TWI831858B - Addition curable polysilicone resin composition, its cured product, and optical semiconductor device - Google Patents

Abstract

[Problem] To provide an addition-curable polysiloxane resin composition capable of obtaining a cured product having excellent hardness and grain shear strength. [Solution] An addition curable polysiloxane resin composition containing the following components: (A) Organopolysiloxane represented by the following formula, (B) Branched organopolysiloxane represented by the following formula, (C) Organohydrogen polysiloxane represented by the following formula, (In the above formula, R ¹ and R ³ are monovalent hydrocarbon groups not containing an alkenyl group, and R ² is an alkenyl group), and (D) a platinum group metal catalyst.

Description

Addition curable polysilicone resin composition, its cured product, and optical semiconductor device

The present invention relates to an addition-curable polysiloxane resin composition, the cured product, and an optical semiconductor device using the same.

Recently, for sealing materials and die bonding materials of light-emitting diode (hereinafter referred to as "LED") elements, because the brightness of the LED element increases and the heat generated by the element increases, polysiloxane resin with good durability is used (Patent Documents 1 and 2 ). Especially in die-bonding materials, if the resin is too soft, an undesirable situation will occur in which bonding is impossible during the wire bonding step performed after the die-bonding step. Therefore, a die-bonding material with high hardness is required.

In addition, due to the progress in miniaturization of LED devices in recent years, die bonding materials with higher adhesion are required. If the adhesion force of the die bonding material is insufficient, fatal manufacturing problems such as chip peeling may occur during the wire bonding step of LED manufacturing. So far, although polysiloxane crystal bonding materials have excellent durability, their adhesion is insufficient, and materials with higher grain shear strength are needed. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2006-342200 [Patent Document 2] Japanese Patent Application Publication No. 2010-285571

[Problem to be solved by the invention]

The present invention was made in consideration of the above-mentioned circumstances, and it is an object of the present invention to provide an addition-curable polysiloxane resin composition capable of obtaining a cured product having excellent hardness and grain shear strength. [Means used to solve problems]

In order to solve the above problems, the present invention provides an addition curable polysilicone resin composition (A) characterized by containing the following components, represented by the following average composition formula (1), and having a viscosity of 500 mPa at 25°C. ･Organopolysiloxane below s, (In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group without an alkenyl group, which may be the same or different, and R ² is an alkenyl group, which may be the same or different. a, b, c, d, e , f and g are respectively numbers that satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, but, b+c+e>0 and a +b+c+d+e+ f+g=1.) (B) Branched organopolysiloxane represented by the following average composition formula (2): relative to component (A) and (B) The total of 100 parts by mass of the ingredients is 70 to 95 parts by mass, (In the formula, R ¹ and R ² are the same as above. h, i, j, k, l, m, n and o are respectively consistent with h≧0, i>0, j≧0, k≧0, l≧0, The numbers m≧0, n≧0, and o≧0, however, are the numbers m+n+o>0 and h+i+j+k+l+m+n+o=1.) (C) Organohydrogen polysiloxane represented by the following average composition formula (3) and having at least two hydrogen atoms bonded to silicon atoms in one molecule, (In the formula, R ³ is an alkenyl-free substituted or unsubstituted monovalent hydrocarbon group that may be the same or different, p and q are in compliance with 0.7≦p≦2.1, 0.001≦q≦1.0 and 0.8≦p+q ≦3.0.) (D) Platinum group metal catalyst.

If it is the addition curable polysiloxane resin composition of the present invention, a cured product excellent in hardness and grain shear strength can be obtained.

In the present invention, the component (A) is preferably a branched organopolysiloxane represented by the following average composition formula (1a). (In the formula, a, b, e, f are numbers that satisfy a+b>0, b+e>0, e+f>0 and a+b+e+f=1.)

With such an addition-curable polysiloxane resin composition, a cured product having higher hardness and grain shear strength can be obtained.

In the present invention, it is preferable that at least 80 mol% of all monovalent hydrocarbon groups other than alkenyl groups bonded to silicon atoms in the aforementioned composition are methyl groups.

With such an addition-curable polysiloxy resin composition, a cured product can be obtained that is excellent in heat resistance, light resistance (ultraviolet resistance), and resistance to deterioration such as discoloration due to stress such as heat and ultraviolet rays.

In the present invention, it is preferable to further contain an organic peroxide.

With such an addition curable polysiloxane resin composition, a cured product with enhanced strength can be obtained.

In this case, 1,6-bis(t-butylperoxycarbonyloxy)hexane is more preferred as the organic peroxide.

With such an addition curable polysiloxane resin composition, a cured product with further enhanced strength can be obtained.

Furthermore, the present invention provides a polysilicone cured product characterized by the cured product of the above-mentioned addition curable polysilicone resin composition.

