JP2010285571A - Silicone resin composition for die bonding - Google Patents

Abstract

Silicone resin useful for die bonding of LED elements and the like, which can give a cured product having high hardness, excellent heat resistance, transparency and light transmittance in a low wavelength region, and exhibiting high die shear strength. A composition is provided.
(A) A linear organopolysiloxane represented by the formula (1):
(B) a three-dimensional network organopolysiloxane resin represented by the formula (2) and waxy or solid at 23 ° C.
(C) an organohydrogenpolysiloxane represented by formula (3) and having at least two hydrogen atoms bonded to silicon atoms in one molecule;
(D) a platinum group metal catalyst,
(E) A silicone resin composition for die bonding containing fumed silica.
[Selection figure] None

Description

  The present invention relates to a silicone resin composition useful for die bonding of a light emitting diode (hereinafter referred to as “LED”) element or the like.

  Conventionally, an epoxy resin is used as a sealing material for LED elements and a die bonding material (that is, an adhesive for bonding a die such as an LED element and a substrate such as a package). In particular, if the resin is too soft in the die bond material, there is a problem that bonding cannot be performed in the wire bonding process performed after the die bond process. Therefore, conventionally, as the die bond material, an epoxy resin that is a high-hardness adhesive is used. Have been used. However, when used for blue LEDs, white LEDs, etc., the sealing material and die bond material made of epoxy resin may be yellowed by strong ultraviolet rays and absorb light. There is a problem.

  In recent years, expectations for the durability of LEDs have further increased, and the sealing material of LED elements has been replaced by epoxy resins having good durability instead of epoxy resins. Like the sealing material, the die bond material is also required to have durability. Further, it is expected that the die bond material is required to further improve the heat resistance as well as the luminance. There is a possibility that more LEDs will be used in the future from the viewpoint of glossiness.

From such a viewpoint, a die bond material using a silicone resin has been developed. However, since the silicone die-bonding material is inferior to the conventional epoxy resin in terms of elastic modulus and adhesive force, the die shear strength may be insufficient.
In addition, the following literature is mentioned as a prior art relevant to this invention.

JP 2002-60719 A JP 2006-342200 A JP 2007-63299 A JP 2007-258317 A

  The present invention has been made in view of the above circumstances, and can provide a cured product having high hardness, excellent heat resistance, transparency, and light transmittance in a low wavelength region, and high die shear strength. It aims at providing the silicone resin composition useful for die bonding of LED element etc. to show.

  As a result of intensive studies to achieve the above object, the present inventor has (A) a linear organopolysiloxane represented by an average composition formula (1) and (B) an average composition formula (2). A waxy or solid three-dimensional network organopolysiloxane resin at 23 ° C., (C) an organohydrogen represented by an average composition formula (3) and having at least two hydrogen atoms bonded to silicon atoms in one molecule Silicone resin composition for die bonding containing specific amounts of polysiloxane, (D) platinum group metal catalyst and (E) fumed silica has high hardness, heat resistance, transparency and light transmission in low wavelength region It has been found that a cured product having excellent properties and high die shear strength can be provided, and is useful for die bonding of LED elements and the like, and has led to the present invention.

Therefore, this invention provides the silicone resin composition for die bonding shown below.
[Claim 1]
(A) The following average composition formula (1):
(R ³ ₃ SiO _1/2 ) ₂ (R ¹ R ² SiO) _x (R ² ₂ SiO) _y (1)
(Wherein R ¹ independently represents an alkenyl group, R ² independently represents a monovalent hydrocarbon group containing no aliphatic unsaturated bond, and at least 80 mol% of all R ² is a methyl group; ³ is R ¹ or R ^2. x is an integer of 1 or more, y is an integer of 3 or more, and is a number satisfying 0.01 ≦ x / y ≦ 0.30.
Linear organopolysiloxane represented by: 40 to 10 parts by mass,
(B) The following average composition formula (2):
(R ⁵ ₃ SiO _1/2 ) _k (R ⁴ R ⁵ ₂ SiO _1/2 ) _m (R ⁴ R ⁵ SiO) _n (R ⁵ ₂ SiO) _p
(R ⁴ SiO _3/2 ) _q (R ⁵ SiO _3/2 ) _r (SiO ₂ ) _s (2)
(In the formula, R ⁴ independently represents an alkenyl group, R ⁵ independently represents a monovalent hydrocarbon group containing no aliphatic unsaturated bond, and at least 80 mol% of all R ⁵ is a methyl group; > K ≧ 0, 1> m ≧ 0, 1> n ≧ 0, 1> p ≧ 0, 1> q ≧ 0, 1> r ≧ 0 and 1> s ≧ 0, and m + n + q> 0, q + r + s> 0. And a number satisfying k + m + n + p + q + r + s = 1.)
And a waxy or solid three-dimensional network organopolysiloxane resin at 23 ° C .: 60 to 90 parts by mass (provided that the total of component (A) and component (B) is 100 parts by mass).
(C) The following average composition formula (3):
R ⁶ _a H _b SiO _{(4-ab) / 2} (3)
(In the formula, R ⁶ independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, provided that at least 50 mol% of all R ⁶ is a methyl group; (7 ≦ a ≦ 2.1, b is a number satisfying 0.001 ≦ b ≦ 1.0, where a + b is a number satisfying 0.8 ≦ a + b ≦ 3.0.)
And an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule: (C) component with respect to all silicon atom-bonded alkenyl groups in component (A) and component (B) An amount in which hydrogen atoms bonded to silicon atoms are 0.5 to 5.0 times mol,
(D) Platinum group metal catalyst: effective amount, and (E) fumed silica: silicone resin composition for die bonding containing 1 to 20 parts by mass with respect to 100 parts by mass in total of components (A) to (C). object.
[Claim 2]
2. The composition according to claim 1, wherein in the components (A) to (C) in the composition, 90 mol% or more of all monovalent hydrocarbon groups bonded to silicon atoms other than alkenyl groups are methyl groups.
[Claim 3]
The composition according to claim 1 or 2, wherein a Shore D hardness of a cured product obtained by curing the composition is 30 or more.

