TW201525073A - Polysiloxane - Google Patents

Abstract

A curable composition, which is containing: polysiloxane (A) having alkenyl group and adhesive group, polysiloxane (B) having per molecule at least two hydrogen atom that is combined with silicon atom (but polysiloxane (A)), and catalyst (C) for the hydrosilylation reaction. It is characterized by the content ratio of polysiloxane (A) is 40 to 90 mass% when total content of all ingredients of the curable composition is 100 mass%. The curable composition of the present invention is capable of forming a hydrosilyl series polysiloxane composition which is having both high adhesiveness for substrates or metal lines, and high Initial luminance of LED etc. Therefore, an optical semiconductor device which is obtained by covering the semiconductor light-emitting element by the cured article obtained from the curable composition, the initial luminance is high, even in the case of undergoing heat cycle, the cured article is having high adhesiveness and could not separate of package and the like.

Description

Polyoxane

The present invention relates to a curable composition, a cured product, an optical semiconductor device, and a polyoxyalkylene.

A hydrogenation-reaction-hardening polyoxane composition (hereinafter also referred to as a hydrosilyl-based polyoxane composition) used for a sealing agent for a semiconductor light-emitting device (LED), etc., is required to improve the LED package. Adhesive technology.

As a technique for improving the adhesion of a hydroxane-based polyoxane composition, a technique of adding an adhesion promoter such as an epoxy group-containing polyoxyalkylene to a hydroquinone-based polyoxane composition is known.

Patent Document 1 describes a hydroquinane-based polyoxoxane composition containing 0.01 to 50 parts by weight of an alkenyl group as an adhesion promoter, based on 100 parts by weight of the organopolyoxane as a main component. An epoxy group of polyoxyalkylene.

Patent Document 2 describes a hydroquinane-based polyoxoxane composition containing 0.01 to 20 parts by weight as an adhesive per 100 parts by weight of an organic polyfluorene-containing resin containing an alkenyl group and a phenyl group as a main component. An epoxy group-containing polyoxyalkylene of a promoter.

Patent Document 3 describes a hydroquinane-based polyoxoxane composition containing 0.01 to 10 parts by mass as an adhesion promoter, based on 100 parts by mass of the alkenyl group-containing organopolyoxane component as a main component. An epoxy group-containing polyoxyalkylene having an alkenyl group.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2007-327019

Patent Document 2 Japanese Patent Laid-Open Publication No. 2007-008996

Patent Document 3 Japanese Patent Laid-Open Publication No. 2010-229402

In order to improve the adhesion of the substrate, the metal wiring, and the sealant, it is necessary to increase the epoxy group content of the epoxy group-containing polyoxyalkylene as an adhesion promoter. However, in the case where a large amount of such an adhesion promoter is used, there is a possibility that the brightness is lowered.

An object of the present invention is to provide a curable composition which is a hydroquinane-based polyoxane composition and which can form a cured product which can achieve adhesion to a substrate or a metal wiring or the like.

The present invention is a curable composition which is a polyoxyalkylene containing a polyoxyalkylene (A) having an alkenyl group and an adhesion group, and having at least two hydrogen atoms bonded to a halogen atom per molecule ( B) (except for the polyoxane (A)) and the curable composition of the catalyst for hydrogenation reaction (C), characterized in that the content of all the components contained in the curable composition is combined When the content is 100% by mass, the content of the polyoxyalkylene (A) is from 40 to 90% by mass.

In the above curable composition, when the number of all Si atoms contained in the polyoxyalkylene (A) is 100 mol%, it is preferred that the polyoxyalkylene (A) has an alkenyl group content of 3 to 50. The content of the molar group is preferably 0.01 to 10 mol%.

In the curable composition, the adhesion group is preferably a group having an epoxy group.

In the above curable composition, the polyoxyalkylene (A) is preferably represented by the following chemical formula: (R ^Vi R ¹ ₂ SiO _1/2 ) _a (R ¹ ₃ SiO _1/2 ) _b (R ^Vi R ¹ SiO _2/2 ) _c (R ^Ep R ¹ SiO _2/2 ) _d (R ¹ ₂ SiO _2/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _h (XO _1/2 ) _i

(wherein R ^Vi represents a group having an alkenyl group. R ^Ep represents a group having an epoxy group. R ¹ each independently represents a monovalent hydrocarbon group (except for a group having an alkenyl group). X represents a hydrogen atom. Or an alkyl group having 1 to 3 carbon atoms. a represents an integer of 0 or more, b represents an integer of 0 or more, c represents an integer of 0 or more, d represents an integer of 1 or more, e represents an integer of 0 or more, and f represents 0 or more. An integer, h represents an integer of 0 or more, i represents an integer of 0 or more, and a+c is an integer of 1 or more).

In the aforementioned hardenable composition, the polyoxyalkylene (A) has an aryl group, and when the number of all Si atoms contained in the polyoxyalkylene (A) is 100 mol%, the polyoxyalkylene (A) The content of the aryl group contained in the ) is preferably from 30 to 120 mol%.

Another invention is a cured product characterized by being obtained from the aforementioned curable composition.

Further, another invention is an optical semiconductor device characterized by having a semiconductor light-emitting element and the aforementioned cured material covering the semiconductor light-emitting element.