Such hardened polysiloxane has excellent hardness and grain shear strength, and can be used as a die bonding material for die bonding of components with high adhesion to substrates and LED chips, especially LED components.

Furthermore, the present invention provides an optical semiconductor device in which an optical semiconductor element is die-bonded using the above-mentioned polysiloxane cured material.

Such an optical semiconductor device has excellent hardness and grain shear strength, and uses the above-mentioned polysiloxane cured material as a die bonding material with high adhesion to substrates, LED chips, etc., making it highly reliable. [Effects of the invention]

As mentioned above, if the addition curable polysiloxane resin composition of the present invention is used, a polysiloxane cured product with excellent hardness and grain shear strength can be obtained, which can be especially used as a die bonding material for die bonding of LED components and the like. . Next, in the wire bonding step performed after the die bonding step, undesirable situations such as peeling off of the wafer or failure to bond are less likely to occur. Therefore, an optical semiconductor device in which the optical semiconductor element is die-bonded with the cured polysiloxane grains has high reliability and Its productivity is also improved. [The best way to implement the invention]

As mentioned above, there is a need to develop a polysiloxane composition that can obtain a cured product that is excellent in hardness and grain shear strength and can be used as a die-bonding material for die bonding of LED elements and the like.

As a result of diligent examination of the above-mentioned problems, the inventors found that the above-mentioned problems can be solved by using an addition-hardening polysiloxane composition containing the components (A), (B), (C), and (D) described below. Complete the present invention.

That is, the present invention is an addition-hardening polysiloxy resin composition characterized by containing the following composition: (A) An organic compound represented by the following average composition formula (1) and having a viscosity of 500 mPa･s or less at 25°C. polysiloxane, (In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group without an alkenyl group, which may be the same or different, and R ² is an alkenyl group, which may be the same or different. a, b, c, d, e , f and g are respectively numbers that satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, but, b+c+e>0 and a +b+c+d+e+ f+g=1.) (B) Branched organopolysiloxane represented by the following average composition formula (2): relative to component (A) and (B) The total of 100 parts by mass of the ingredients is 70 to 95 parts by mass, (In the formula, R ¹ and R ² are the same as above. h, i, j, k, l, m, n and o are respectively consistent with h≧0, i>0, j≧0, k≧0, l≧0, The numbers m≧0, n≧0, and o≧0, however, are the numbers m+n+o>0 and h+i+j+k+l+m+n+o=1.) (C) Organohydrogen polysiloxane represented by the following average composition formula (3) and having at least two hydrogen atoms bonded to silicon atoms in one molecule, (In the formula, R ³ is an alkenyl-free substituted or unsubstituted monovalent hydrocarbon group that may be the same or different, p and q are in compliance with 0.7≦p≦2.1, 0.001≦q≦1.0 and 0.8≦p+q ≦3.0.) (D) Platinum group metal catalyst.

The present invention will be described in detail below, but the present invention is not limited thereto.

[Addition hardening polysiloxane composition] The addition curable polysiloxane composition of the present invention contains components (A) to (D) described below. Each ingredient is described in detail below.

<(A) component> The (A) component is an organopolysiloxane represented by the following average composition formula (1). (In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group without an alkenyl group, which may be the same or different, and R ² is an alkenyl group, which may be the same or different. a, b, c, d, e , f and g are respectively numbers that satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, but, b+c+e>0 and a +b+c+d+e+ f+g=1.)

The viscosity of the component (A) measured by a rotational viscometer at 25°C is 500 mPa･s or less, preferably 100 mPa･s or less. When it exceeds 500mPa･s, the viscosity of the composition becomes high, making it difficult to apply the composition to the LED substrate with a die bonding machine. In addition, unless otherwise specified below, the viscosity is measured using a rotational viscometer at 25°C.

The substituted or unsubstituted monovalent hydrocarbon group represented by R ¹ that does not have an alkenyl group is not particularly limited, but is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the monovalent hydrocarbon include alkyl groups such as methyl, ethyl, propyl and butyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, and aryl groups such as phenyl, tolyl and xylyl. , benzyl, phenylethyl, etc. aralkyl groups, chloromethyl, chloropropyl, chlorocyclohexyl, etc. halogenated hydrocarbon groups, etc. An alkyl group is preferred, and a methyl group is particularly preferred.

The alkenyl group represented by R ² is preferably an alkenyl group having 2 to 10 carbon atoms, especially an alkenyl group having 2 to 6 carbon atoms, such as vinyl, allyl, or ethynyl, and vinyl is particularly preferred.

The component (A) is preferably a branched organopolysiloxane represented by the following average composition formula (1a). (In the formula, a, b, e, f are numbers that satisfy a+b>0, b+e>0, e+f>0 and a+b+e+f=1.)

