TW201843282A - Silicone resin composition for die-bonding and cured product - Google Patents

Abstract

The present invention provides a silicon resin composition which provides a cured product having high thermal conductivity to have good workability and high adhesive strength and effectively dissipate heat generated from a chip, in a transfer method on a substrate. The silicon resin composition for die bonding comprises: linear organopolysiloxane (A) having at least two alkenyl groups bonded to a silicon atom in one molecule and having no alkoxy group bonded to the silicon atom; 3D net-like organopolysiloxane (B) represented by average composition formula (1); organohydrogenpolysiloxane (C) represented by average composition formula (2); straight chain organopolysiloxane (D) having at least one alkenyl group bonded to a silicon atom in one molecule, and having an alkoxy group bonded to a silicon atom at both molecular chain ends; a platinum group metal catalyst (E); and thermally conductive filler (F) having an average particle diameter of 0.1 [mu]m or more and less than 1 [mu]m.

Description

Silicone resin composition and hardened material for die bonding

The present invention relates to a silicone resin composition useful for the adhesion of crystal grains of light-emitting diode (hereinafter referred to as "LED") devices.

Conventionally, epoxy resin has been used as a die attaching agent (adhesive) for fixing LED elements (wafers). However, adhesives to which blue or white LED elements are fixed turn yellow due to long-term use. Similarly, the sealing material absorbs light and causes a decrease in brightness (Patent Document 1).

At present, the durability requirements of light-emitting devices using LEDs as modules have been further increased. Although LED sealing materials can be replaced with polysiloxane, die-attach agents are also required to have the same durability as sealing materials. In addition, as a method for bonding a light-emitting element to a substrate, a transfer method in which a die-bonding agent is formed into a thin film on a mesh plate and transferred to a substrate on which an LED element is provided by stamping has been widely used. Therefore, it is required for the die-bonding agent to have good workability at the time of adhesion by a transfer method.

In addition, the luminous efficiency of LEDs tends to decrease due to the deterioration of the components due to the increase in the temperature of the light-emitting element. Therefore, it is required to further improve the heat dissipation property of the die attaching agent. On the other hand, as a heat-dissipative grain adhesive polysiloxane, a polysiloxane composition having a thermally conductive filler is proposed (Patent Document 2). According to the conventional technology, although a composition having a thermal conductivity of 1 W / m ･ K or less can be obtained, with the increase in power in recent years, the thermal conductivity of the conventional heat-dissipating grain adhesive polysilicon has been improved. Insufficient language is required, and higher heat dissipation is required, specifically, a polycrystalline silicon adhesive having a thermal conductivity of 1 W / m ･ K or more. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-342200 [Patent Document 2] Japanese Patent Laid-Open No. 2015-93970

[Questions to be Solved by the Invention]

The present invention has been made in view of the above circumstances, and an object thereof is to provide a hardened product having a high thermal conductivity which can be imparted to a substrate with a good workability in a transfer method to a substrate, has a high adhesion force, and can efficiently dissipate heat generated from a wafer. Silicone resin composition. [Means to solve the problem]

In order to solve the above problems, the present invention provides a polysiloxane resin composition for crystal grain adhesion, which comprises: (A) an alkenyl group having at least two bonds to silicon atoms in one molecule, and no bond to silicon A linear alkoxy group at 25 ° C having a viscosity of 100 mm ² / s or less in a linear organic polysiloxane, (B) represented by the following average composition formula (1), which is waxy or solid at 23 ° C Three-dimensional reticulated organopolysiloxane: 60 to 90 parts by mass relative to 100 parts by mass of the aforementioned (A) component and the aforementioned (B) component, (In the formula, R ¹ may be the same or different. It is a substituted or unsubstituted monovalent hydrocarbon group without an aliphatic unsaturated bond, R ² is an alkenyl group, and a, b, c, d, e, f, and g are Meet the following numbers: a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0, g ≧ 0, b + c + e> 0, e + f + g> 0, and a + b + c + d + e + f + g = 1) (C) An organic hydrogen polysilicon oxide having at least 2 hydrogen atoms bonded to a silicon atom in a molecule represented by the following average composition formula (2) Alkanes: 0.5 to 5.0 times the hydrogen atoms bonded to silicon atoms in the (C) component with respect to all silicon atoms in the (A) component, (B) component, and (D) component. The amount of moore, (In the formula, R ³ may be the same or different. It is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and h and i are positive numbers satisfying the following: 0.7 ≦ h ≦ 2.1, 0.001 ≦ i ≦ 1.0 And 0.8 ≦ h + i ≦ 3.0) (D) A linear organic compound having at least one alkenyl group bonded to a silicon atom in one molecule and an alkoxy group bonded to a silicon atom at both ends of the molecular chain Polysiloxane: 3 to 30 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B), (E) Platinum group metal catalyst: with respect to the component (A) and (B) ) Component, (C) component and (D) component, calculated as the mass of the catalyst metal element is 1 ~ 500ppm, and (F) thermally conductive filler with an average particle size of 0.1 μm or more and less than 1 μm: It is 100 to 300 parts by mass with respect to a total of 30 parts by mass of the component (A), the component (B), the component (C), and the component (D).