Further, another invention is a polyoxyalkylene which is represented by the following chemical formula: (R ^Vi R ¹ ₂ SiO _1/2 ) _a (R ¹ ₃ SiO _1/2 ) _b (R ^Vi R ¹ SiO _2/2 ) _c (R ^Ep R ¹ SiO _2/2 ) _d (R ¹ ₂ SiO _2/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _h (XO _1/2 ) _i

(wherein R ^Vi represents a group having an alkenyl group. R ^Ep represents a group having an epoxy group. R ¹ each independently represents a monovalent hydrocarbon group (except for a group having an alkenyl group). X represents a hydrogen atom. Or an alkyl group having 1 to 3 carbon atoms. a represents an integer of 0 or more, b represents an integer of 0 or more, c represents an integer of 0 or more, d represents an integer of 1 or more, e represents an integer of 0 or more, and f represents 0 or more. An integer, h represents an integer of 0 or more, i represents an integer of 0 or more, and a+c is an integer of 1 or more).

The curable composition of the present invention is a hydroquinane-based polyoxane composition, which can form a cured product which can achieve adhesion to a substrate or a metal wiring or the like.

Therefore, the optical semiconductor device obtained by covering the semiconductor light-emitting device with the cured product obtained from the curable composition is an optical semiconductor device excellent in reliability.

1‧‧‧Optical semiconductor device

2‧‧‧Semiconductor light-emitting elements

3‧‧‧ reflector

4‧‧‧ Sealing material

5‧‧‧ particles

6‧‧‧Electrode

7‧‧‧Wire

Fig. 1 is a schematic view showing a specific example of an optical semiconductor device.

[Formation of the Invention] <Sclerosing composition>

The curable composition of the present invention is a polysiloxane having a polyoxyalkylene (A) having an alkenyl group and an adhesion group, and a hydrogen atom having at least two hydrogen atoms bonded to a ruthenium atom per molecule (B) (a) the curable composition of the catalyst for hydrogenation reaction (C), and the total content of all the components contained in the curable composition is 100% by mass. In the case, the content of the polyoxyalkylene (A) is from 40 to 90% by mass.

In the present invention, "polyoxyalkylene oxide" means a siloxane having a molecular skeleton in which two or more siloxane units (Si-O) are bonded.

[polyoxane (A)]

The polyoxyalkylene (A) is a polyoxyalkylene having an alkenyl group and an adhesion group. The polyoxyalkylene (A) is a main component of the composition, and is hardened by hydrogenation reaction with polyhydrazine (B) to form a main body of the cured product. Further, since the polyoxyalkylene (A) has an adhesive group, it also has a function of improving the adhesion between the cured product and the LED package.

Examples of the alkenyl group of the polyoxyalkylene (A) include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a heptenyl group, and a hexenyl group. Cyclohexenyl and the like. Preferred among these are vinyl, allyl and hexenyl.

The content of the alkenyl group in the polyoxyalkylene (A) is preferably from 3 to 50 mol%, more preferably from 3 to 50 mol%, based on the total number of Si atoms contained in the polyoxyalkylene (A). 5 to 40% by mole, and further preferably 10 to 30% by mole. When the content of the alkenyl group is within the above range, the hydrazine hydrogenation reaction of the polyoxyalkylene oxide (A) and the polyoxyalkylene oxide (B) is initiated in a suitable range, and a cured product having high strength can be obtained.

The adhesion-bonding group is a group having adhesion to a metal or an organic resin which is a material such as a substrate of a semiconductor device or the like.

Examples of the adhesion group which the polysiloxane (A) has include a group having an epoxy group, a sulfinylene group, an isocyanate group, a triallyl isocyanate group, and the like.

In this case, it is difficult to prevent the hydrazine hydrogenation reaction caused by the curing of the curable composition, and to form a cured product having high adhesion to the substrate and the metal wiring, etc., and a group having an epoxy group is preferable. .

Examples of the group having an epoxy group include a glycidoxy group such as a glycidoxy group or a 3-glycidoxypropyl group, and a 3,4-epoxycyclopentyl group. An epoxycycloalkyl group such as 4-epoxycyclohexyl, 2-(3,4-epoxycyclopentyl)ethyl or 2-(3,4-epoxycyclohexyl)ethyl. Specific examples of the group having an epoxy group include groups represented by the following structural formulae (1) to (4). When the group having an epoxy group is such a group, the cured product can be formed in a millimeter order.

[R ² in the structural formula (1) represents a methylene group or a divalent linear alkyl group having 2 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. ]

[In the structural formula (2), R ³ represents a methylene group or a divalent linear alkyl group having 2 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. ]

[R ⁴ in the structural formula (3) represents a methylene group or a divalent linear alkyl group having 2 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. ]

[R ⁵ in the structural formula (4) represents a methylene group or a divalent linear alkyl group having 2 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. ]

Specific examples of the group represented by the structural formula (1) include 2-(3,4-epoxycyclohexyl)ethyl and the like.

Specific examples of the group represented by the structural formula (2) include a glycidyl group and the like.

Specific examples of the group represented by the structural formula (3) include 3-glycidoxypropyl group and the like.

Specific examples of the group represented by the structural formula (4) include 2-(4-methyl-3,4-epoxycyclohexyl)ethyl and the like.

The content of the adhesion group in the polyoxyalkylene (A) is preferably 0.01 to 10 mol% when the number of all Si atoms contained in the polyoxyalkylene (A) is 100 mol%. More preferably, it is 0.05 to 5 mol%, and further preferably 0.05 to 3 mol%. When the content of the adhesion group is within the above range, a cured film having high adhesion and high brightness between the cured product obtained from the composition and the LED package can be obtained.

