yellowishness, good light resistance (UV) resistance, and excellent optical properties. In addition, Examples 1 and 2 have a smaller curing shrinkage rate and better mechanical properties than Comparative Examples 1 to 3. Therefore, the curable composition of the present invention is useful for semiconductor encapsulation, particularly for optical semiconductor encapsulation.

FIG. 1 shows a ¹ H-NMR chart of the product of Synthesis Example 1. FIG. 2 shows a ¹³ C-NMR chart of the product of Synthesis Example 1. FIG. 3 shows an IR chart of the product of Synthesis Example 1. FIG. 4 shows a ¹ H-NMR chart of the product of Synthesis Example 2. FIG. 5 shows a ¹³ C-NMR chart of the product of Synthesis Example 2. FIG. 6 shows an IR chart of the product of Synthesis Example 2.

Claims (7)

A curable composition for encapsulating a semiconductor comprising the following components (A) and (B):
(A) Epoxy group-containing organosiloxane compound represented by the following general formula (1), (2) or (3) (B) 5- or 6-membered acid anhydride

(In the above formulas (1) to (3), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a methyl group or a phenyl group, R ³ is a hydrogen atom or a methyl group, and R ⁴ , R ⁵ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁶ and R ⁷ are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms or It is a monovalent hydrocarbon group represented by the following general formula (4), R ⁸ is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, n and q are integers of 1 or more, and p is 0 or more. And m is an integer from 3 to 6.);

(In the above formula (4), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a methyl group or a phenyl group, R ³ is a hydrogen atom or a methyl group, and * represents a bond. .) The curable composition for semiconductor encapsulation according to claim 1, wherein the acid anhydride (B) is a compound represented by the following general formula (5) or (6):

(In the above formulas, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a chlorine atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ¹³ and R ¹⁴ are Independently a hydrogen atom, a chlorine atom, or a substituted or unsubstituted monovalent hydrocarbon group having 1 or 2 carbon atoms. An epoxy compound having two or more epoxy groups and having an aromatic ring or an alicyclic skeleton;
The curable composition for semiconductor encapsulation according to claim 1, further comprising a curing accelerator. The functional group ratio (epoxy group / acid anhydride group) between the epoxy group and the acid anhydride group in the curable composition for encapsulating a semiconductor is 0.6 to 2.0. The curable composition for semiconductor encapsulation according to any one of 1 to 3. Hydrosilylation reaction of an organohydrosiloxane compound represented by the following general formula (7), (8) or (9) and an epoxy group and alkenyl group-containing compound represented by the following general formula (10) The manufacturing method of the curable composition for semiconductor sealing in any one of the Claims 1 thru | or 4 characterized by including the process of manufacturing an epoxy-group-containing organosiloxane compound by this:

(In the above formulas (7) to (9), R ⁴ and R ⁵ are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ⁶ and R ⁷ are independently hydrogen atoms or A substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁸ is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, n and q are integers of 1 or more, and p is 0 And m is an integer from 3 to 6.);

(In the above formula (10), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a methyl group or a phenyl group, and R ³ is a hydrogen atom or a methyl group). A substrate,
An electrode disposed on the substrate;
A light emitting element electrically connected to the electrode;
A lamp comprising a sealing material for sealing the light emitting element,
The lamp | ramp characterized by the said sealing material being the hardened | cured material of the curable composition for semiconductor sealing in any one of Claims 1 thru | or 4.   The lamp according to claim 6, wherein a phosphor is dispersed in the sealing material.

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