According to these polysiloxane resin compositions, it is possible to impart a good workability in a transfer method to a substrate, and a hardened product having a high thermal conductivity and a high subsequent force, which can effectively dissipate heat generated from the wafer.

The (F) component preferably contains one or two or more kinds selected from zinc oxide and alumina.

According to these (F) components, it becomes a silicone resin composition which can provide hardened | cured material with more favorable heat radiation.

The component (D) is preferably a siloxane compound represented by the following formula (3), (In the formula, the arrangement of the repeating units of siloxane is arbitrary, and m and n are respectively positive numbers satisfying the following: 1 ≦ m ≦ 50, 0 ≦ n ≦ 100).

According to these (D) components, the effect of this invention can be acquired more efficiently.

Moreover, this invention provides the hardened | cured material obtained by hardening | curing the said silicone resin composition for crystal grain adhesion.

According to these hardened materials, they have high adhesive force, high strength, and heat generated from the wafer can effectively dissipate heat. [Inventive effect]

As described above, the silicone resin composition according to the present invention can provide a hardened product with high workability in a transfer method to a substrate, high thermal conductivity, and high heat generation, which can effectively dissipate heat generated from a wafer. Therefore, the polysiloxane resin composition is particularly useful as a die-bonding material for die-bonding of LED elements and the like.

As described above, a silicone resin composition has been developed which can impart good workability to the substrate transfer method, high hardening force, and high thermal conductivity of heat generated from the wafer to effectively dissipate heat.

As a result of repeated active research on the above-mentioned subject by the present inventors, it has been found that a polysiloxane resin composition containing the components (A) to (F) described later contains an alkoxy group having a bond to a silicon atom at both ends of a molecular chain The linear polyorganosiloxane based on the present invention can be filled with a thermally conductive filler, and the above-mentioned problems can be achieved, and the present invention has been completed.

That is, the present invention provides a polysiloxane resin composition for crystal grain adhesion, which comprises: (A) an alkenyl group having at least two bonds to silicon atoms in one molecule, and having no bond to silicon atoms; Linear siloxanes having an alkoxy group viscosity at 25 ° C of 100 mm ² / s or less, (B) represented by the following average composition formula (1), three times waxy or solid at 23 ° C Element net-like organic polysiloxane: 60 to 90 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B), (In the formula, R ¹ may be the same or different. It is a substituted or unsubstituted monovalent hydrocarbon group without an aliphatic unsaturated bond, R ² is an alkenyl group, and a, b, c, d, e, f, and g are Meet the following numbers: a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0, g ≧ 0, b + c + e> 0, e + f + g> 0, and a + b + c + d + e + f + g = 1) (C) An organic hydrogen polysilicon oxide having at least 2 hydrogen atoms bonded to a silicon atom in a molecule represented by the following average composition formula (2) Alkanes: 0.5 to 5.0 times the hydrogen atoms bonded to silicon atoms in the (C) component with respect to all silicon atoms in the (A) component, (B) component, and (D) component. The amount of moore, (In the formula, R ³ may be the same or different. It is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and h and i are positive numbers satisfying the following: 0.7 ≦ h ≦ 2.1, 0.001 ≦ i ≦ 1.0 And 0.8 ≦ h + i ≦ 3.0) (D) A linear organic compound having at least one alkenyl group bonded to a silicon atom in one molecule and an alkoxy group bonded to a silicon atom at both ends of the molecular chain Polysiloxane: 3 to 30 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B), (E) Platinum group metal catalyst: with respect to the component (A) and (B) ) Component, (C) component and (D) component, calculated as the mass of the catalyst metal element is 1 ~ 500ppm, and (F) thermally conductive filler with an average particle size of 0.1 μm or more and less than 1 μm: It is 100 to 300 parts by mass with respect to a total of 30 parts by mass of the component (A), the component (B), the component (C), and the component (D).

Hereinafter, the present invention is described in detail, but the present invention is not limited to these.

[Polysiloxane Resin Composition for Grain Adhesion] The silicone resin composition for grain adhesion of the present invention contains the following components (A) to (F). Hereinafter, each component will be described in detail.

<(A) component> (A) Component is an alkenyl group having at least 2 bonds to a silicon atom in one molecule and no alkoxy group bonded to a silicon atom. The viscosity at 25 ° C is 100 mm ² / Linear organopolysiloxane below s.