The content of the polysiloxane (A) contained in the curable composition of the present invention is preferably from 40 to 90% by mass based on 100% by mass of the total of all the components contained in the composition. 50 to 85% by mass, more preferably 65 to 85% by mass.

In the conventional hydroquinone-based polyoxane composition, in order to improve the adhesiveness, a polyoxynitane as a main component is added in an amount of about 0.01 to 20% by mass based on the total amount of the composition as an adhesion promoter. Alkoxy polyoxyalkylene. On the other hand, in the curable composition of the present invention, the polyoxyalkylene oxide (A) containing an epoxy group-containing polyoxyalkylene is used as a main component, and the content thereof is 40 to 90% by mass as described above. When the content of the polyoxyalkylene (A) is in the above range, the cured product obtained from the composition has high adhesion to a substrate or a metal wiring, and the LED or the like is maintained when used as a sealing material such as an LED. High initial brightness.

Further, the polyoxyalkylene (A) preferably has an aryl group. When the polyoxyalkylene (A) has an aryl group, it is used as an LED sealing material. High brightness characteristics are obtained. When the number of all Si atoms contained in the polyoxyalkylene (A) is 100 mol%, the content of the aryl group contained in the polyoxyalkylene (A) is preferably from 30 to 120 mol%, more preferably Good is 50~110%, and further better is 70~100%. When the content of the aryl group is in the range of 30 to 120 mol%, a cured film having high luminance and high refractive index can be obtained from the composition. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of polyoxyalkylene (A) is preferably in the range of from 100 to 50,000, more preferably in the range of from 500 to 5,000. When the weight average molecular weight of the polyoxyalkylene (A) is within the above range, it is easy to handle when the sealing material is produced using the composition, and the cured product obtained from the composition has sufficient material strength as an optical semiconductor sealing material and characteristic.

Examples of the polyoxyalkylene oxide (A) include polyoxyalkylene represented by the following chemical formula (1): [Chemical Formula (1)] (R ^Vi R ¹ ₂ SiO _1/2 ) _a (R ¹ ₃ SiO _{1/2 b} (R ^Vi R ¹ SiO _2/2 ) _c (R ^Ad R ¹ SiO _2/2 ) _d (R ¹ ₂ SiO _2/2 ) _e (R ¹ SiO _3/2 ) _f (R ^Ad SiO _3/2 ) _g (SiO _4/2 ) _h (XO _1/2 ) _i

(wherein R ^Vi represents a group having an alkenyl group. R ^Ad represents a group having an adhesion group. R ¹ each independently represents a monovalent hydrocarbon group (except for a group having an alkenyl group). X represents hydrogen An atom or an alkyl group having 1 to 3 carbon atoms. a represents an integer of 0 or more, b represents an integer of 0 or more, c represents an integer of 0 or more, d represents an integer of 0 or more, e represents an integer of 0 or more, and f represents 0. The above integer, g represents an integer of 0 or more, h represents an integer of 0 or more, i represents an integer of 0 or more, and a+c is an integer of 1 or more. d+g is an integer of 1 or more).

With respect to the total of a, b, c, d, e, f, g, h, and i, the ratio of a is preferably 0% or more and 60% or less, more preferably 5% or more, when the total amount is 100%. 40% or less. The ratio of b is preferably 0% or more and 50% or less, more preferably 0% or more and 20% or less. The ratio of c is preferably 0% or more and 30% or less, more preferably 0% or more and 20% or less. The ratio of d is preferably 0% or more and 10% or less, more preferably 0% or more and 5% or less. The ratio of e is preferably 0% or more and 50% or less, more preferably 0% or more and 30% or less. The ratio of f is preferably 20% or more and 90% or less, more preferably 40% or more and 80% or less. The ratio of g is preferably 0% or more and 10% or less, more preferably 0% or more and 5% or less. The ratio of h is preferably 0% or more and 50% or less, more preferably 0% or more and 30% or less. The ratio of i is preferably 0% or more and 10% or less, more preferably 0% or more and 5% or less. And the ratio of a+c is greater than 0%, and the ratio of d+g is greater than 0%.

Among the polyoxanes represented by the chemical formula (1), a polyoxyalkylene represented by the following chemical formula (2) is used to form a cured product which can achieve a high degree of adhesion to a substrate, a metal wiring or the like, and a cured product. good.

[Chemical Formula (2)] (R ^Vi R ¹ ₂ SiO _1/2 ) _a (R ¹ ₃ SiO _1/2 ) _b (R ^Vi R ¹ SiO _2/2 ) _c (R ^Ep R ¹ SiO _2/2 ) _d (R ¹ ₂ SiO _2/2 ) _e (R ¹ SiO _3/2 ) _f (SiO ₄ / ₂ ) _h (XO _1/2 ) _i

(wherein R ^Vi represents a group having an alkenyl group. R ^Ep represents a group having an epoxy group. R ¹ each independently represents a monovalent hydrocarbon group (except for a group having an alkenyl group). X represents a hydrogen atom. Or an alkyl group having 1 to 3 carbon atoms. a represents an integer of 0 or more, b represents an integer of 0 or more, c represents an integer of 0 or more, d represents an integer of 1 or more, e represents an integer of 0 or more, and f represents 0 or more. An integer, h represents an integer of 0 or more, i represents an integer of 0 or more, and a+c is an integer of 1 or more)

As the group having an alkenyl group, the same group as the above-mentioned group having an alkenyl group is exemplified. As the group having an adhesion group, a group having the same group as the above-mentioned adhesion group is exemplified. As the group having an epoxy group, the same group as the above-mentioned group having an epoxy group is exemplified. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a heptyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group; a benzyl group and a benzene group; An aralkyl group such as ethyl; a substituted alkyl group such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or nonafluorobutylethyl.

