TWI542637B - Curable silicone resin composition for led devices - Google Patents

Description

Hardenable siloxane resin composition for LED components

The present invention relates to a hardenable siloxane resin composition, and more particularly to an encapsulant formulation using the curable siloxane resin composition in an LED component, and also to a composition comprising using the hardenable siloxane resin LED components for encapsulation formulations.

In the prior art, U.S. Patent No. 7,615,387 B2, issued Nov. 10, 2009, the disclosure of which is incorporated herein by reference in its entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire all An episulfide resin composition which is hardenable by an addition reaction, which can be used as an encapsulant material for an LED, is disclosed. The naphthenic composition disclosed in the above U.S. Patent includes: a network vinyl polysiloxane having a straight chain segment in its structure; a hydrogen-containing polyoxyl An organohydrogen polysiloxane; an addition reaction catalyst; and an organohydrogen polysiloxane compound containing an epoxy group or/and an alkoxy group.

In terms of synthesis, the polyoxyalkylene disclosed in US '387 utilizes a straight chain of dichloropolysiloxane (ClMe ₂ SiC ₂ H ₄ SiMe ₂ O(SiPh ₂ O) ₂ (SiMe ₂ O). ₂ SiMe ₂ C ₂ H ₄ SiMe ₂ Cl) is hydrolyzed and condensed with chlorodecane to prepare a network vinyl polysiloxane having a straight chain segment in the structure; The polyoxyalkylene disclosed in the present invention utilizes a straight-chain dichloropolysiloxane (Cl(Me ₂ SiO) ₁₇ Cl) to be hydrolyzed and condensed together with chlorosilane to prepare a linear segment in the structure ( Straight chain segment) of a network vinyl polysiloxane. The chlorodecane may be, for example, phenyltrichlorosilane, vinyldimethylchlorosilane, dimethyldichlorosilane or the like.

The oxoxane compositions disclosed in the above-mentioned U.S. Patent Nos. 3,387 and 4,104, although having the properties of adhesion, temperature difference impact resistance, etc., are quite complicated in the synthesis process, and are used such as chlorodecane. The reactants of chloranil (oxygen) alkane such as chloropolyoxyalkylene are also unstable and difficult to store.

As a package material for a light emitting diode (LED), it is required to be able to withstand the thermal shock between the LED on and off after 24 hours of treatment at a temperature of 85 ° C and a relative humidity of 85% (thermo) Shock) does not crack, and the resin portion and the metal portion of the lead frame must have good adhesion.

The siloxane-based material is generally used for forming a crosslinked oxime-based resin composition, and has properties such as weather resistance, heat resistance, crack resistance, elongation, hardness, etc., and can be applied to various uses, such as in recent years. The polyoxyalkylene-based composition is used as an encapsulating material, in particular, for encapsulating an LED element, but the known polyoxyalkylene encapsulating adhesive formulation is prone to deterioration, hardening, and cracking in a high-temperature, high-humidity environment. .

Accordingly, the present invention provides a hardenable decane resin composition comprising mainly an alkenyl group-containing high cross-linking network polyoxy siloxane and an alkenyl group-containing low cross-linking network polyoxy siloxane, which is simplified a process for synthesizing a linear polyoxane; it can be synthesized by an alkoxysilane reaction, which is more stable than the chlorosilane used in the prior art; moreover, the hardenable siloxane resin composition is particularly suitable for use in The package component of the LED component has excellent anti-cracking property and high temperature and high humidity resistance.

It is an object of the present invention to provide a hardenable siloxane resin composition comprising:

(A) Alkenyl-containing high cross-linking network polyoxyalkylene having an overall average composition as shown in Structural Formula (1):

R ¹ _n SiO _(4-n)/2 (1)

Wherein R ¹ is, independently of each other, a monovalent hydrocarbon group, an alkoxy group, a hydroxyl group having no substituent or a substituent, n is a positive number, and 0≦n≦2, wherein the alkenyl group accounts for 0.1 to 80 of all R ¹ groups. Mohr%, and R ¹ SiO _3/2 and/or SiO _4/2 units account for 55 mol% or more of (A);

(B) an alkenyl group-containing low cross-linking network polyoxyalkylene having an overall average composition as shown in the structural formula (2):

R ² _n SiO _(4-n)/2 (2)