(A) The component is a component used to relax the stress after the composition is hardened. Usually, the main chain is a repeat of two organosiloxane units, and the two ends of the molecular chain are terminated by three organosiloxane groups. Molecular structure of organic polysiloxane. (A) When the viscosity of the component exceeds 100 mm ² / s, since this component functions as a soft segment that is more than necessary, it is difficult to obtain high hardness and high adhesion strength, and a problem that the viscosity of the composition is significantly increased occurs.

The alkenyl group bonded to the silicon atom described above is preferably vinyl, allyl, ethynyl, and the like having 2 to 10 carbon atoms, especially 2 to 6 alkenyl groups, particularly preferably vinyl. The molecule of the linear organic polysiloxane based on the (A) component of the ene-based silicon bond may be present at either the molecular chain end or the molecular chain side chain, or may exist in the two Of these, it is preferably present at both ends of the molecular chain.

(A) In the linear organic polysiloxane compound of the component, the organic group bonded to a silicon atom other than the alkenyl group is not particularly limited as long as it does not have an alkoxy group, but is preferably 1 carbon number ~ 8 substituted or unsubstituted monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group 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. Aralkyl groups such as benzyl and phenethyl, halogenated hydrocarbon groups such as chloromethyl, chloropropyl, and chlorocyclohexyl. An alkyl group is preferred, and a methyl group is particularly preferred.

The linear organic polysiloxane as the component (A) is preferably represented by the following average composition formula (4). (In the formula, R ⁴ may be the same or different, and is a substituted or non-substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, R ⁵ may be the same or different and is an alkenyl group, and j is a number of 1.9 to 2.1, k is a number from 0.005 to 1.0, and j + k satisfies 1.95 to 3.0).

In the above average composition formula (4), the substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond represented by R ⁴ may be exemplified by an organic group bonded to a silicon atom other than the alkenyl group described above. The instantiator is the same.

The alkenyl group represented by R ⁵ in the average composition formula (4) may be the same as those exemplified as the alkenyl group bonded to the silicon atom.

A specific example of the component (A) is a linear organic polysiloxane represented by the following formula. (In the formula, the arrangement of repeating units of siloxane is arbitrary).

(A) A component may be used individually by 1 type, and may use 2 or more types together.

<(B) component> (B) component is an essential component which maintains the transparency of a silicone resin composition, and is used for obtaining reinforcement. Specifically, the component (B) is a three-dimensional network-like organopolysiloxane represented by the following average composition formula (1) as waxy or solid at 23 ° C. The "wax-like" means a rubbery state (raw rubbery state) that does not show self-flowability at 23 ° C and is 10,000 Pa · s or more, especially 100,000 Pa · s or more. (In the formula, R ¹ may be the same or different. It is a substituted or unsubstituted monovalent hydrocarbon group without an aliphatic unsaturated bond, R ² is an alkenyl group, and a, b, c, d, e, f, and g are Meet the following numbers: a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0, g ≧ 0, b + c + e> 0, e + f + g> 0, and a + b + c + d + e + f + g = 1).

In the above average composition formula (1), the substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond represented by R ¹ may be exemplified by bonding to a silicon other than the alkenyl group in the component (A) described above. Atom organic groups are the same as those exemplified, and 80% or more of all R ¹ is preferably a methyl group. When the proportion of the methyl group is 80 mol% or more of all R ¹ , the compatibility with the component (A) is good, the composition is not white, and a highly transparent hardened material can be obtained.

In the above average composition formula (1), the alkenyl group represented by R ² may be the same as those exemplified as the alkenyl group bonded to the silicon atom in the component (A), but based on availability and price The aspect is preferably vinyl.

In the above average composition formula (1), a, b, c, d, e, f, and g are each a number satisfying the following: a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0, g ≧ 0, b + c + e> 0, e + f + g> 0 and a + b + c + d + e + f + g = 1, preferably a is 0 ~ 0.65, and b is 0 to 0.65, c is 0 to 0.5, d is 0 to 0.5, e is 0 to 0.8, f is 0 to 0.8, and g is a number from 0 to 0.6. And b + c + e is preferably a number from 0.1 to 0.8, especially 0.2 to 0.65, e + f + g is preferably from 0.1 to 0.8, and particularly preferably from 0.2 to 0.6.

The content of the alkenyl group bonded to the silicon atom in the component (B) is preferably in the range of 0.01 to 1 mol, more preferably in the range of 0.05 to 0.5 mol, per 100 g of the component (B). When the content is in the range of 0.01 to 1 mol, the cross-linking reaction proceeds sufficiently, and a hardened product with higher hardness is obtained.

(B) The organopolysiloxane based component has a branch structure. (B) The composition of the organopolysiloxane is composed of SiO _4/2 units and / or SiO _3/2 units (that is, SiO _4/2 units, R ² SiO _3/2 units, and / or R ¹ SiO _3/2 Unit) is necessary, but may further contain SiO _2/2 units such as methylvinylsiloxy units, dimethylsiloxy units, dimethylvinylsiloxy units, and SiO _1/2 units such as methylsiloxy units. The content of SiO _4/2 units and / or SiO _3/2 units is preferably 5 mol% or more of the total siloxane units in the organic polysiloxane resin of the component (B), more preferably 10 mol ~ 95 mol%, especially good for 20 ~ 60 mol%.