For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A well-known method described in, for example, Japanese Laid-Open Patent Publication No. 2010- 059427, and the like, for example, a method of co-hydrolyzing a chlorodecane or an alkoxy decane derived from each unit, through an alkali metal catalyst A method of equalizing a cohydrolyzate, etc.

By using such a polyoxyalkylene, the cured product obtained from the curable composition of the present invention can obtain the necessary strength, exhibits adhesion to a metal or organic resin film, and is also obtained when used as an LED sealing material. High brightness characteristics.

[polyoxane (B)]

The polyoxyalkylene (B) is a polyoxyalkylene having at least two hydrogen atoms bonded to a halogen atom per molecule (except for polyoxyalkylene (A)). That is, the polyoxyalkylene (B) has at least two Si-H groups (hydroalkylene groups) per molecule. The polyoxyalkylene (B) is a crosslinking agent for polyoxyalkylene (A), which is formed by hydrogenation with hydrazine of polyoxyalkylene (A) to form a cured product.

The polyoxyalkylene (B) is a polysiloxane having at least two hydrogen atoms bonded to a ruthenium atom per molecule, which is used as a crosslinking agent in a conventional hydrooxane-based polyoxane composition. It can be used without particular limitation.

Specific examples of the polyoxyalkylene oxide (B) include organic hydrogenated polyoxyalkylenes described in Patent Documents 1 to 3.

The polyoxyalkylene (B) can be, for example, alkoxydecane such as phenyltrimethoxydecane or diphenyldimethoxydecane and 1,1,3,3-tetramethyldioxane by a known method. Obtained by reacting a hydrogenated oxane such as an alkane.

As the content of the polyoxyalkylene (B) in the curable composition of the present invention, the amount of hydrogen atoms bonded to the ruthenium atom in the polysiloxane (B) relative to the amount of the alkenyl group in the polyoxyalkylene (A) The molar amount is preferably from 0.1 to 5, more preferably from 0.5 to 2, still more preferably from 0.7 to 1.4. If the content of the polyoxyalkylene (B) is within the above range, the hardening of the composition proceeds sufficiently, and the obtained cured product can obtain sufficient heat resistance.

[矽 Catalyst for hydrogenation reaction (C)]

The catalyst for hydrogenation reaction (C) is a catalyst for hydrogenation of a polyfluorene oxide (A) with a polyoxane (B).

The catalyst for the hydrogenation reaction (C) is not particularly limited as long as it is a catalyst used in the conventional hydroquinone-based polyoxane composition as a catalyst for the hydrogenation reaction.

Specific examples of the catalyst (C) for the hydrogenation reaction include a platinum catalyst, a rhodium catalyst, and a palladium catalyst. From the viewpoint of promoting the hardening of the present composition, among these, a platinum-based catalyst is preferred. Examples of the platinum-based catalyst include a platinum-alkenyl alkane complex and the like. Examples of the alkenyl alkane include 1,3-divinyl-1,1,3,3-tetramethyldioxane and 1,3,5,7-tetramethyl-1,3. 5,7-tetravinylcyclotetraoxane, and the like. In particular, from the viewpoint of the stability of the complex, 1,3-divinyl-1,1,3,3-tetramethyldioxane is preferred.

The catalyst (C) for the hydrogenation reaction of the hydrazine in the curable composition of the present invention is an amount which is practically carried out by hydrogenating a polyfluorene oxide (A) and a polyoxyalkylene (B).

The curable composition of the present invention is limited to the object of the present invention, and may contain, in addition to the above-mentioned components, particulate vermiculite such as gas phase ceria or quartz powder, or inorganic filler such as titanium oxide or zinc oxide. Retardant such as cyclo-tetramethyltetravinyltetraoxane; diphenyl bis(dimethylvinyl decyloxy) decane, phenyl tris(dimethyl vinyl decyloxy) decane, etc. Thinner; pigment; flame retardant; heat resistant agent; antioxidant.

The curable composition of the present invention can be prepared by uniformly mixing the above components by a known method such as a mixer.

The viscosity of the curable composition of the present invention at 25 ° C is preferably from 1 to 1,000,000 mPa. s, more preferably 10~10000mPa. s. When the viscosity is within this range, the handleability of the composition is improved.

The curable composition of the present invention can be prepared as a single dose, or can be divided into two doses, and used in combination at the time of use. A hardening inhibitor such as acetylene alcohol may also be added in small amounts as needed.

<hardened matter>

A cured product can be obtained by hardening the curable composition of the present invention. When the semiconductor element is sealed and hardened by the curable composition of the present invention, a cured product of the sealing material can be obtained.

The method of curing the curable composition of the present invention is, for example, a method in which the curable composition is applied onto a substrate and then heated at 100 to 180 ° C for 1 to 13 hours.

As described above, the cured product obtained by curing the curable composition of the present invention has high adhesion to a substrate or a metal wiring or the like, and achieves high initial brightness of an LED or the like.

<Optical semiconductor device>

An optical semiconductor device according to the present invention includes a semiconductor light emitting element and the cured material covering the semiconductor light emitting element. The optical semiconductor device of the present invention is obtained by coating the curable composition on a semiconductor light-emitting device and curing the composition. The method of hardening the curable composition is as described above.