Specific examples of branched organopolysiloxane include those represented by the following formulas.

As the component (A), an organopolysiloxane having a linear molecular structure can be used. Specific examples of the linear organopolysiloxane of component (A) include double-terminal methylphenylvinyl-blocked diphenylsiloxane and single-terminal methylphenylvinyl single-terminated diphenylsiloxane. Vinyl-blocked diphenylsiloxane, diphenylvinyl-blocked diphenylsiloxane, diphenylvinyl-blocked diphenylsiloxane, methylphenylsiloxane Alkane copolymer, two-terminal dimethylvinyl chain-capped diphenylsiloxane, one-terminal dimethylvinyl, one-terminal methylphenylvinyl chain-capped diphenylsiloxane, two-terminal dimethylethylene Base-blocked methylphenylsiloxane, single-terminal dimethylvinyl single-terminal methylphenylvinyl chain-blocked methylphenylsiloxane, etc. The above-mentioned organopolysiloxane may be used alone or in combination of two or more kinds.

Other specific examples of the linear organopolysiloxane include compounds represented by the following formulas. (In the above formula, the order of the siloxane units in parentheses is arbitrary.)

(A) Component may be used individually by 1 type or in combination of 2 or more types.

<(B) Component> The (B) component is a branched organopolysiloxane represented by the following average composition formula (2). (In the formula, R ¹ and R ² are the same as above. h, i, j, k, l, m, n and o are respectively consistent with h≧0, i>0, j≧0, k≧0, l≧0, The numbers m≧0, n≧0, and o≧0, however, are consistent with the numbers m+n+o>0 and h+i+j+k+l+m+n+o=1.)

Examples of R ¹ include the same ones as those exemplified in component (A), and an alkyl group is preferred, and a methyl group is particularly preferred.

Examples of R ² include the same ones as those exemplified in component (A), preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group.

In the above average composition formula (2), h is 0~0.65, i is 0.1~0.65, j is 0~0.65, k is 0~0.5, l is 0~0.5, m is 0~0.8, and n is 0~ 0.8, o is a number between 0 and 0.6. m+n+o is preferably 0.05 or more, more preferably 0.1 to 0.9, and particularly preferably 0.2 to 0.6.

In component (B), the content of the alkenyl group bonded to the silicon atom is preferably in the range of 0.01 to 1 mol per 100 g of component (B), and more preferably in the range of 0.1 to 0.6 mol. When the above content is in the range of 0.01~1 mol, the cross-linking reaction is sufficient and a hardened product with higher hardness can be obtained.

From the viewpoint of easy separation, the organopolysiloxane of component (B) preferably has a weight average molecular weight in the range of 500 to 100,000.

Since the component (B) has R ² ₃ SiO _1/2 units (ie, i>0), it can impart bonding strength to the cured product obtained from the composition of the present invention. In addition, component (B) must have a branched structure composed of SiO _4/2 units and/or SiO _3/2 units, but may further contain methylvinylsilyloxy units, dimethylsilyloxy units, etc. SiO _2/2 (SiO) units, dimethylvinylsilyloxy units, trimethylsilyloxy units, etc. SiO _1/2 units. The content of SiO _4/2 units and/or SiO _3/2 units is preferably at least 5 mol% of the total siloxane units of the organopolysiloxane resin of component (B), more preferably 10 mol~ 90 mol%, especially 20~60 mol%.

The blending amount of component (B) is 70 to 95 parts by mass, preferably 75 to 95 parts by mass, and more preferably 80 to 90 parts by mass based on 100 parts by mass of the total of component (A) and component (B). If the blending amount of component (B) is less than 70 parts by mass, the adhesion may be poor and a high-hardness cured product may not be obtained. If the blending amount exceeds 95 parts by mass, the viscosity of the composition will significantly increase, making transfer difficult, and the result will be The composition becomes difficult to operate when used for crystal bonding materials and the like.

Specific examples of the branched organopolysiloxane of component (B) include the following.

(B) Component may be used individually by 1 type or in combination of 2 or more types.

<(C) component> The (C) component serves as a cross-linking agent that cross-links the alkenyl group contained in the (A) component and (B) component through a hydrosilylation reaction. Component (C) is an organohydrogen polysiloxane represented by the following average composition formula (3) and having at least two hydrogen atoms (that is, Si-H groups) bonded to silicon atoms in one molecule. (In the formula, R ³ is an alkenyl-free substituted or unsubstituted monovalent hydrocarbon group that may be the same or different, p and q are in compliance with 0.7≦p≦2.1, 0.001≦q≦1.0 and 0.8≦p+q ≦3.0, preferably 1.0≦p≦2.0, 0.01≦q≦1.0 and 1.5≦p+q≦2.5.)