Wherein R ² is, independently of each other, a monovalent hydrocarbon group, an alkoxy group or a hydroxyl group which is unsubstituted or substituted, n is a positive number, and 0≦n≦2, wherein the alkenyl group accounts for 0.1 to 80 of all R ² groups. Mohr%, and R ² SiO _3/2 and/or SiO _4/2 units account for 37 mol% or less of (B);

(C) Polyoxane containing hydrazine hydrogen bond, the overall average composition of which is shown in structural formula (3):

R ³ _a H _b SiO _(4-ab)/2 (3)

Wherein R ³ is, independently of each other, a monovalent hydrocarbon group, an alkoxy group, a hydroxyl group having no substituent or a substituent, but excluding an alkenyl group, and at least 30 mol% of all R ³ groups are a methyl group, and a is a positive number. And 0.7≦a≦2.1, b is a positive number, and 0.001≦b≦1.0, wherein 0.8≦a+b≦3.0, at least two hydrogen atoms in each molecule are bonded to the ruthenium;

(D) A catalyst for the hydroquinonelation reaction.

The hardenable siloxane resin composition of the present invention optionally further comprises (E) a hydrazine-containing hydrogen-bonded polyoxyalkylene having an epoxy group.

Another object of the present invention is to provide an encapsulant formulation for an LED component, characterized in that the encapsulant formulation comprises the hardenable siloxane resin composition of the present invention as an encapsulating material.

Still another object of the present invention is to provide an LED component comprising an encapsulant material, characterized in that the encapsulating material comprises the hardenable siloxane resin composition of the present invention.

The hardenable siloxane resin composition of the present invention mainly comprises an alkenyl group-containing high cross-linking network polyoxy siloxane and an alkenyl group-containing low cross-linking network polyoxy siloxane, which is used for packaging LED component applications. It can have excellent temperature difference thermal shock resistance, crack resistance and stability.

In the hardenable siloxane resin composition of the present invention, the (A) alkenyl group-containing high cross-linking network polysiloxane has an overall average composition as shown in the structural formula (1):

R ¹ _n SiO _(4-n)/2 (1)

Wherein R ¹ is, independently of each other, a monovalent hydrocarbon group, an alkoxy group or a hydroxyl group which has no substituent or a substituent, wherein the substituent may be selected from a halogen group, an alkyl group, a cycloalkyl group, an aryl group and an alkoxy group. group.

R ^{1 is} preferably a monovalent hydrocarbon group, more preferably a C1-15 monovalent hydrocarbon group, such as selected from the group consisting of alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl. , pentyl or hexyl; cycloalkyl, such as cyclohexyl or norbornyl; alkenyl, such as ethenyl, propenyl, isopropenyl, allyl or alkenyl; and aryl, such as phenyl , the group. R ^{1 is} most preferably a C1-10 alkyl group, a C 2-10 alkenyl group or a phenyl group.

When R ¹ is an alkoxy group, it is preferably a C1-10 alkoxy group such as a methoxy group or an ethoxy group.

n is a positive number, and 0 ≦ n ≦ 2, preferably 1 ≦ n ≦ 2, more preferably 1.2 ≦ n ≦ 1.6.

In the present invention, in the (A) alkenyl group-containing highly crosslinked network polyoxyalkylene, the alkenyl group accounts for 0.1 to 80 mol% based on the total R ¹ group content.

In the present invention, the composition (A) alkenyl group-containing high cross-linking network polyoxyalkylene is composed of R ¹ SiO _3/2 unit and R ¹ ₃ SiO _1/2 unit, R ¹ ₂ SiO _{2 /} A copolymer composed of at least one of ₂ units or SiO _4/2 units.

According to a specific embodiment of the present invention, in the (A) alkenyl group-containing highly crosslinked network polyoxyalkylene, the R ¹ SiO _3/2 and/or SiO _4/2 units account for 55 mol% or more. Jia is responsible for 55 to 71% of the total.

According to a preferred embodiment of the present invention, the R ¹ SiO _3/2 unit accounts for 55 mol% or more, preferably 55 to 71 mol%.

According to the hardenable siloxane resin composition of the present invention, the form of the (A) alkenyl group-containing high cross-linking network polysiloxane is not limited and may be liquid or solid, preferably at 25 ° C. A liquid having a lower viscosity of 10 mPa·s or more.