Examples of the optical semiconductor device include an LED (Light Emitting Diode) and an LD (Laser Diode).

Fig. 1 is a schematic view showing a specific example of an optical semiconductor device of the present invention. The optical semiconductor device 1 includes an electrode 6, a semiconductor light-emitting element 2 that is electrically connected to the electrode 6 and is electrically connected to the electrode 6 by a wire 7, and a reflector 3 that is disposed to house the semiconductor light-emitting device 2, and is filled in the reflector. 3 is a sealing material 4 that seals the semiconductor light emitting element 2. The sealing material 4 is obtained by hardening the curable composition of the present invention. Particles 5 such as vermiculite, phosphor, and the like are dispersed in the sealing material 4.

As described above, the sealing material obtained by curing the curable composition of the present invention has a strong adhesion to the organic resin film of the material of the reflector or the metal of the electrode material, and is even subjected to thermal cycling. In this case, the sealing material will not peel off from the LED package. Further, the sealing material maintains a high initial luminance of the LED or the like. That is, it is possible to achieve both high adhesion and high initial brightness.

[Examples] (1) Synthesis of polyoxyalkylene oxide (1-1) Synthesis of polyoxyalkylene oxide [Synthesis Example 1] Synthesis of polyoxyalkylene (AR1)

Into a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, charged and mixed 1,3-divinyl-1,1,3,3-tetramethyldioxane 82g, phenyltrimethoxy 525 g of decane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were heated under reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer of the toluene solution was washed with water. 0.4 g of potassium hydroxide was added to the toluene solution layer after washing with water, and the water was refluxed while removing water from the water separation tube. After the removal of water was completed, the mixture was concentrated to a solid concentration of 75 mass%, and refluxed for 5 hours. After cooling, the mixture was neutralized with 0.6 g of acetic acid, and the toluene solution obtained by filtration was washed with water. Thereafter, concentration under reduced pressure was carried out to obtain polyoxyalkylene (AR1). The polystyrene-equivalent weight average molecular weight of (AR1) was measured by gel permeation chromatography to be 2,000. The chemical formula of polyoxyalkylene (AR1) is (ViMe ₂ SiO _1/2 ) ₂₅ (PhSiO _3/2 ) ₇₅ (Vi represents a vinyl group, Me represents a methyl group, and Ph represents a phenyl group. The subscript number represents mol%).

[Synthesis Example 2] Synthesis of polyoxyalkylene (A1)

Into a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, 82 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane, 143 g of water, and benzene were charged and mixed. 521 g of methoxymethoxysilane, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were heated under reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer of the toluene solution was washed with water. To the toluene solution layer after washing with water, 4 g of 3-glycidoxypropylmethyldimethoxydecane and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Next, the methanol was distilled off, and excess water was removed by azeotropic dehydration. It was then heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After removing water, the toluene was distilled off under reduced pressure to obtain a molar ratio of 25 mol% of an alkenyl group and 0.5 mol% of an epoxy group (the number of all Si atoms contained in the polysiloxane was 100 mol). %) polyoxyalkylene (A1). The polystyrene-equivalent weight average molecular weight of (A1) was determined by gel permeation chromatography to be 2,000. The chemical formula of polyoxyalkylene (A1) is (ViMe ₂ SiO _1/2 ) ₂₅ (PhSiO _3/2 ) _74.5 (EpMeSiO _2/2 ) _0.5 (Vi represents vinyl, Me represents methyl, Ph represents phenyl, Ep Represents a glycidoxypropyl group. The subscript number indicates mol%). When the number of all Si atoms contained in the polyoxyalkylene (A1) is 100 mol%, the content ratio of the alkenyl group is 25 mol%, the content ratio of the epoxy group is 0.5 mol%, and the content ratio of the aryl group is 74.5 mol%.

[Synthesis Example 3] Synthesis of polyoxyalkylene (A2)

Into a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, charged and mixed 1,3-divinyl-1,1,3,3-tetramethyldioxane 82g, phenyltrimethoxy 518 g of decane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were heated under reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer of the toluene solution was washed with water. To the toluene solution layer after washing with water, 8 g of 3-glycidoxypropylmethyldimethoxydecane and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Next, the methanol was distilled off, and excess water was removed by azeotropic dehydration. It was then heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After removing water, the toluene was distilled off under reduced pressure to obtain a molar ratio of 25 mol% of an alkenyl group and 1 mol% of an epoxy group (the number of all Si atoms contained in the polyoxyalkylene was 100 mol. %) polyoxyalkylene (A2). The polystyrene-equivalent weight average molecular weight of (A2) was measured by gel permeation chromatography to be 2,000. The chemical formula of polyoxyalkylene (A2) is (ViMe ₂ SiO _1/2 ) ₂₅ (PhSiO _3/2 ) ₇₄ (EpMeSiO _2/2 ) ₁ (Vi represents vinyl, Me represents methyl, Ph represents phenyl, Ep Represents a glycidoxypropyl group. The subscript number indicates mol%). When the number of all Si atoms contained in the polyoxyalkylene (A2) is 100 mol%, the content ratio of the alkenyl group is 25 mol%, the content ratio of the epoxy group is 1 mol%, and the content ratio of the aryl group is 74 mol. %.