From the viewpoint of the ease of isolation of the organopolysiloxane of the component (B), the weight average molecular weight is preferably in the range of 500 to 100,000.

The ratio of the component (B) to the component (A) is also one of the important factors of the composition of the present invention. The amount of the component (B) must be 60 to 90 parts by mass, preferably 65 to 80 parts by mass, and more preferably 65 to 75 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). (B) When the blending amount of the component is less than 60 parts by mass, the adhesiveness may be poor and a hardened material with high hardness may not be obtained. When it exceeds 90 parts by mass, the viscosity of the composition becomes significantly higher, and the transfer becomes difficult. It is difficult to handle it when it is used in grain bonding materials.

Specific examples of the component (B) include, for example, the following.

(B) A component may be used individually by 1 type, and may use 2 or more types together.

<(C) component> (C) component functions as a crosslinking agent which crosslinks by the hydrosilylation reaction with the alkenyl group contained in (A) component, (B) component, and (D) component The component is an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule represented by the following average composition formula (2). (In the formula, R ³ may be the same or different. It is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and h and i are positive numbers satisfying the following: 0.7 ≦ h ≦ 2.1, 0.001 ≦ i ≦ 1.0 , And 0.8 ≦ h + i ≦ 3.0).

The compounding amount of the (C) component is 0.5 to about the silicon atom-bonded alkenyl group in the (A) component, (B) component, and (D) component. 5.0 times mole, preferably 0.7 to 3.0 times mole. When it is less than this range, crosslinking may not be sufficiently performed, and a hardened product with high hardness may not be obtained. When it is higher than this range, the cross-linking density is lowered, and the strength of the cured product may be reduced.

The content of the hydrogen atom bonded to the silicon atom in the component (C) is preferably in the range of 0.001 to 0.02 mol%, and more preferably in the range of 0.002 to 0.017 mol per 1 g of the component (C).

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

In the above average composition formula (2), the substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond represented by R ³ may be exemplified by bonding to a silicon other than the alkenyl group in the component (A) described above. Atom organic groups are the same as those exemplified, and it is preferred that at least 50 mole% of all R ³ be a methyl group. More preferably, 60 to 100 mole% is methyl. When the ratio of the methyl group is within the above range, the compatibility with the component (A) and the component (B) is excellent, and problems such as cloudiness and phase separation of the composition can be suppressed.

In the above average composition formula (2), h and i are positive numbers satisfying the following: 0.7 ≦ h ≦ 2.1, 0.001 ≦ i ≦ 1.0, and 0.8 ≦ h + i ≦ 3.0, preferably 1.0 ≦ h ≦ 2.0, 0.01 ≦ i ≦ 1.0, and 1.5 ≦ h + i ≦ 2.5.

The component (C) contains at least two hydrogen atoms bonded to a silicon atom in one molecule. The number of hydrogen atoms bonded to the silicon atom in one molecule is preferably 2 to 200, more preferably 3 to 100, and still more preferably 4 to 50.

In the component (C), the hydrogen atom bonded to the silicon atom may be located at any one of the molecular chain end and the molecular chain, or may be located at both of them. In addition, the molecular structure of the organohydrogenpolysiloxane of the component (C) may be any of linear, cyclic, branched, and three-dimensional network structures, and the number of silicon atoms (or degree of polymerization) in one molecule It is preferably 2 to 300, more preferably 3 to 200.

The organohydrogenpolysiloxane represented by the average composition formula (2) can be exemplified by 1,1,3,3-tetramethyldisilazane, 1,3,5,7-tetramethylcyclotetrasiloxane Oxane, tris (hydrodimethylsiloxy) methylsilane, tris (hydrodimethylsiloxy) phenylsilane, methyl hydrogen cyclopolysiloxane, methylhydrosiloxane, dimethyl Siloxane cyclic copolymer, trimethylsiloxy-terminated methylhydropolysiloxane at both ends, trimethylsiloxy-terminated dimethylsiloxane, methylhydrosiloxane copolymer at both ends Substance, dimethylhydrosiloxy-terminated dimethylpolysiloxane at both ends, dimethylhydrosiloxy-terminated dimethylhydrosiloxane at both ends, dimethylhydrosiloxy-terminated at both terminals Dimethylsiloxane-terminated, methylhydrosiloxane copolymer, trimethylsiloxane-terminated at both ends, methylhydrosiloxane-diphenylsiloxane copolymer, trimethylsiloxane at both ends Base-terminated methylhydrosiloxane, diphenylsiloxane, dimethylsiloxane copolymer, trimethylsiloxy-terminated methylhydrosiloxane, methylphenylsiloxane・ Dimethicone copolymer, dimethylhydrosiloxy-terminated methyl groups at both ends Siloxane, dimethylsiloxane, diphenylsiloxane copolymer, dimethylhydrosiloxy terminated methylhydrosiloxane, dimethylsiloxane, methylphenylsilicon Oxane copolymers and the like.