  The composition of the present invention can provide a cured product having high hardness (Shore D hardness of 30 or more in a preferred embodiment) and high die shear strength, and is particularly useful as a die bond material used for die bonding of LED elements and the like. It is a thing.

Hereinafter, each component will be described in detail. In the present specification, “Me” represents a methyl group, and “Vi” represents a vinyl group.
The composition of the present invention comprises the following components (A) to (E).

<(A) component>
The component (A) is a component for reducing the viscosity of the composition, causing stress relaxation after the composition is cured, and increasing the die shear strength. The component (A) has the following average composition formula (1):
(R ³ ₃ SiO _1/2 ) ₂ (R ¹ R ² SiO) _x (R ² ₂ SiO) _y (1)
(Wherein R ¹ independently represents an alkenyl group, R ² independently represents a monovalent hydrocarbon group containing no aliphatic unsaturated bond, and at least 80 mol% of all R ² is a methyl group; ³ is R ¹ or R ^2. x is an integer of 1 or more, y is an integer of 3 or more, and is a number satisfying 0.01 ≦ x / y ≦ 0.30, x + y is a viscosity at 25 ° C. The range of 50 to 50,000 mPa · s is preferable.)
And a siloxane unit having an alkenyl group (R ¹ R ² SiO unit, hereinafter referred to as a D ^Vi unit (Vi is described as a representative alkenyl group, but is not limited to a vinyl group)) and It is a random copolymer of siloxane units (R ² ₂ SiO units, hereinafter referred to as D units) having no aliphatic unsaturated bonds, and both ends of the molecular chain are blocked with triorganosiloxy groups. It is an organopolysiloxane having a chain molecular structure.

In order to relieve stress after the composition is cured, the ratio of D ^Vi / D needs to be reduced to some extent, and in order to increase the die shear strength, the ratio of D ^Vi / D needs to be increased to some extent. That is, the ratio of D ^Vi / D (x / y in the above formula (1)) needs to be 0.01 ≦ D ^Vi /D≦0.30, particularly 0.02 ≦ D ^Vi / D ≦ 0. .15 is preferred. When this ratio is too small, stress relaxation of the cured product is lost, and cracks are likely to occur. When this ratio is too large, the die shear strength is lowered.

The alkenyl group bonded to the silicon atom (R ¹ in the above formula (1)) usually has 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group, and a vinyl group is preferable.

In the organopolysiloxane molecule of component (A), the organic group bonded to the silicon atom other than the aliphatic unsaturated bond (R ² in the above formula (1)) does not have an aliphatic unsaturated bond. There is no particular limitation as long as it is, for example, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12, preferably 1 to 10, carbon atoms. Examples of the unsubstituted or substituted monovalent hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a cycloalkyl group such as a cyclohexyl group; Aryl groups such as a group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as a benzyl group and a phenethyl group; some or all of hydrogen atoms of these groups are halogen atoms such as a chlorine atom, a fluorine atom and a bromine atom Examples thereof include halogenated alkyl groups such as substituted chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group, preferably an alkyl group, and more preferably a methyl group.