[Synthesis Example 4] Synthesis of polyoxyalkylene (A3)

Into a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, charged and mixed 1,3-divinyl-1,1,3,3-tetramethyldioxane 82g, phenyltrimethoxy 511 g of decane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid, and 500 g of toluene were heated under reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer of the toluene solution was washed with water. To the toluene solution layer after water washing, 16 g of 3-glycidoxypropylmethyldimethoxydecane and 30 g of potassium hydroxide and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Next, the methanol was distilled off, and excess water was removed by azeotropic dehydration. It was then heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After removing water, the toluene was distilled off under reduced pressure to concentrate to obtain an alkenyl group of 25 mol% and an epoxy group of 2 mol% (the number of all Si atoms contained in the polyoxyalkylene was 100 mol%). Polyoxyalkylene (A3). The polystyrene-equivalent weight average molecular weight of (A3) was determined by gel permeation chromatography to be 2,000. The chemical formula of polyoxyalkylene (A3) is (ViMe ₂ SiO _1/2 ) ₂₅ (PhSiO _3/2 ) ₇₃ (EpMeSiO _2/2 ) ₂ (Vi represents vinyl, Me represents methyl, Ph represents phenyl, Ep Represents a glycidoxypropyl group. The subscript number indicates mol%). When the number of all Si atoms contained in the polyoxyalkylene (A3) is 100 mol%, the content ratio of the alkenyl group is 25 mol%, the content ratio of the epoxy group is 2 mol%, and the content ratio of the aryl group is 73 mol. %.

[Synthesis Example 5] Synthesis of polyoxyalkylene (A4)

In a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, 1,3-divinyl-1,1,3,3-tetramethyldioxane 49g and phenyltrimethoxy were charged and mixed. 442 g of decane, 85 g of dimethyldimethoxydecane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were heated under reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer of the toluene solution was washed with water. To the toluene solution layer after washing with water, 8 g of 3-glycidoxypropylmethyldimethoxydecane and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Next, the methanol was distilled off, and excess water was removed by azeotropic dehydration. It was then heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After removing water, the toluene was distilled off under reduced pressure to concentrate to obtain an alkenyl group of 15 mol% and an epoxy group of 1 mol% (the number of all Si atoms contained in the polyoxyalkylene was 100 mol%). Polyoxyalkylene (A4). The polystyrene-equivalent weight average molecular weight of (A4) was measured by gel permeation chromatography to be 1800. The chemical formula of polyoxyalkylene (A4) is (ViMe ₂ SiO _1/2 ) ₁₅ (PhSiO _3/2 ) ₆₄ (Me ₂ SiO _2/2 ) ₂₀ (EpMeSiO _2/2 ) ₁ (Vi represents vinyl, Me represents Methyl, Ph represents phenyl, and Ep represents glycidoxypropyl. The subscript number indicates mol%). When the number of all Si atoms contained in the polyoxyalkylene (A4) is 100 mol%, the content of the alkenyl group is 15 mol%, the content of the epoxy group is 1 mol%, and the content of the aryl group is 64 mol. %.

[Synthesis Example 6] Synthesis of polyoxyalkylene (A5)

Into a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, charged and mixed 1,3-divinyl-1,1,3,3-tetramethyldioxane 82g, phenyltrimethoxy 525 g of decane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were heated under reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer of the toluene solution was washed with water. To the toluene solution layer after water washing, 314 g of 3-glycidoxypropylmethyldimethoxydecane, 130 g of water, and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Next, the methanol was distilled off, and excess water was removed by azeotropic dehydration. It was then heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After removing water, the toluene was distilled off under reduced pressure to concentrate to obtain an alkenyl group of 25 mol% and an epoxy group of 40 mol% (the number of all Si atoms contained in the polyoxyalkylene was 100 mol%). Polyoxyalkylene (A5). The polystyrene-equivalent weight average molecular weight of (A5) was measured by gel permeation chromatography to be 1600. The chemical formula of polyoxyalkylene (A5) is (ViMe ₂ SiO _1/2 ) ₂₅ (PhSiO _3/2 ) ₇₅ (EpMeSiO _2/2 ) ₄₀ (Vi represents vinyl, Me represents methyl, Ph represents phenyl, Ep Represents a glycidoxypropyl group. The subscript number indicates mol%). When the number of all Si atoms contained in the polyoxyalkylene (A5) is 100 mol%, the content of the alkenyl group is 25 mol%, the content of the epoxy group is 40 mol%, and the content of the aryl group is 75 mol. %.

[Synthesis Example 7] Synthesis of polyoxyalkylene (A6)

Into a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, 33 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane and phenyltrimethoxy 442 g of decane, 85 g of dimethyldimethoxydecane, 43 g of diphenyldimethoxydecane, 155 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were heated under reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer of the toluene solution was washed with water. To the toluene solution layer after water washing, 8 g of 3-glycidoxypropylmethyldimethoxydecane and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Next, the methanol was distilled off, and excess water was removed by azeotropic dehydration. It was then heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After removing water, the toluene was distilled off under reduced pressure to concentrate to obtain an alkenyl group of 10 mol% and an epoxy group of 1 mol% (the number of all Si atoms contained in the polyoxyalkylene was 100 mol. %) polyoxyalkylene (A6). The polystyrene-equivalent weight average molecular weight of (A6) was measured by gel permeation chromatography to be 1800. The chemical formula of polyoxyalkylene (A6) is (ViMe ₂ SiO _1/2 ) ₁₀ (PhSiO _3/2 ) ₆₄ (Ph ₂ SiO _2/2 ) ₅ (Me ₂ SiO _2/2 ) ₂₀ (EpMeSiO _2/2 ) ₁ (Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, and Ep represents a glycidoxypropyl group. The subscript number indicates mol%). When the number of all Si atoms contained in the polyoxyalkylene (A6) is 100 mol%, the content of the alkenyl group is 10 mol%, the content of the epoxy group is 1 mol%, and the content of the aryl group is 74 mol. %.