Specific examples of the component (C) include the following. (In the formula, the arrangement of repeating units of siloxane is arbitrary).

(C) A component may be used individually by 1 type, and may use 2 or more types together.

<(D) component> The (D) component is a linear organic polysilicon having at least one alkenyl group bonded to a silicon atom in one molecule, and an alkoxy group bonded to a silicon atom at both ends of the molecular chain. Oxane.

This component functions as a wetting agent, and contains an alkoxy group, and is an essential component for filling the (F) component mentioned later highly. Furthermore, in order to efficiently fill the component (F), the degree of polymerization of the component (D) is preferably 150 or less. If it is this range, the viscosity increase of a composition can be suppressed.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is particularly preferred.

The (D) component has at least one alkenyl group bonded to a silicon atom in one molecule. The number of alkenyl groups bonded to a silicon atom in one molecule is preferably from 1 to 50, more preferably from 1 to 20. When the molecule does not contain an alkenyl group, since the cross-linking reaction with the component (C) does not proceed, the component will bleed out from the LED chip after curing. When exudation occurs, not only the appearance of the product is impaired, but also the adhesion strength may be reduced, which is not good. In addition, if the number of alkenyl groups in one molecule is 50 or less, there is no fear that the cured product becomes brittle after the cross-linking reaction and the degree of adhesion is reduced.

Examples of the alkenyl group include the same as those exemplified for the alkenyl group bonded to the silicon atom in the component (A).

The blending amount of the component (D) is 3 to 30 parts by mass, preferably 10 to 25 parts by mass, and more preferably 12 to 20 parts by mass based on 100 parts by mass of the total of the components (A) and (B). When the blending amount is less than the above range, the (F) component described later cannot be filled with high efficiency, and workability during transfer is deteriorated, and a cured product having high thermal conductivity cannot be obtained. Moreover, when the compounding quantity of (D) component exceeds the said range, the hardness of hardened | cured material will fall, and the crystal shear strength may be inferior.

As an example of the component (D), a siloxane compound represented by the following formula (3) is exemplified. (In the formula, the arrangement of the repeating units of siloxane is arbitrary, and m and n are respectively positive numbers satisfying the following: 1 ≦ m ≦ 50, 0 ≦ n ≦ 100).

The following are examples of specific structural examples.

(D) A component may be used individually by 1 type, and may use 2 or more types together.

<(E) component> 的 The platinum group metal catalyst of the (E) component of the present invention promotes the bond between the alkenyl group in the (A) component, the (B) component, and the (D) component and the (C) component to Addition of silicon atoms to hydrogen atoms. Specific examples thereof include platinum-group metals such as platinum, palladium, rhodium, or platinum chloride, platinum modified by alcohol, platinum chloride chloride, platinum chloride acid, and complex compounds of olefins, ethylene siloxanes, or acetylene compounds. Platinum group metal compounds such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium, especially platinum-based compounds.

(E) A component may be used individually by 1 type, and may use 2 or more types together.

(E) The compounded amount of the component is an effective amount of the catalyst, and is converted to 1 by the mass of the catalyst metal element relative to the total amount of the (A) component, (B) component, (C) component, and (D) component. The range is from ~ 500 ppm, preferably from 1 to 100 ppm. If it is in the said range, the reaction rate of an addition reaction becomes appropriate, and the hardened | cured material which has high strength can be obtained.

<(F) component> 之 The (F) component of the present invention is a thermally conductive filler that imparts thermal conductivity (heat dissipation) to the obtained silicone resin composition, and has an average particle diameter of 0.1 μm or more and less than 1 μm. .

Examples of the thermally conductive filler include zinc oxide, aluminum oxide, boron nitride, and aluminum nitride. Among these, from the viewpoints of thermal conductivity, moisture resistance, and average particle diameter, zinc oxide and aluminum oxide are preferred.

(F) A component may be used individually by 1 type, and may use 2 or more types together.

In order to efficiently dissipate heat from the light-emitting element, the average particle diameter of the thermally conductive filler must be 0.1 μm or more and less than 1 μm, preferably 0.1 to 0.9 μm, and more preferably 0.3 to 0.9 μm. When the average particle diameter is 1 μm or more, the thickness of the polysiloxane resin composition when used as a crystal grain bonding material becomes large, and the heat radiation property of heat generated from the following light-emitting element is deteriorated. On the other hand, when the average particle diameter is less than 0.1 μm, the viscosity of the composition becomes high, and the transferability deteriorates.