  In the present invention, at least 80 mol% (80 to 100 mol%), preferably 90 to 100 mol%, more preferably 98 to 100 mol in all organic groups bonded to silicon atoms other than the aliphatic unsaturated bonds. % Is a methyl group. When the methyl group is less than 80 mol% of all organic groups bonded to silicon atoms other than the aliphatic unsaturated bond, light resistance and weather resistance are lowered, and the cured product is easily discolored.

  The viscosity of the organopolysiloxane (A) at 25 ° C. is preferably 50 to 50,000 mPa · s, more preferably 100 to 10,000 mPa · s. If the viscosity is too low or too high, the workability of the die bond material may be reduced. In the present invention, the viscosity is a value measured with a rotational viscometer (hereinafter the same).

The organopolysiloxane of component (A) is represented by, for example, the following average composition formula (4).
R ⁷ _c R ⁸ _d SiO _{(4-cd) / 2} (4)
(Wherein, R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds independently, R ⁸ is independently an alkenyl group, c is the 1.7 to 2.1 The number d is a number from 0.01 to 0.3, provided that c + d satisfies 2.0 to 2.2.

The above average composition formula (4), the monovalent hydrocarbon radical unsubstituted or substituted no aliphatic unsaturated bond represented by R ⁷ is an organic group bonded to a silicon atom other than the aliphatic unsaturated bonds It is the same kind as what was illustrated as. Moreover, the alkenyl group represented by R ⁸ is the same kind as that exemplified as the alkenyl group bonded to the silicon atom.

Examples of the organopolysiloxane of the component (A) include the following general formulas (5) to (8):
R ⁹ ₃ SiO (ViR ⁹ SiO) _e (R ⁹ ₂ SiO) _f SiR ⁹ ₃ (5)
ViR ⁹ ₂ SiO (ViR ⁹ SiO) _e (R ⁹ ₂ SiO) _f SiR ⁹ ₂ Vi (6)
Vi ₂ R ⁹ SiO (ViR ⁹ SiO) _e (R ⁹ ₂ SiO) _f SiR ⁹ Vi ₂ (7)
Vi ₃ SiO (ViR ⁹ SiO) _e (R ⁹ ₂ SiO) _f SiVi ₃ (8)
(Wherein, R ⁹ represents a substituted or unsubstituted monovalent hydrocarbon radical independently contains no aliphatic unsaturated bonds, e + f is 10 to 1,000, preferably 50 to 500, e / f is 0.01 to 0.30, preferably 0.02 to 0.15.)
What is represented by etc. is illustrated.

In the general formula (5) to (8), monovalent hydrocarbon radical unsubstituted or substituted as represented by R ⁹ has a number of carbon atoms, preferably 1 to 10, more preferably those of 1 to 6 is there. Specific examples thereof include those exemplified as an organic group bonded to a silicon atom other than the aliphatic unsaturated bond, and among them, the same type as those other than an aryl group and an aralkyl group may be mentioned. And since it is excellent in heat resistance, it is more preferably an alkyl group, particularly preferably a methyl group.

（式中、ｘ、ｙは上記と同じである。）
で表されるものが好ましい。 The organopolysiloxane of component (A) is, for example,

(Wherein x and y are the same as above)
The thing represented by these is preferable.

等が挙げられる。
（Ａ）成分は、一種単独で用いても二種以上を併用してもよい。 As a specific example of the component (A),

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

<(B) component>
The component (B) is a component for obtaining reinforcing properties while maintaining the transparency of the cured product. The component (B) is represented by the following average composition formula (2) and is waxy or solid at 23 ° C., and in the molecule, an alkenyl group bonded to a silicon atom, a trifunctional siloxane unit and / or SiO _{4. This is} a three-dimensional network-like organopolysiloxane resin that essentially contains ₂ units. In addition, “wax” means a gum (raw rubber) that shows no self-fluidity at 23 ° C. of 10,000,000 mPa · s or more, particularly 100,000,000 mPa · s or more. means.

(R ⁵ ₃ SiO _1/2 ) _k (R ⁴ R ⁵ ₂ SiO _1/2 ) _m (R ⁴ R ⁵ SiO) _n (R ⁵ ₂ SiO) _p
(R ⁴ SiO _3/2 ) _q (R ⁵ SiO _3/2 ) _r (SiO ₂ ) _s (2)
Wherein R ⁴ represents an alkenyl group, R ⁵ represents a monovalent hydrocarbon group containing no aliphatic unsaturated bond, and at least 80 mol% of all R ⁵ is a methyl group, and 1> k ≧ 0 1> m ≧ 0, 1> n ≧ 0, 1> p ≧ 0, 1> q ≧ 0, 1> r ≧ 0 and 1> s ≧ 0, and m + n + q> 0, q + r + s> 0, and k + m + n + p + q + r + s = A number that satisfies 1.)