The viscosity of the component (C) at 25°C is preferably 100 mPa･s or less, more preferably in the range of 5 to 100 mPa･s.

Examples of R ³ include the same ones as those exemplified as R ¹ in component (A), and an alkyl group is preferred, and a methyl group is particularly preferred.

Furthermore, in the composition of the present invention, the proportion of methyl groups in the total number of all monovalent hydrocarbon groups bonded to silicon atoms other than the alkenyl groups represented by R ¹ and R ³ is 80 mol% or more (the above-mentioned all monovalent hydrocarbon groups are Preferably, at least 80 mol% of the valent hydrocarbon groups are methyl groups. In particular, those with more than 90 mol% have excellent heat resistance, light resistance (ultraviolet resistance), and resistance to deterioration such as discoloration caused by stress such as heat and ultraviolet rays. And good.

(C) The component has at least 2 hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, preferably 2 to 200, more preferably 3 to 100, and particularly preferably 4 to 50. .

The molecular structure of the organohydrogen polysiloxane of component (C) can be any of linear, cyclic, branched, or three-dimensional network structures, but the number of silicon atoms in one molecule is preferably 2~ 300 pcs, preferably 3~200 pcs.

Examples of the organohydrogenpolysiloxane of component (C) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and (Hydrogendimethylsilyloxy)methylsiloxane, (hydrodimethylsilyloxy)phenylsiloxane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane･dimethylsiloxane ring copolymer, two-terminal trimethylsiloxy blocked methyl hydrogen polysiloxane, both terminal trimethylsiloxy blocked dimethylsiloxane and methyl hydrogen siloxane copolymer, both terminal Dimethyl hydrogen siloxane chain-blocked dimethyl polysiloxane, both terminal dimethyl hydrogen silanoxy chain-blocked methyl hydrogen polysiloxane, both terminal dimethyl hydrogen silanoxy chain-blocked dimethyl Siloxane･methylhydrogensiloxane copolymer, double-terminal trimethylsiloxy chain-blocked methylhydrogensiloxane･diphenylsiloxane copolymer, double-terminal trimethylsiloxy chain-blocked methylhydrogensiloxane Hydrogensiloxane, diphenylsiloxane, dimethylsiloxane copolymer, trimethylsiloxy-blocked methylhydrogensiloxane, methylphenylsiloxane, dimethylsiloxane Siloxane copolymer, both terminal dimethylhydrogensilaneoxy-blocked methylhydrogensiloxane, dimethylsiloxane, diphenylsiloxane copolymer, both terminally-blocked dimethylhydrogensilyloxy groups Chain methyl hydrogen siloxane, dimethyl siloxane, methyl phenyl siloxane copolymer, (CH ₃ ) ₂ HSiO _1/2 unit and (CH ₃ ) ₃ SiO _1/2 unit and SiO _4/ Copolymer composed of ₂ units, copolymer composed of (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit, (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit and (C ₆ In addition to copolymers composed of H ₅ ) ₃ SiO _1/2 units, examples may include those represented by the following general formula (4) or (5). (In the formula, R ³ is the same as above, r is an integer from 2 to 40, preferably 8 to 35, and s is an integer from 6 to 8.)

Specific examples of the component (C) include those represented by the following general formula (6): (In the formula, r is the same as above. Me is methyl.) or represented by the following formula, etc. (In the formula, the order of the siloxane units in parentheses is arbitrary.)

The organohydrogen polysiloxane of component (C) can be used individually by 1 type or in combination of 2 or more types.

From the perspective of cross-linking balance, the blending amount of component (C) is based on the total number of alkenyl groups bonded to all silicon atoms in components (A) and (B). The number of hydrogen atoms (Si-H groups) relative to silicon atoms is preferably 0.5 to 5.0 times, more preferably 0.7 to 3.0 times. If it is within this range, crosslinking will proceed sufficiently and a cured material with excellent hardness will be obtained.

＜(D)Component＞ The platinum group metal catalyst of component (D) is a component used to advance and accelerate the hydrogenation reaction of components (A) to (C).

The platinum group metal catalyst is not particularly limited, and examples thereof include platinum group metals such as platinum, palladium, and rhodium; chlorinated platinic acid, alcohol-modified chlorinated platinic acid, chlorinated platinic acid and olefins, and vinyl siloxane. Or platinum compounds such as coordination compounds of acetylene compounds, platinum group metal compounds such as quaternary (triphenylphosphine) palladium, chloroparaben (triphenylphosphine) rhodium, etc., but because of the combination with components (A) ~ (C) It has good compatibility and contains almost no chlorine impurities. It is preferably chlorinated platinic acid modified with polysiloxane. (D) Component may be used individually by 1 type or in combination of 2 or more types.