Composition (A) based on the weight of the whole alkenyl polyoxyalkylene (ie, the alkenyl-containing high cross-linking network polyoxyalkylene and the alkenyl-containing low cross-linking network polyoxyalkylene) The alkenyl group-containing high degree of cross-linking network polysiloxane has a content of from 0.1 to 60% by weight, preferably from 20 to 60% by weight, more preferably from 40 to 60% by weight.

In the hardenable siloxane resin composition of the present invention, the (B) alkenyl group-containing low cross-linking network polysiloxane has an overall average composition as shown in the structural formula (2):

R ² _n SiO _(4-n)/2 (2)

Wherein R ² is, independently of each other, a monovalent hydrocarbon group, an alkoxy group or a hydroxyl group which has no substituent or a substituent, wherein the substituent may be selected from a halogen group, an alkyl group, a cycloalkyl group, an aryl group and an alkoxy group. group.

Preferably, R ² is a monovalent hydrocarbon group, more preferably a C1-15 monovalent hydrocarbon group, selected from the group consisting of: an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl Or a pentyl group; a cycloalkyl group such as a cyclohexyl group or a norbornyl group; an alkenyl group such as a vinyl group, a propenyl group, an isopropenyl group, an allyl group or a butyl group; and an aryl group such as a phenyl group; , the group. R ^{2 is} most preferably C1-10 alkyl, C 2-10 alkenyl or phenyl.

When R ² is an alkoxy group, it is preferably a C1-10 alkoxy group such as a methoxy group or an ethoxy group.

n is a positive number, and 0≦n≦2, preferably 1≦n≦2, more preferably 1.5≦n≦2.

In the low-crosslinking degree network polyoxyalkylene having an alkenyl group of the present invention (B), the alkenyl group accounts for 0.1 to 80 mol% based on the total R ² group content.

In the present invention, the low-crosslinking degree network polyoxyalkylene having an alkenyl group of the composition (B) is composed of a unit of R ² SiO _{3/2 and a} unit selected from the group consisting of R ² ₃ SiO _1/2 unit, R ² ₂ SiO _{2 /} A copolymer composed of at least one of ₂ units or SiO _4/2 units.

According to a specific example of the present invention, in the (B) alkenyl group-containing low crosslinking degree network polyoxane, the R ² SiO _3/2 and/or SiO _4/2 unit accounts for 37 mol% or less, and more Jia is 27% to 37%.

According to a preferred embodiment of the invention, the R ² SiO _3/2 unit accounts for 37 mol% or less, preferably 37 to 27 mol%.

In the hardenable siloxane resin composition of the present invention, the form of the (B) alkenyl group-containing low cross-linking network polysiloxane is not limited and may be liquid or solid, preferably 25 A liquid having a viscosity of 10 mPa·s or more at ° C.

The content of the (B) alkenyl group-containing low crosslinking network polyoxyxane is from 40 to 99.9% by weight, preferably from 40 to 80% by weight, more preferably based on the weight of the whole alkenyl polysiloxane. It is 40 to 60% by weight.

In the hardenable siloxane resin composition of the present invention, the composition (C) is a polyhydrazine having a hydrogen bond, and has an overall average composition as shown in the structural formula (3):

R ³ _a H _b SiO _(4-ab)/2 (3)

Wherein R ³ is, independently of each other, a monovalent hydrocarbon group, an alkoxy group, a hydroxyl group having no substituent or a substituent, but does not include an alkenyl group, wherein the substituent may be selected from a halogen group, an alkyl group, a cycloalkyl group, and an aromatic group. a group of alkoxy groups and alkoxy groups.

R ^{3 is} preferably a monovalent hydrocarbon group, more preferably a C 1-15 monovalent hydrocarbon group, such as selected from the group consisting of: an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl a group of a cyclyl group, a pentyl group or a hexyl group; a cycloalkyl group such as a cyclohexyl group or a norbornyl group; and an aryl group such as a phenyl group. R ^{3 is} most preferably a C1-10 alkyl group or a phenyl group.

When R ³ is an alkoxy group, a C1-10 alkoxy group such as a methoxy group or an ethoxy group is preferred.

a is a positive number and 0.7≦a≦2.1.

b is a positive number and 0.001 ≦ b ≦ 1.0, preferably 0.2 ≦ b ≦ 0.8, more preferably 0.4 ≦ b ≦ 0.8.