(F) The blending amount of the component is 100 to 300 parts by mass, and preferably 100 to 200 parts by mass, based on 30 parts by mass of the total of (A), (B), (C), and (D) components. . When the above-mentioned blending amount is less than 100 parts by mass, the intended thermal conductivity (1.0 W / mK or more) may not be obtained. When the above-mentioned compounding amount is more than 300 parts by mass, the viscosity of the obtained silicone resin composition becomes excessively high and stringiness occurs, and it is difficult to apply the composition by a transfer method.

<Other components> 成分 In the silicone resin composition of the present invention, depending on the purpose, components such as an adhesion promoter or a reaction inhibitor may be added.

As the adhesiveness-improving agent, from the viewpoint of imparting self-adhesion to the composition of the present invention which is an addition reaction-hardening type, organosilicon compounds such as silanes and siloxanes containing functional groups that impart adhesiveness, non-silicon compounds, Polysiloxane-based organic compounds.

Specific examples of the functional group imparting adhesiveness include an alkenyl group or a hydrogen atom such as a vinyl group, an allyl group, or the like bonded to a silicon atom; an epoxy group (for example, γ-shrinking) bonded to a silicon atom through a carbon atom; Glyceryloxypropyl, β- (3,4-epoxycyclohexyl) ethyl, etc.), acryloxy (e.g. γ-acryloxypropyl, etc.), or methacryloxy (e.g. γ-methacryloxypropyl, etc.); alkoxysilyl (for example, may be bonded to a silicon atom through an alkylene group which may contain 1 to 2 ester structures, urethane structures, and ether structures Trimethoxysilyl, triethoxysilyl, alkoxysilyl such as methyldimethoxysilyl, etc.).

Examples of the organosilicon compound containing a functional group imparting adhesiveness include a silane coupling agent, a siloxane having an alkoxysilyl group and an organic functional group, and an alkoxysilane introduced into an organic compound having a reactive organic group. Based compounds.

Examples of the non-polysiloxane-based organic compound include an allyl organic acid, an epoxy ring-opening catalyst, an organic titanium compound, an organic zirconium compound, and an organic aluminum compound.

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-based compounds; hydrogen peroxide compounds; horses Maleic acid derivatives; 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, ethynylmethyldecylcarbitol, 1,3,5,7-tetramethyl A conventional compound such as -1,3,5,7-tetravinylcyclotetrasiloxane, which has a hardening inhibitory effect on the platinum group metal catalyst of the component (E).

The degree of the hardening inhibitory effect of the reaction inhibitor varies depending on the chemical structure of the reaction inhibitor. Therefore, it is desirable to adjust the amount of the reaction inhibitor to an optimum amount according to the reaction inhibitor used. Preferably, it is 0.001-5 mass parts with respect to 30 mass parts of the total of (A) component, (B) component, (C) component, and (D) component. If the blending amount is 0.001 parts by mass or more, the long-term storage stability of the composition at room temperature can be sufficiently obtained. When the blending amount is 5 parts by mass or less, the composition may be prevented from curing.

Examples of other optional components include inorganic fillers such as crystalline silica, hollow fillers, and silsesquioxane, and organic alkoxysilane compounds, organic chlorosilane compounds, organic silazane compounds, and low molecular weights. Organosilicon compounds such as siloxane compounds, fillers, etc., which are used to surface-hydrophobize these fillers; silicone rubber powder, silicone resin powder, etc.

In addition, in order to improve the workability of the transfer method, the measured value of the viscosity of the silicone resin composition of the present invention at 25 ° C is preferably 5 to 100 Pa ･ s, more preferably 20 to 50 Pa ･. s.

[Hardened product] Furthermore, the present invention provides a hardened product obtained by hardening the polysiloxane resin composition for crystal grain adhesion described above.

The hardening method and conditions of the silicone resin composition of the present invention can adopt conventional hardening methods and conditions. As an example, it can be cured at 100 to 180 ° C for 10 minutes to 5 hours.

The thermal conductivity of the cured product obtained by curing the silicone resin composition of the present invention is preferably 1.0 W / m ･ K or more, and the D-type hardness of the cured product is preferably 30 or more. The crystal grain shear strength is preferably 15 MPa or more at 25 ° C.

As described above, the silicone resin composition according to the present invention is a hardened product which can be imparted with good workability to a substrate transfer method, has a high bonding force, and can generate heat efficiently from a wafer and can dissipate heat efficiently. Polysiloxane resin composition. These silicone resin compositions are particularly useful as a die attach material for die attach of LED elements and the like. [Example]

Hereinafter, the present invention will be specifically described using synthesis examples, examples, and comparative examples, but the present invention is not limited to these. In addition, each symbol used here represents the following structure, respectively.