The blending amount of component (D) is sufficient to be an effective amount as a catalyst, but relative to the total of components (A) to (C), it is preferably 1 to 500 ppm in mass conversion of platinum group metal elements, and more preferably 3~100ppm, preferably 5~40ppm. When the blending amount is appropriate, the hydrogenation reaction can be promoted more effectively.

＜Other ingredients＞ In addition to the above-mentioned components (A) to (D), the composition of the present invention may also contain other components exemplified below.

Organic peroxide: In the present invention, by adding organic peroxide, the resin strength can be further improved. Examples of organic peroxides include 1,6-bis(t-butylperoxycarbonyloxy)hexane, benzyl peroxide, t-butyl perbenzoate, and o-methylbenzene Formyl peroxide, p-methylbenzoyl peroxide, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,3-tri Methylcyclohexane, bis(4-methylbenzylperoxy)hexamethylene biscarbonate, etc., but 1,6-bis(t-butylperoxycarbonyloxy)hexane Better. The added amount is an effective amount, but usually 0.01 to 5 parts by mass relative to 100 parts by mass of the total amount of organopolysiloxane of components (A) and (B), especially blending 0.05 to 3 parts by mass is preferred. . These can be used individually by 1 type or in combination of 2 or more types.

Reaction inhibitors: In the composition of the present invention, a conventional reaction inhibitor (reaction control agent) of a compound having a hardening inhibitory effect on the addition reaction catalyst of component (D) can be used if necessary. Examples of the reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene compounds; Hydrogen peroxide compounds; maleic acid derivatives, etc. The degree of the hardening inhibitory effect caused by the reaction inhibitor greatly differs depending on the chemical structure of the reaction inhibitor, so the blending amount of the reaction inhibitor is preferably adjusted to the optimal amount of each reaction inhibitor used. Usually, it is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total of (A) component, (B) component, (C) component and (D) component.

Adhesion enhancer: In order to improve the adhesion to the resin in this composition, an adhesion improving agent can be added. Regarding the adhesiveness improving agent, from the viewpoint of imparting adhesiveness to the addition reaction curable composition of the present invention itself, organosilicon compounds such as silane and siloxane containing functional groups for imparting adhesiveness, non-polymer compounds and the like can be used. Silicone organic compounds, etc. Specific examples of the functional group that imparts adhesiveness include, for example, alkenyl groups such as vinyl and allyl groups bonded to silicon atoms, and hydrogen atoms; and epoxy groups bonded to silicon atoms through carbon atoms (for example, γ- Glycidoxypropyl, β-(3,4-epoxycyclohexyl)ethyl, etc.) or acryloyloxy (such as γ-acryloxypropyl, etc.) or methacryloxy ( For example, γ-methacryloxypropyl, etc.); alkoxysilyl group (for example, it may contain 1 to 2 ester structures, urethane structures, or ether structures bonded to silicon atoms through an alkylene group. Trimethoxysilyl, triethoxysilyl, methyldimethoxysilyl, alkoxysilyl, etc.), etc. Organosilicon compounds containing functional groups that impart adhesion, such as silane coupling agents, siloxanes having an alkoxysilyl group and an organic functional group, and organic compounds having a reactive organic group in which an alkoxysilyl group is introduced Compounds etc. Examples of the non-polysilicone-based organic compound include organic acid allyl ester, epoxy ring-opening catalyst, organic titanium compound, organic zirconium compound, and organic aluminum compound.

Filling agent: The composition of the present invention can be filled with inorganic fillers such as crystalline silica, hollow fillers, and silsesquioxane, and these fillers can be filled with organoalkoxysilane compounds, organochlorosilane compounds, organic Fillers for surface hydrophobization of organic silicon compounds such as silazane compounds and low molecular weight siloxane compounds; polysilicone rubber powder, polysiloxy resin powder, etc. Regarding this component, it is particularly preferable to use a filler that can impart thixotropy. By imparting thixotropy, a cured product with excellent workability and grain shear strength can be obtained.

These other components may be used alone or in combination of two or more.

In addition, since the workability of die bonding (transfer method) becomes better, the viscosity of the addition curable polysiloxane resin composition of the present invention is preferably 5~100 Pa･s at 25°C, and more preferably 20~ 50Pa･s.

[hardened material] Furthermore, the present invention provides a cured product (polysiloxane cured product) of the addition-curable polysiloxane composition.

The addition-hardening polysiloxane composition of the present invention can be hardened under conventional conditions. For example, it can be hardened at 100 to 180° C. for 10 minutes to 5 hours.