According to a specific embodiment of the present invention, a+b is a positive number, and 0.8≦a+b≦3.0, preferably 1.4≦a+b≦3.0, more preferably 1.9≦a+b≦3.0.

According to a specific example of the present invention, in the structural formula (3), the methyl group accounts for at least 30 mol% based on the content of all the R ³ groups, and at least two hydrogen atoms bonded to the oxime are contained in each molecule.

The content of the (C) hydrazine-containing hydrogen-containing polyoxane is from 0.1 to 100% by weight, preferably from 14 to 30% by weight, more preferably from 22 to 28% by weight based on the weight of the whole alkenyl polysiloxane. %.

According to the hardenable decane resin composition of the present invention, a composition (D) hydrosilylation catalyst selected from a platinum-based, palladium- or rhodium-based catalyst may be added, and the catalysts may be used alone or in combination. As the above various catalysts, a platinum-based catalyst is preferred, and a platinum/alcohol catalyst is more preferred.

In the present invention, the amount of the composition (D) catalyst is not particularly limited and is usually an effective catalytic amount. The composition (D) catalyst is used in an amount of up to 500 ppm, preferably from 0.1 to 100 ppm, more preferably from 1 to 50 ppm, based on the weight of the monopolysiloxane.

According to another embodiment of the present invention, the hardenable decane resin composition optionally incorporates a hydrazine-containing hydrogen-bonded polyoxyalkylene having a composition (E) having an epoxy group as a adhesion promoter. The composition (E) is used in an amount of from 0.1 to 30% by weight, preferably from 0.1 to 10% by weight, more preferably from 1 to 5% by weight, based on the weight of the whole alkenyl polysiloxane.

The hardenable siloxane resin composition of the present invention is suitable for the encapsulant material of the LED component, and therefore another object of the present invention is to provide an encapsulant formulation for an LED component, characterized in that the encapsulant formulation comprises the invention The hardenable siloxane resin composition.

Still another object of the present invention is to provide an LED element characterized in that the LED element is packaged with the hardenable siloxane resin composition of the present invention as a packaging material. In detail, the present invention provides an LED element comprising: a frame as a substrate; a wire electrode disposed on the frame; a light-emitting element bonded to the wire electrode by an adhesive material; and a wire (such as a gold wire) electrically connecting the light-emitting element to another conductive And an encapsulant covering the frame, the light-emitting element, the wire electrode and the wire, wherein the encapsulant comprises the hardenable siloxane resin composition of the invention as a packaging material.

[Specific embodiment]

The invention is illustrated by the following examples without restricting the invention. In the following examples, M represents a R ₃ SiO _1/2 unit, D represents a R ₂ SiO _2/2 unit, T represents a RSiO _3/2 unit, and Q represents a SiO _4/2 unit, wherein R may be substituted A C1-10 monovalent hydrocarbon group, a methoxy group or an OH group having a substituent or a substituent, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group unless otherwise specified.

[Production of test samples]

The formulated encapsulant formulation is poured into a model or a PPA (polyphthalamide resin) LED holder (Lead frame 5630). A test sample was prepared by thermal crosslinking and hardening at 50 ° C / 1 hour, 100 ° C / 2 hours, 150 ° C / 5 hours.

[Feature evaluation] 1) Hardness test

The hardened sheet samples were tested for hardness using a Shore A durometer.

2) Light transmittance.

A hardened sheet sample having a thickness of 0.5 mm (mm) was taken, and the light transmittance at a wavelength of 400 nm (nm) was measured by a UV-Vis spectrometer.

3) Red ink test

After hardening, the LED holder was immersed in Merck red ink and heated at 90 ° C for 4 hours. After the heating was completed, the holder was taken out and rinsed with water. After being dried, the red ink was observed by an optical microscope.

O: No red ink penetration was observed under an optical microscope

×: Red ink penetration was observed under an optical microscope

4) Reflow test (reflow test)

After hardening, the LED holder was reflowed at 260 ° C for 3 minutes for 3 times, and then observed by an optical microscope.