[Synthesis Example 1] A 500 mL 4-necked flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer was fed with a linear organic polysiloxane represented by M ^OH ₂ D ₇ D ^Vi (OH content: 0.18 mol / 100 g) 200 g, and 89 g of the compound represented by the following structural formula (I) was dropped with stirring. Subsequently, the mixture was mixed at 85 ° C for 2 hours for reaction, and cooled to 25 ° C. After cooling, 16 g of methanol was added and mixed at 25 ° C for 2 hours, and then concentrated under reduced pressure at 150 ° C for 1 hour to obtain a linear organic polysiloxane (D-1) represented by M ^OMe ₂ D ₉ D ^Vi .

[Synthesis Example 2] A 500 mL 4-necked flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer was fed with a linear organic polysiloxane represented by M ^OH ₂ D ₂₇ D ^Vi ₉ (OH content: 0.07 mol) / 100g) 200g, and 33g of the compound represented by the structural formula (I) was dropped while stirring. Subsequently, the mixture was mixed at 85 ° C for 2 hours for reaction, and cooled to 25 ° C. After cooling, 16 g of methanol was added and mixed at 25 ° C for 2 hours, and then concentrated under reduced pressure at 150 ° C for 1 hour to obtain a linear organic polysiloxane (D-2) represented by M ^OMe ₂ D ₂₉ D ^Vi ₉ .

[Synthesis Example 3] A 500 mL 4-necked flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer was fed with a linear organic polysiloxane represented by M ^OH ₂ D ₈ (OH amount: 0.18 mol / 100 g) 200 g, and 89 g of the compound represented by the structural formula (I) was dropped while stirring. Subsequently, the mixture was mixed at 85 ° C for 2 hours for reaction, and cooled to 25 ° C. After cooling, 16 g of methanol was charged and mixed at 25 ° C for 2 hours, and then concentrated under reduced pressure at 150 ° C for 1 hour to obtain a linear organic polysiloxane (D-3) represented by M ^OMe ₂ D ₁₀ .

[Examples 1 to 3, Comparative Examples 1 to 4] The following components were mixed in the blending amounts shown in Table 1 to prepare a silicone resin composition. In addition, the numerical value of each component in Table 1 shows a mass part. In addition, the viscosity is a value measured at 25 ° C using a rotary viscometer, and the [Si-H] / [Si-Vi] value indicates that the hydrogen atom bonded to the silicon atom in the (C) component is relative to the (A) component, ( Molar ratio of all silicon atom-bonded alkenyl groups in component B and component (D).

(A) Component: Vinyl-terminated linear dimethylpolysiloxane represented by (CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) ₂ ((CH ₃ ) ₂ SiO) ₁₀ Alkane (viscosity at 25 ° C 8.7 mm ² / s) (B) Composition: (CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) _1.2 ((CH ₃ ) ₃ SiO _1/2 ) _7.4 (SiO ₂ ) ₁₀ branched polysiloxane resin (solid at 23 ° C, vinyl content of solid content 0.085 mol / 100g) (C) component: ((CH ₃ ) ₃ SiO _1/2 ) ₂ ((CH ₃ ) ₂ SiO) _14.5 (H (CH ₃ ) SiO) ₃₈ methyl hydrogen polysilane D component: (D-1) Synthesis Example 1 linear dimethyl polysiloxane (D- 2) Linear dimethyl polysiloxane (D-3) prepared in Synthesis Example 2 Linear dimethyl polysiloxane (E) prepared in Synthesis Example 3 Components: Platinum hexachloride and 1, Siloxanes produced by the reaction of 3-divinyltetramethyldisilazane {viscosity 60mm ² / s, average molecular formula (CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) ₂ ((CH ₃ ) ₂ SiO) ₄₀ ) solution (platinum content is 0.004% by mass) (F) component: true spherical alumina with an average particle diameter of 0.9 μm (manufactured by Showa Denko, AL-47-1) (G) component: control agent ( 1-Ethynylcyclohexanol) (H) Component: Next Lifting agent (triallyl isocyanurate)

The following evaluations were performed on the silicone resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 4, and the results are shown in Table 2.

[Hardness of Hardened Product] 组成 The compositions obtained in the examples and comparative examples were heated at 150 ° C for 2 hours, and the D-type hardness of the obtained hardened product was measured in accordance with JIS K 6253.

[Thermal conductivity] 加热 The composition obtained in each example and each comparative example was heated at 150 ° C for 2 hours, and the obtained hardened product was subjected to a thin wire heating method (hot metal wire method, manufactured by Kyoto Electronics Industry Co., Ltd., a rapid thermal conductivity meter QTM-500 ) Measure.

[Transferability] The composition obtained in each example and each comparative example was prepared by using a crystal adhesive (manufactured by ASM, AD-830) for SMD5050 package (I-CHIUN PRECSION INDUSTRY CO., Company, resin PPA). ) The silver-plated electrode portion was quantitatively transferred by stamping, and evaluated for workability when an optical semiconductor element (SemiLED Corporation, EV-B35A, 35mil) was mounted thereon. If it is transferable, it is recorded as "good", and if it cannot be transferred, it is recorded as "bad".