The hardened product of the addition-hardening polysiloxane composition of the present invention can be used as a die bonding material for compositions with high adhesion to substrates, LED chips, etc., especially for die bonding of LED components, etc. As described above, the polysiloxane cured product of the present invention can be used to form an adhesive with high adhesion to substrates, LED chips, etc.

[Optical semiconductor device] Furthermore, the present invention provides an optical semiconductor device in which an optical semiconductor element is die-bonded using the above-mentioned hardened material.

An example of a method for die bonding an optical semiconductor element using the composition of the present invention is to fill a syringe with the composition of the present invention, use a dispenser, and dry it on a substrate such as a package to a thickness of 5 to 100 μm. After coating with a thickness of 0.05 Å, an optical semiconductor element (such as a light emitting diode) is arranged on the coated composition, and the optical semiconductor element grain is bonded to the substrate by hardening the composition. Alternatively, the composition may be placed on a squeegee pan, and the composition may be applied to the substrate by stamping using the squeegee so that the dry state becomes a thickness of 5 to 100 μm, and then placed on the coated composition. An optical semiconductor element is a method of bonding the optical semiconductor element grains to a substrate by hardening the composition. The hardening conditions of the composition can be the same as above. In this way, a highly reliable optical semiconductor device in which an optical semiconductor element is bonded with the polysiloxane hardened material grains of the present invention can be produced.

[Example]

The following examples will be used to specifically illustrate the present invention, but these examples do not limit the present invention in any way. In addition, the molecular weight is the weight average molecular weight in terms of standard polystyrene by colloidal permeation chromatography (GPC). The viscosity at 25°C is the value measured by a rotational viscometer. In addition, the meaning of the abbreviation of each siloxane unit is as follows.

[Synthesis Example 1] In a 3,000 mL 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, [(CH ₃ O) ₃ SiO _1/2 ] ₂ [(CH ₃ O) ₂ SiO] ₂ was added It represents 352.5g of organopolysiloxane, 45.6g of hexavinyldisiloxane, 182.3g of hexamethyldisiloxane, 58g of isopropyl alcohol, and 6.7g of methanesulfonic acid was dropped while stirring. Thereafter, 90 g of water was dropped, and the mixture was mixed at 65° C. for 2 hours to react. After adding 700 g of hexene therein, 10.9 g of a 50% potassium hydroxide aqueous solution was added, the temperature was raised to distill off the low boiling point components, and the reaction was carried out at 120° C. for 5 hours. 3.5 g of methanesulfonic acid was added as an additive, and neutralization treatment was performed at 120° C. for 2 hours. After cooling, it was filtered to obtain a branched organopolysiloxane (B-1: molecular weight 3,350, vinyl content relative to solid content 0.287 mol/100g) with an average structure M ^Vi3 _0.07 M _0.4 Q _0.53 .

[Synthesis Example 2] Into a 3,000 mL 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, add [(CH3O) ₃ SiO _1/2 ] ₂ [(CH ₃ O) ₂ SiO] ₂ 353.5g of organopolysiloxane, 94.8g of hexavinyldisiloxane, 145.8g of hexamethyldisiloxane, 59g of isopropyl alcohol, and 7.5g of methanesulfonic acid were dropped while stirring. Thereafter, 90 g of water was dropped, and the mixture was mixed at 65° C. for 2 hours to react. After adding 800 g of hexene therein, 12.3 g of a 50% potassium hydroxide aqueous solution was added, the temperature was raised to distill off the low boiling point components, and the reaction was carried out at 120° C. for 5 hours. 3.9 g of methanesulfonic acid was added as an additive, and neutralization treatment was performed at 120° C. for 2 hours. After cooling, it was filtered to obtain a branched organopolysiloxane (B-2: molecular weight 3,630, vinyl content relative to solid content 0.567 mol/100g) with an average structure M ^Vi3 _0.14 M _0.32 Q _0.54 .

[Synthesis Example 3] In a 3000 mL 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer, add an organic compound represented by [(CH3O) ₃ SiO _1/2 ] ₂ [(CH ₃ O) ₂ SiO] ₂ 352.5g of polysiloxane, 38.6g of hexavinyldisiloxane, 133.7g of hexamethyldisiloxane, 52g of isopropyl alcohol, and 7.1g of methanesulfonic acid were dropped while stirring. Thereafter, 90 g of water was dropped, and the mixture was mixed at 65° C. for 2 hours to react. After adding 600 g of hexene thereto, 13.3 g of a 50% potassium hydroxide aqueous solution was added, the temperature was raised to distill off the low boiling point components, and the reaction was carried out at 120° C. for 5 hours. 4.3 g of methanesulfonic acid was added as an additive, and neutralization treatment was performed at 120° C. for 2 hours. After cooling, it was filtered to obtain a branched organopolysiloxane (B-3: molecular weight 7,890, vinyl content relative to solid content 0.263 mol/100g) with an average structure M ^Vi3 _0.07 M _0.33 Q _0.60 .