[Synthesis Example 8] Synthesis of polyoxyalkylene (B1)

195 g of phenyltrimethoxydecane and 0.2 g of trifluoromethanesulfonic acid were placed and mixed in a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, and 13 g of water was dropped into the mixture for 15 minutes while stirring. After the end, it was heated to reflux for 1 hour. After cooling to room temperature, 119 g of 1,1,3,3-tetramethyldioxane was added, and 88 g of acetic acid was added dropwise while stirring. After the completion of the dropwise addition, the mixture was stirred and heated to 50 ° C for 3 hours. After cooling to room temperature, toluene and water were added, and the mixture was thoroughly mixed and allowed to stand, and the aqueous layer was separated and removed. After washing the upper layer of the toluene solution with water, it was concentrated under reduced pressure to obtain methylphenyl hydrogenated polyoxane (B1). The chemical formula of polyoxyalkylene (B1) is (HMe ₂ SiO _1/2 ) ₆₀ (PhSiO _3/2 ) ₄₀ (Me represents a methyl group, and Ph represents a phenyl group. The subscript number indicates mol%).

[Synthesis Example 9] Synthesis of polyoxyalkylene (B2)

In a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, 220 g of diphenyldimethoxydecane and 0.6 g of trifluoromethanesulfonic acid were added and mixed, and 1,1,3,3-tetramethyl was added. 147 g of bisoxane was added dropwise to 108 g of acetic acid over 30 minutes while stirring. After the completion of the dropwise addition, the mixture was stirred and heated to 50 ° C and reacted for 3 hours. After cooling to room temperature, toluene and water were added, and the mixture was thoroughly mixed and allowed to stand, and the aqueous layer was separated and removed. The upper layer of the toluene solution was washed with water three times, and then concentrated under reduced pressure to obtain diphenylhydrogenated polyoxane (B2). The chemical formula of polyoxyalkylene (B2) is (HMe ₂ SiO _1/2 ) ₅₀ (Ph ₂ SiO _2/2 ) ₅₀ (Me represents a methyl group, and Ph represents a phenyl group. The subscript number indicates mol%).

(1-2) Weight average molecular weight

The weight average molecular weight (Mw) of the obtained polyoxyalkylene was measured by gel permeation chromatography (GPC) under the following conditions, and was determined as a value in terms of polystyrene.

Device: HLC-8120C (manufactured by TOSOH CORPORATION)

Column: TSK-gel MultiporeHXL-M (manufactured by TOSOH CORPORATION)

Developer: THF, flow rate 0.5 mL/min, loading amount 5.0%, 100 μL (1-3) alkenyl group, epoxy group and aryl group content ratio, and chemical formula of polyoxyalkylene.

The content ratio of the alkenyl group, the epoxy group, and the aryl group contained in the obtained polyoxyalkylene (100 mol% based on the total number of Si atoms contained in the polyoxyalkylene), and polyoxyalkylene oxide The chemical formula was calculated by ²⁹ Si NMR and ¹³ C NMR.

(2) Preparation of hardenable composition [Examples 1 to 5 and Comparative Examples 1 and 2]

The components shown in the following Table 1 were mixed at a normal pressure of 95 ° C under the normal amount shown in Table 1, and the curable compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were obtained. The numerical values in Table 1 represent parts by mass. Further, the details of the respective components in Table 1 are as follows.

C1: a complex of platinum with 1,3-divinyl-1,1,3,3-tetramethyldioxane (amount of platinum metal 4% by mass)

D1: cyclo-tetramethyltetravinyltetraoxane

D2: diphenyl bis(dimethylvinyl decyloxy) decane

D3: phenyl tris(dimethylvinyl nonyloxy) decane

(3) Evaluation of hardenable composition

The curable compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated by the following methods (3-1) to (3-6). The evaluation results are shown in Table 2.

(3-1) Viscosity

The viscosity of the curable composition was measured at 25 ° C using an E-type viscometer.

(3-2) hardness

A frame of 2 mm thick was placed on a flat plate of TEFLON (registered trademark), and the curable composition was applied to the height of the frame, and a cured product of 50 mm × 50 mm × 1 mm was produced by heating in a hot air circulating oven at 150 ° C for 5 hours. The hardness of the cured product was measured by a D-type hardness meter defined in JIS K6253.

(3-3) Refractive index

The cured product for hardness measurement was prepared using a curable composition, and the refractive index at 25 ° C was measured using a Model 2010 total reflection refractometer manufactured by Metricon Corporation. Further, the measurement wavelength was 408 nm.

(3-4) Light transmittance change

A circular (diameter: 2 cm, thickness: 1 mm) frame was placed on a 1 mm quartz plate, and the frame was filled with a curable composition, and a cured product prepared by heating in a hot air circulating oven at 150 ° C for 5 hours was measured ( Light path length 1.0 mm) Light transmittance at a wavelength of 460 nm at 25 °C. Next, in order to investigate the degree of coloring after the accelerated deterioration test, the light transmittance at a wavelength of 460 nm at 25 ° C after heat-aging the cured product in a heat cycle oven at 150 ° C for 1,000 hours was measured in the same manner. The ratio of the light transmittance after heat aging to the light transmittance before heat aging was evaluated by the following criteria.