O: No cracking, colloidal blistering, peeling or blistering with PPA, desorption or blistering with metal adhesion surface, etc. under the optical microscope

×: Under the optical microscope, it can be observed that cracking, colloidal foaming, debonding or foaming with PPA, debonding with metal adhesion surface or foaming

5) Cold and hot cycle test after high temperature and high humidity

After curing, the LED bracket is placed under the condition of 85 ° C / 85% relative humidity for 24 hours, and then subjected to a thermal cycle of 10 times at a temperature of 260 ° C and 0 ° C for 10 seconds, or 30 minutes at a temperature of 100 ° C and -40 ° C. Hot and cold cycle 50 times. After that, it was observed with an optical microscope.

O: No cracking, colloidal foaming, debonding or foaming on the surface of the PPA, desorption or blistering with the metal surface was observed under the optical microscope.

×: Under the optical microscope, it can be observed that cracking, colloidal foaming, debonding or foaming with PPA, debonding with metal adhesion surface or foaming

[Synthesis Example]

The polyaoxanes in the examples are composed of M(R ₃ SiO _1/2 ) units, D(R ₂ SiO _2/2 ) units, T(RSiO _3/2 ) units, and Q(SiO _4/2 ) units, respectively. Composition.

1) polyoxyalkylene (1) (alkenyl-containing high cross-linking network polyoxyalkylene, T unit accounted for 70.1 mol%)

Add 7.25 g of a 25% aqueous solution of Tetramethyl Ammonium Hydroxide and 45 g of water to the reaction flask, mix well and mix to form a mixture; then add 400 g of toluene and methylphenyldimethoxydecane. (methylphenyl dimethoxysilane) 104 g (0.57 mol), vinyl trimethoxysilane (59.3 g (0.4 mol), phenyl trimethoxysilane (204.2 g (1.03 mol)), obtained one The reaction mixture was subjected to a reaction at 65 ° C for 3 hours, after which 3.3 g (0.02 mol) of hexamethyl disiloxane (hexamethyl disiloxane) was added, and the reaction was further carried out for 7 hours. After the reaction is completed, it is washed with water until neutral, and the solvent is removed under reduced pressure to obtain an alkenyl group-containing high cross-linking network polyoxyalkylene 200 g having an average molecular formula:

(Me ₃ SiO _1/2 ) _0.020 (MePhSiO _2/2 ) _0.279 (PhSiO _3/2 ) _0.505 (ViSiO _3/2 ) _0.196

2) Polyoxane (2) (alkenyl-containing high cross-linking network polyoxyalkylene, T unit accounts for 55 mol%)

Add 2.25 g of 25% tetramethylammonium hydroxide aqueous solution and 45 g of water to the reaction flask, mix well and mix to form a mixture; add 400 g of toluene and methylphenyl dimethoxy decane 162.1 g (0.889 mol) 59.3 g (0.4 mol) of vinyltrimethoxydecane and 141 g (0.711 mol) of phenyltrimethoxydecane gave a reaction mixture; the reaction mixture was reacted at 65 ° C for 3 hours, after which six were added. 3.3 g (0.02 mol) of methyldioxane was further reacted for 7 hours. After the reaction was completed, it was washed with water to neutrality, and the solvent was removed under reduced pressure to obtain 211 g of an alkenyl group-containing highly crosslinked network polyoxyalkylene having an average molecular formula:

(Me ₃ SiO _1/2 ) _0.020 (MePhSiO _2/2 ) _0.435 (PhSiO _3/2 ) _0.349 (ViSiO _3/2 ) _0.196

3) Polyoxane (III) (low-crosslinking degree network polyoxyalkylene containing alkenyl group, T unit accounts for 36.5 mol%)

7.4 g of a 25% aqueous solution of tetramethylammonium hydroxide and 31 g of water were added to the reaction flask, and the mixture was uniformly stirred to form a mixture; then, 200 g of toluene and 2,4,6,8-tetramethyl were added to the mixture. 41.4 g (0.12 mol) of 2,4,6,8-tetravinyl-cyclotetrasiloxane (2,4,6,8-Tetramethyl-2,4,6,8-tetravinyl-cyclotetrasiloxane), To obtain a reaction mixture; the reaction mixture was subjected to a reaction at 85 ° C for 30 minutes; then the temperature was lowered to 65 ° C, and then added with methyl phenyl dimethoxy decane 145.8 g (0.8 mol), phenyl trimethoxy 150.7 g (0.76 mol) of decane, the reaction was carried out for 3 hours, 3.3 g (0.02 mol) of hexamethyldioxane was added, and the reaction was further carried out for 3 hours; after completion of the reaction, 200 g of toluene was added, and washed with water. To neutral, the solvent was removed under reduced pressure to obtain an alkenyl group-containing low cross-linking network polyoxyalkylene 210 g having an average molecular formula:

(Me ₃ SiO _1/2 ) _0.019 (MePhSiO _2/2 ) _0.385 (ViMeSiO _2/2 ) _0.231 (PhSiO _3/2 ) _0.365

4) Polyoxane (4) (low-crosslinking degree network polyoxyalkylene containing alkenyl group, T unit accounts for 27.7 mol%)

7.4 g of a 25% aqueous solution of tetramethylammonium hydroxide and 31 g of water were added to the reaction flask, and the mixture was uniformly stirred to form a mixture; then, 200 g of toluene and 2,4,6,8-tetramethyl-2 were added. 41.4 g (0.12 mol) of 4,6,8-tetravinyl-cyclotetraoxane, a reaction mixture was obtained; the reaction mixture was subjected to a reaction at 85 ° C for 30 minutes; then the temperature was lowered to 65 ° C, and then Adding 179.2 g (0.983 ears) of methylphenyl dimethoxydecane and 114.4 g (0.577 mol) of phenyltrimethoxydecane, after reacting for 3 hours, adding 3.3 g of hexamethyldioxane (0.02 mol) The ear was further reacted for 3 hours; after the reaction was completed, 200 g of toluene was added, washed with water until neutral, and the solvent was removed under reduced pressure to obtain 215 g of a low cross-linking network polyoxyalkylene having an alkenyl group. Has the average composition of the formula:

(Me ₃ SiO _1/2 ) _0.019 (MePhSiO _2/2 ) _0.473 (ViiMeSiO _2/2 ) _0.231 (PhSiO _3/2 ) _0.277

5) Polyoxane (5) (low-crosslinking degree network polyoxyalkylene containing alkenyl group, T unit accounts for 28 mol%)

0.71 g of a 25% aqueous solution of tetramethylammonium hydroxide and 39.2 g of water were added to the reaction flask, and the mixture was uniformly stirred to form a mixture; then, 100 ml of cyclohexane and 2,4,6,8-tetramethyl- were added. 20.7 g (0.06 mol) of 2,4,6,8-tetravinyl-cyclotetraoxane, a reaction mixture was obtained; the reaction mixture was refluxed at 85 ° C for 30 minutes; after that, the temperature was lowered. At 65 ° C, 33.7 g (0.28 mol) of dimethyl dimethoxysilane, 40.4 g (0.18 mol) of diphenyl dimethoxysilane, and phenyltrimethoxy group were further added. 55.52 g (0.28 mol) of decane was reacted for 3 hours, and then 1.65 g (0.01 mol) of hexamethyldioxane was added, and the reaction was further carried out for 3 hours. After completion of the reaction, 200 g of toluene was added, and water and cyclohexane were removed by azeotropic removal, washed with water until neutral, and the solvent was removed under reduced pressure. Obtaining 208 g of a low cross-linking network polyoxyalkylene having an alkenyl group, having an average molecular formula:

(Me ₃ SiO _1/2 ) _0.020 (Me ₂ SiO _2/2 ) _0.280 (Ph ₂ SiO _2/2 ) _0.180 (ViMeSiO _2/2 ) _0.240 (PhsiO _3/2 ) _0.280

6) Polyoxane (VI) (a polyoxyalkylene containing a hydrogen bond, having the structural formula shown below)

7) Polyoxane (7) (polyoxyalkylene containing epoxy groups and hydrazine hydrogen bonds)

Take 7.5 g of 38% concentrated hydrochloric acid and dilute to 150 g with water, add 250 g of isopropanol to the reaction flask, and add 2,4,6,8-tetramethyl-2,4,6,8-tetrahydro - 60 g (0.25 mol) of cyclotetraoxane, 122.5 g (0.5 mol) of diphenyldimethoxydecane, 49.5 g of tetramethyl disiloxane, to give a reaction mixture; The reaction mixture was reacted at room temperature for 24 hours. After the reaction is completed, it is extracted with toluene, washed with water until neutral, and the solvent is removed under reduced pressure to obtain a polyhydrazine having a hydrogen bond, having an average molecular formula:

(Ph ₂ SiO _2/2 ) _0.26 (HMeSiO _2/2 ) _0.38 (HMe ₂ SiO _1/2 ) _0.36

Taking (Ph ₂ SiO _2/2 ) _0.26 (HMeSiO _2/2 ) _0.38 (HMe ₂ SiO _1/2 ) _0.36 100 g and a concentration of 5000 ppm of Pt/1-octanol solution 0.9 g, allyl glycidyl ether 55 g of (allyl glycidyl ether) were mixed to obtain a reaction mixture; the reaction mixture was subjected to a reaction at 84 ° C for 15 hours. After the reaction was completed, 1 g of charcoal was added, and the mixture was placed in an oil bath at 84 ° C for further 2 hours. After cooling, it was filtered through a 0.45 μm filter cake and concentrated in vacuo to give an epoxy. A polyoxyalkylene group having a hydrogen bond and a hydrogen bond, having a molecular formula:

Example 1

2.88 g of polyoxyalkylene (1) and 2.7 g of polyoxyalkylene (tetra) were mixed and homogenized at 90 ° C to form a mixture; after that, the temperature was lowered to room temperature, and then 1.45 g of polyoxyalkylene was added. (6) to obtain a reaction mixture; adding 0.036 g of a Pt/1-octanol solution (concentration: 5000 ppm) as a catalyst for the addition reaction, and adding 0.2 g of polyoxyalkylene (seven) to the reaction mixture, After thorough mixing, vacuum defoaming is performed to prepare an encapsulant formulation.

Examples 2 to 6

The composition weight (g) of the formulation shown in Table 1 is taken from the alkenyl-containing high cross-linking network polyoxyalkylene and the alkenyl-containing low cross-linking network polyoxyalkylene, mixed at 90 ° C Uniformly to form a mixture; after that, the temperature was lowered to room temperature, and polyoxyalkylene (six) was added to obtain a reaction mixture; 0.036 g of Pt/1-octanol solution (concentration) was added to each reaction mixture. It was 5000 ppm) and 0.2 g of polyoxyalkylene (seven), and was thoroughly mixed and then vacuum defoamed to prepare the encapsulant formulations of Examples 2 to 6.

The encapsulant formulations prepared in the above Examples 1 to 6 were prepared into a sheet-like test sample, and the characteristics evaluation method described above was performed, and hardness, light transmittance, red ink test, reflow test, high temperature and high humidity were performed on each sample. After the hot and cold cycle test (0 ° C / 260 ° C, -40 ° C / 100 ° C), the evaluation results are shown in Table 1.

As shown in Table 1, Examples 1 to 6 of the encapsulant material obtained by using the hardenable decane resin composition of the present invention were simultaneously used (A) an alkenyl group-containing high cross-linking network polyoxyalkylene with ( B) Alkenyl group-containing low cross-linking degree network polysiloxane, after the hydroquinone reaction, no red ink infiltration was observed by optical microscopy, and the reflow test and the hot and cold cycle test after high temperature and high humidity were tested. Tested at 0 ° C / 260 ° C and -40 ° C / 100 ° C conditions) also found no cracking, blistering, desorption and so on. In contrast, Comparative Examples 1 and 2 lack the (A) or (B) of the present invention, respectively, and although the penetration is good, the properties of the red ink test, the reflow test, and the hot and cold cycle test are not good. Therefore, the hardenable siloxane resin composition of the present invention can make the composition harden and has excellent light transmittance, crack resistance and temperature difference impact resistance, and has the advantages of simple synthesis, and is suitable for application. Encapsulant material or other commercial use.

The above-described embodiments of the present invention are not intended to be limited thereto, and various modifications and improvements may be made without departing from the spirit and scope of the invention. Equivalent changes or modifications of the meaning and range of the substance are intended to be included in the scope of the invention.