[Synthesis Example 4] In a 3000 mL 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, 408.0 g of methyltrimethoxysilane, 70.2 g of hexavinyldisiloxane, and dimethyldimethoxy were added. 63.0g of silane and 54g of isopropyl alcohol were added, and 6.8g of methanesulfonic acid was added dropwise while stirring. Thereafter, 90 g of water was dropped, and the mixture was mixed at 65° C. for 2 hours to react. After adding 600 g of hexene thereto, 11.1 g of a 50% potassium hydroxide aqueous solution was added, the temperature was raised to distill off the low boiling point components, and the reaction was carried out at 120° C. for 5 hours. 3.5 g of methanesulfonic acid was added as an additive, and neutralization treatment was performed at 120° C. for 2 hours. After cooling, it was filtered to obtain a branched organopolysiloxane (B-4: molecular weight 2,890, vinyl content relative to solid content 0.586 mol/100g) with an average structure M ^Vi3 _0.14 D _0.14 T _0.72 .

[Comparative Synthesis Example 1] In a 3000 mL 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer, add [(CH3O) ₃ SiO _1/2 ] ₂ [(CH ₃ O) ₂ SiO] ₂ 352.5g of organopolysiloxane, 111.6g of 1,3-divinyltetramethyldisiloxane, 89.2g of hexamethyldisiloxane, 55g of isopropyl alcohol, and 7.0g of methanesulfonic acid were dropped while stirring. Thereafter, 90 g of water was dropped, and the mixture was mixed at 65° C. for 2 hours to react. After adding 550 g of hexene therein, 11.4 g of a 50% potassium hydroxide aqueous solution was added, the temperature was raised to distill off the low boiling point components, and the reaction was carried out at 120° C. for 5 hours. 3.7 g of methanesulfonic acid was added as an additive, and neutralization treatment was performed at 120° C. for 2 hours. After cooling, the mixture was filtered to obtain a branched organopolysiloxane (B-6: molecular weight 7,890) with an average structure M ^Vi _0.21 M _0.23 Q _0.56 .

[Synthesis Example 5] The reaction product of platinum hexachloride and 1,3-divinyltetramethyldisiloxane was prepared with a viscosity of 60 mPa･s and M ^Vi so that the platinum content became 0.004% by mass. ₂ Dilute linear dimethylpolysiloxane represented by D ₄₀ to prepare a platinum catalyst (D).

[Examples 1 to 5, Comparative Examples 1 to 3] The following components were mixed in the blending amounts shown in Table 1 to prepare an addition curable polysiloxane composition. In addition, the numerical value of each component in Table 1 is parts by mass. The [Si-H]/[Si-Vi] value is the hydrogen bonded to the silicon atom of the component (C) relative to the total number of alkenyl groups fully bonded to the silicon atom of the component (A) and (B). The ratio of the number of atoms (Si-H groups) (Molar ratio).

(A) Component: Branched organopolysiloxane represented by (A-1)M ^Vi _0.47 T _0.53 (viscosity at 25°C 17mPa･s) represented by (A-2)M ^Vi _0.0097 D _0.9903 (M ^Vi ₂ D ₂₀₄ ) represents linear dimethylpolysiloxane with both ends blocked by vinyl groups (viscosity 600mPa･s at 25°C)

(B)Ingredients: (B-1) Branched organopolysiloxane obtained in Synthesis Example 1 (B-2) Branched organopolysiloxane obtained in Synthesis Example 2 (B-3) Branched organopolysiloxane obtained in Synthesis Example 3 (B-4) Branched organopolysiloxane obtained in Synthesis Example 4

(Comparative ingredient): (B-5) Branched organopolysiloxane represented by M ^Vi _0.064 M _0.398 Q _0.538 (M ^Vi _1.2 M _7.4 Q ₁₀ ) (vinyl content relative to solid content: 0.085 mol/100g) (B-6) Branched organopolysiloxane obtained in Comparative Synthesis Example 1

(C) Ingredients: (C) Methylhydrogensiloxane represented by M _0.037 D _0.266 D ^H _0.697 (M ₂ D _14.5 D ^H ₃₈ )

(D)Ingredients: (D) Platinum catalyst obtained in Synthesis Example 5

Other ingredients: (E) Reaction inhibitor: 1-ethynylcyclohexanol (F-1) Adhesion promoter: Cyclic organopolysiloxane (F-2) expressed as D ^Vi ₄ Adhesion promoter: Triallyl isocyanurate (F-3) adhesion enhancer: a compound represented by the following formula (G) Organic peroxide: 1,6-bis(t-butylperoxycarbonyloxy)hexane

The following evaluation was performed on the addition curable polysiloxy resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3, and the results are shown in Table 2.