[Adhesion] The package produced in the transferability evaluation test was heated in a 150 ° C. oven for 2 hours to harden the silicone resin composition. The measurement of the grain shear strength was performed using an adhesion tester (manufactured by Dage, Series 4000).

[Exudability] (2) Evaluation of transferability The package produced by the test was left at 25 ° C for 1 hour, and then the appearance was visually observed. If no bleeding out occurred around the wafer, it was recorded as "good", and when bleeding occurred, it was recorded as "bad".

As shown in Table 2, in Examples 1 to 3 in which the silicone resin composition of the present invention was used, the hardness of any hardened product was high, and the (D) component containing an alkoxy group and an alkenyl group was used as a wetting agent. It functions and blends a thermally conductive filler at a high content, and it is also excellent in transferability without oozing out, and it is excellent as a grain adhesive. In addition, the hardened material has a relatively high shear strength of about 20 MPa and a thermal conductivity of 1.3 W / m ･ K or more. It can be seen that the heat dissipation property is very excellent.

On the other hand, in Comparative Example 1, since the thermally conductive filler is small, the thermal conductivity is decreased by 0.9 W / m ･ K. In Comparative Example 2, the thermally conductive filler was filled with a high density, and although the thermal conductivity was high, the component (D) of the present invention was not contained, so the transferability was poor, and the LED chip could not be fixed. In Comparative Example 3, since the component (D) contains an alkoxy group and does not have an alkenyl group, although the thermal conductivity is high, the bleeding of the wetting agent and the reduction of the grain shear strength are caused, which damages the appearance and adhesion of the product. result. In Comparative Example 4, the blending amount of the component (B) was less than 50 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B), which was a result of poor crystal shear strength.

From these results, it can be seen that the silicone resin composition of the present invention has good workability for the substrate transfer method, can provide a hardened material with no bleeding, high adhesion, and high thermal conductivity.

The present invention is not limited to the embodiments described above. The above embodiment is an example. Anyone having substantially the same structure as the technical idea described in the patent application scope of the present invention and exhibiting the same function and effect is included in the technical scope of the present invention.

Claims (4)

A polysiloxane resin composition for crystal grain adhesion, which is characterized by: (A) an alkenyl group having at least two bonds to silicon atoms in one molecule, and an alkoxy group not bonded to silicon atoms; A linear organic polysiloxane having a viscosity at 25 ° C. of 100 mm ² / s or less, (B) a three-dimensional network organic which is waxy or solid at 23 ° C. as represented by the following average composition formula (1) Polysiloxane: 60 to 90 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B), (In the formula, R ¹ may be the same or different. It is a substituted or unsubstituted monovalent hydrocarbon group without an aliphatic unsaturated bond, R ² is an alkenyl group, and a, b, c, d, e, f, and g are Meet the following numbers: a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0, g ≧ 0, b + c + e> 0, e + f + g> 0, and a + b + c + d + e + f + g = 1) (C) An organohydrogenpolysiloxane having at least 2 hydrogen atoms bonded to a silicon atom in a molecule represented by the following average composition formula (2) Alkanes: 0.5 to 5.0 times the hydrogen atoms bonded to silicon atoms in the (C) component with respect to all silicon atoms in the (A) component, (B) component, and (D) component. The amount of moore, (In the formula, R ³ may be the same or different. It is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and h and i are positive numbers satisfying the following: 0.7 ≦ h ≦ 2.1, 0.001 ≦ i ≦ 1.0 And 0.8 ≦ h + i ≦ 3.0) (D) A linear organic compound having at least one alkenyl group bonded to a silicon atom in one molecule and an alkoxy group bonded to a silicon atom at both ends of the molecular chain Polysiloxane: 3 to 30 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B), (E) Platinum group metal catalyst: with respect to the component (A) and (B) ) Component, (C) component and (D) component, calculated as the mass of the catalyst metal element is 1 ~ 500ppm, and (F) thermally conductive filler with an average particle size of 0.1 μm or more and less than 1 μm: It is 100 to 300 parts by mass with respect to a total of 30 parts by mass of the component (A), the component (B), the component (C), and the component (D). The polysiloxane resin composition for crystal grain adhesion according to claim 1, wherein the component (F) contains one or two or more kinds selected from zinc oxide and alumina. For example, the polysiloxane resin composition for crystal grain adhesion of claim 1 or 2, wherein the component (D) is a siloxane compound represented by the following formula (3), (In the formula, the arrangement of the repeating units of siloxane is arbitrary, and m and n are respectively positive numbers satisfying the following: 1 ≦ m ≦ 50, 0 ≦ n ≦ 100). A hardened product obtained by hardening the silicone resin composition for crystal grain adhesion according to any one of claims 1 to 3.