Claims (12)

A hardenable decane resin composition comprising: (A) an alkenyl group-containing highly crosslinked network polyoxyalkylene having an overall average composition as shown in structural formula (1): R ¹ _n SiO _{(4- n) / 2} (1), wherein R ^{1 is} independently a non-substituted or substituted monovalent hydrocarbon group, alkoxy group, hydroxyl group, n is a positive number, and 0≦n≦2, wherein the alkenyl group accounts for 0.1 to 80 mol% of the R ¹ group, and R ¹ SiO _3/2 and/or SiO _4/2 units account for 55 mol% or more of (A); (B) a low crosslink network having an alkenyl group The polyhalothane has an overall average composition as shown in the structural formula (2): R ² _n SiO _(4-n)/2 (2) wherein R ^{2 is} independently a unitless or substituted unit price a hydrocarbon group, an alkoxy group, a hydroxyl group, n is a positive number, and 0≦n≦2, wherein the alkenyl group accounts for 0.1 to 80 mol% of the entire R ² group, and R ² SiO _3/2 and/or SiO _4/2 The unit accounts for 37 mol% or less of (B); (C) the polyoxyalkylene containing a hydrogen bond having an overall average composition as shown in the structural formula (3): R ³ _a H _b SiO _(4-ab)/ (3) formula _2, R ³ independently of one another unsubstituted monovalent hydrocarbon group not having or having a substituent, an alkoxy group, a hydroxyl group, excluding alkenyl groups, and all groups R ³ 30% less is methyl, a is positive and 0.7≦a≦2.1, b is positive and 0.001≦b≦1.0, where 0.8≦a+b≦3.0, there must be at least two 矽 bonds in each molecule a hydrogen atom of the knot; and (D) a catalyst for the hydroquinonelation reaction. The hardenable decane resin composition of claim 1, wherein in the structural formula (2) of the structural formula (A) and (B), n ranges from 1 to 2. The hardenable decane resin composition of claim 1, wherein the composition (A) contains an alkenyl group having a high degree of cross-linking network polyoxane, R ¹ SiO _3/2 unit and/or SiO _4/2 The unit accounts for 55 to 71 mol% of (A). The hardenable decane resin composition of claim 3, wherein the composition (A) contains an alkenyl group having a high degree of cross-linking network polysiloxane, wherein the R ¹ SiO _3/2 unit accounts for 55 (A) to 71% by mole. The hardenable decane resin composition of claim 1, wherein the composition (B) contains an alkenyl group having a low degree of cross-linking network polysiloxane, R ² SiO _3/2 unit and/or SiO _4/2 The unit accounts for 27 to 37 mol% of (B). The hardenable decane resin composition of claim 5, wherein the composition (B) contains an alkenyl group having a low degree of cross-linking network polysiloxane, wherein the R ² SiO _3/2 unit accounts for 27 of (B) 37 moles %. The hardenable oxirane resin composition according to any one of claims 1 to 6, wherein the (A) alkenyl group-containing high cross-linking degree network polysiloxane has a content of from 0.1 to 60% by weight, (B) The alkenyl group-containing low cross-linking degree network polysiloxane has a content of 40 to 99.9% by weight, and (C) the polyhydrazine having a rhodium hydrogen bond content of 0.1 to 100% by weight, as a whole alkenyl polyoxyalkylene. Based on the weight, and (D) the catalyst content of the hydroquinonelation reaction is an effective catalytic amount based on the weight of the overall polyoxane. The hardenable decane resin composition according to claim 7, wherein the (A) alkenyl group-containing high cross-linking degree network polysiloxane has a content of 40 to 60% by weight, and (B) an alkenyl group-containing low cross-linking agent The content of the networked polysiloxane is 40 to 60% by weight, and the content of the polyoxysilane having a hydrogen bond containing (a) is 14 to 30% by weight based on the weight of the whole alkenyl polysiloxane. (D) The catalyst content of the hydroquinonelation reaction is at most 500 ppm based on the weight of the overall polyoxane. The hardenable decane resin composition according to any one of claims 1 to 6, which further comprises (E) a hydrazine-containing hydrogen-bonded polyoxyalkylene having an epoxy group. The hardenable oxirane resin composition of claim 9, wherein the (E) hydrazine-containing hydrogen-bonded polyoxyalkylene having an epoxy group is contained in an amount of from 0.1 to 30% by weight based on the total weight of the alkenyl polysiloxane As the benchmark. An LED component encapsulant formulation, characterized in that the encapsulant formulation comprises the hardenable siloxane resin composition of any one of claims 1 to 10. An LED component comprising an encapsulant material, characterized in that the encapsulant material comprises the hardenable siloxane resin composition of any one of claims 1 to 10.