A: The aforementioned ratio is 98% or more

B: The aforementioned ratio is 90% or more and less than 98%.

C: the aforementioned ratio is less than 90%

(3-5) subsequent strength

A curable composition was applied to the bottom surface of an aluminum cylinder having a diameter of 5 mm and a height of 5 mm and adhered to various test panels, and placed in a hot air circulating oven at 150 ° C for 1 hour to obtain aluminum having a diameter of 5 mm and a height of 5 mm by using a hardenable composition. The test piece in which the cylinder is in close contact with the test panel. The series-4000 PXY manufactured by Dage Co., Ltd. was used as a measuring device, and the aluminum cylinders adhered to the various test panels were peeled off at a rate of 50 μm/sec. The load at this time was measured as the adhesion strength, and evaluated according to the following criteria.

A: The strength is more than 10kg.

B: The strength is more than 5kg and less than 10kg.

C: Then the strength is less than 5kg

(3-6) heat resistance

The curable composition was applied to quartz glass so that the dried film thickness was 1 mm, and then dried and cured at 100 ° C for 1 hour, and then dried and cured at 150 ° C for 5 hours to prepare a cured product. The cured product was stored at 150 ° C for 500 hours, and the appearance of the cured product after storage was visually observed, and the heat resistance was evaluated by the following criteria.

(Color changes)

A: No color change

B: slightly yellowed

C: Obviously yellowed

(3-7) Total radiation beam measurement (brightness evaluation)

The curable composition was applied to a surface mount type of an optical semiconductor (a topview type including a portion including the photo-semiconductor 2, the electrode 6, the lead 7 and the reflector 3 of FIG. 1), and heated at 150 ° C for 1 hour. A sample for evaluation was prepared.

The radiation beam measurement of the sample for evaluation described above was carried out using a total radiation beam measuring device (ultraviolet, visible, near-infrared spectroscopic spectrometer MCPD-3700, Φ 300 mm integrating sphere (hemispherical integrating sphere)). The radiation beam of the sample for evaluation described above was calculated in %, and the ratio of the initial radiation beam measured by energization of the package before application of the sealing material to light emission was evaluated by the following criteria.

A: The aforementioned ratio is 110% or more

B: The aforementioned ratio is less than 110%, 100% or more

C: The aforementioned ratio is less than 100%

As is apparent from the results shown in Table 2, in Comparative Examples 1 and 2 in which the polyoxyalkylene (A) containing an epoxy group-containing polyoxyalkylene was used as an adhesion promoter, a polyepoxide having a large epoxy group was used. In Comparative Example 1 of oxyalkylene (A5), the total radiation beam had a low luminance, and Comparative Example 2 using a polyoxyalkylene oxide (A3) having a small epoxy group, the strength was lowered, and high luminance and high adhesion were not achieved. . On the other hand, in Examples 1 to 5 in which the polyoxyalkylene (A) containing an epoxy group-containing polyoxyalkylene was used as a main component, the total radiation beam and the subsequent strength were both high, achieving both high brightness and high brightness. Adhesive.

[Industrial availability]

The curable composition of the present invention is transparent, and has a low light transmittance and high adhesion even when placed in a high-temperature gas atmosphere, and is used for an optical semiconductor element and an optical semiconductor component. Sealant, adhesive, potting agent Agent), protective coating agent, underfill, and the like. The cured product of the present invention has a small reduction in light transmittance even when exposed to a high temperature, and has a feature that the light transmittance is reduced in a manufacturing step under high temperature conditions and the long-term reliability is excellent. In the case of an optical semiconductor device such as a high-luminance light-emitting device, the cured product of the present invention has an optical component for use as a high-luminance light source because the total radiation beam is high.

Claims (4)

A polyoxyalkylene which is represented by the following chemical formula: (R ^Vi R ¹ ₂ SiO _1/2 ) _a (R ¹ ₃ SiO _1/2 ) _b (R ^Vi R ¹ SiO _2/2 ) _c (R ^Ep R ¹ SiO _2/2 ) _d (R ¹ ₂ SiO _2/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _h (XO _1/2 ) _i wherein R ^Vi represents an alkenyl group a group; R ^Ep represents a group having an epoxy group; R ¹ each independently represents a monovalent hydrocarbon group, wherein a group having an alkenyl group is excluded; and X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; a represents an integer of 0 or more, b represents an integer of 0 or more, c represents an integer of 0 or more, d represents an integer of 1 or more, e represents an integer of 0 or more, f represents an integer of 0 or more, and h represents an integer of 0 or more; i An integer of 0 or more is represented; wherein a+c is an integer of 1 or more. The polyoxyalkylene of claim 1, wherein the amount of the alkenyl group in the polyoxyalkylene is from 3 to 50 mol%, when the number of all Si atoms contained in the polyoxyalkylene is 100 mol%, The content of the adhesion group is 0.01 to 10 mol%. The polyoxyalkylene as claimed in claim 1, wherein the polyoxyalkylene has an aryl group and is contained in the polyoxane when the number of all Si atoms contained in the polyoxyalkylene is 100 mol%. The content of the aryl group is 30 to 120 mol%. The polyoxyalkylene of claim 1, wherein in the chemical formula, the ratio of f is 20 to 90% with respect to the total of a, b, c, d, e, f, g, h, and i.