[hardness] The composition was poured into a mold to have a thickness of 2 mm, and the Type D hardness of the hardened product obtained by hardening at 150° C. for 4 hours was measured in accordance with JIS K6253.

[Grain shear strength] The composition was pressed into the silver-plated electrode part of the SMD5050 package (manufactured by I-CHIUN PRECSION INDUSTRY CO., resin part: polyphthalamide) using a die bonding machine (AD-830 manufactured by ASM Corporation). A quantitative transfer was performed, and an optical semiconductor element (EV-B35A, 35mil manufactured by SemiLEDs Co., Ltd.) was mounted on it. The prepared package was heated in an oven at 150° C. for 2 hours to harden the composition, and then the grain shear strength was measured using an adhesion tester (Series 4000 manufactured by Dage Corporation). A composition whose viscosity exceeds 100mPa･s and cannot be transferred by stamping is considered "non-transferable".

As shown in Table 2, any of the cured products in Examples 1 to 5 has excellent hardness and grain shear strength, and is excellent as a crystal bonding agent. On the other hand, in Comparative Examples 1 and 2, since component (B) does not have a trienylsilyl group (R ² ₃ SiO _1/2 unit), the crystal grain shear strength of the cured product is poor and insufficient as a binder. Crystal agent. In addition, although the component (B) of Comparative Example 3 contains a branched organopolysiloxane containing a trienylsilyl group, the component (A) has poor transferability due to its high viscosity and cannot perform grain bonding.

As mentioned above, the addition curable polysilicone resin composition of the present invention can obtain a polysilicone cured product with excellent hardness and grain shear strength, and can be especially used as a die bonding material for die bonding of optical semiconductor components and the like. . In particular, due to this feature, in the wire bonding step performed after the die bonding step, undesirable situations such as chip peeling or failure to bond are less likely to occur. Therefore, the optical semiconductor device is an optical semiconductor device in which the optical semiconductor element is die-bonded with the polysiloxane hardened material. In addition to higher reliability, the productivity of the device is also improved. Therefore, the addition curable polysiloxane resin composition and its cured product of the present invention have high utilization value in the technical field of optical semiconductor devices.

In addition, the present invention is not limited to the above-described embodiment. The above-mentioned embodiments are examples, and those having substantially the same configuration as the technical idea described in the patent application scope of the present invention and having the same effects are all included in the technical scope of the present invention.

Claims (6)

An addition-hardening polysiloxane resin composition is characterized by containing the following: (A) It is represented by the following average composition formula (1a) and has a viscosity of 500 mPa at 25°C. Branched organopolysiloxane below s, (R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (1a) (in the formula, a, b, e, f are numbers consistent with a+b>0, b+e>0, e+f>0 and a+b+e+f=1) (B ) A branched organopolysiloxane represented by the following average composition formula (2): 70 to 95 parts by mass, (R ¹ ₃ SiO ₁ ) based on 100 parts by mass of the total of component (A) and component (B) _/2 ) _h (R ² ₃ SiO _1/2 ) _i (R ² R ¹ ₂ SiO _1/2 ) _j (R ² R ¹ SiO) _k (R ¹ ₂ SiO) ₁ (R ² SiO _3/2 ) _m (R ¹ SiO _3/2 ) _n (SiO _4/2 ). (2) (In the formula, R ¹ and R ² are the same as above, h, i, j, k, l, m, n and o are respectively consistent with h≧0, i>0, j≧0, k≧0, l ≧0, m≧0, n≧0, and o≧0, but, m+n+o>0 and h+i+j+k+l+m+n+o=1) ( C) Organohydrogen polysiloxane, R ³ _p H _q SiO _(4-pq)/2 ( 3) (In the formula, R ³ is an alkenyl-free substituted or unsubstituted monovalent hydrocarbon group that may be the same or different, p and q are in compliance with 0.7≦p≦2.1, 0.001≦q≦1.0 and 0.8≦p +q≦3.0 number) (D) Platinum group metal catalyst. The addition curable polysiloxy resin composition according to claim 1, wherein at least 80 mol% of all monovalent hydrocarbon groups other than alkenyl groups bonded to silicon atoms in the composition are methyl groups. The addition curable polysiloxane resin composition according to claim 1 further contains an organic peroxide. The addition curable polysiloxy resin composition according to claim 3, wherein the organic peroxide is 1,6-bis(t-butylperoxycarbonyloxy)hexane. A polysilicone cured product, which is a cured product of the addition-curable polysilicone resin composition according to any one of claims 1 to 4. An optical semiconductor device in which an optical semiconductor element is die-bonded using the polysiloxane cured material described in claim 5.