In the average composition formula (2), the alkenyl group represented by R ⁴ is the same as the alkenyl group represented by R ¹ in the formula (1) of the component (A), but is available. A vinyl group is preferable from the viewpoint of ease of use and price.

The monovalent hydrocarbon group not containing an aliphatic unsaturated bond represented by R ⁵ is an organic compound bonded to a silicon atom other than the aliphatic unsaturated bond represented by R ² in the formula (1) of the component (A). The same as those exemplified as the group, but at least 80 mol% (80 to 100 mol%), preferably 90 to 100 mol%, more preferably 98 to 100 mol% of the total R ⁵ is a methyl group. . When the proportion of methyl groups is less than 80 mol% of the total R ⁵ , the composition becomes cloudy because of poor compatibility with the component (A), and the desired highly transparent cured product is obtained. There may not be.

k is 0 to 0.65, m is 0 to 0.65, n is 0 to 0.5, p is 0 to 0.5, q is 0 to 0.8, r is 0 to 0.8, s is The number is preferably 0 to 0.6. Further, m + n + q is preferably a number of 0.1 to 0.8, particularly 0.2 to 0.65, and q + r + s is a number of 0.1 to 0.8, particularly 0.2 to 0.6. It is preferable.
Moreover, it is preferable that the polystyrene conversion weight average molecular weight in GPC (gel permeation chromatograph) of the organopolysiloxane resin of (B) component is 400-100,000, It is preferable that it is 500-50,000 especially.

  In the component (B), the content of the alkenyl group bonded to the silicon atom is preferably in the range of 0.01 to 1 mol, and in the range of 0.05 to 0.5 mol, per 100 g of the component (B). Is more preferable. When the content of the alkenyl group satisfies the range of 0.01 to 1 mol, the crosslinking reaction proceeds sufficiently, and a cured product with higher hardness can be obtained.

The organopolysiloxane resin of component (B) is, for example,
(R ⁵ ₃ SiO _1/2 ) _k (R ⁴ R ⁵ ₂ SiO _1/2 ) _m (SiO ₂ ) _s
(R ⁴ R ⁵ ₂ SiO _1/2 ) _m (SiO ₂ ) _{s
^{(R 4 R 5 SiO) n}} (R 5 2 SiO) p (R 5 SiO 3/2) r
(R ⁴ R ⁵ ₂ SiO _1/2 ) _m (R ⁵ ₂ SiO) _p (R ⁴ SiO _3/2 ) _q
(R ⁴ R ⁵ ₂ SiO _1/2 ) _m (R ⁵ ₂ SiO) _p (R ⁵ SiO _3/2 ) _r
(R ⁵ ₃ SiO _1/2 ) _k (R ⁴ R ⁵ ₂ SiO _1/2 ) _m (R ⁵ ₂ SiO) _p (R ⁵ SiO _3/2 ) _r
(R ⁵ ₃ SiO _1/2 ) _k (R ⁴ R ⁵ ₂ SiO _1/2 ) _m (R ⁴ R ⁵ SiO) _n (R ⁵ ₂ SiO) _p (R ⁵ SiO _3/2 ) _r
(In the formula, R ⁴ , R ⁵ , k, m, n, p, q, r and s are as defined in the average composition formula (2).)
The thing represented by these is preferable.

As a specific example of the component (B),
(Me ₃ SiO _1/2 ) _0.4 (ViMe ₂ SiO _1/2 ) _0.1 (SiO ₂ ) _0.5 ,
(ViMeSiO) _0.4 (Me ₂ SiO) _0.15 (MeSiO _3/2 ) _0.45 ,
(ViMe ₂ SiO _1/2 ) _0.2 (Me ₂ SiO) _0.25 (MeSiO _3/2 ) _0.55
Etc.
(B) A component may be used individually by 1 type, or may use 2 or more types together.

  The ratio of the component (B) to the component (A) is also an important factor of the composition of the present invention. (B) The compounding quantity of a component needs to be 60-90 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 65-80 mass parts, More preferably, it is 70. ~ 80 parts by mass. When the blending amount of the component (B) is less than 60 parts by mass, sufficient hardness may not be obtained, and when it exceeds 90 parts by mass, the viscosity of the composition becomes remarkably high, and the composition is LED Workability when used as a die-bonding material for an element or the like is significantly reduced.

<(C) component>
The component (C) acts as a crosslinking agent that crosslinks with the alkenyl group in the component (A) and the component (B) by a hydrosilylation reaction and dilutes the composition to a viscosity suitable for the intended use. Is a component that also works as a The component (C) is represented by the following average composition formula (3), and has at least two hydrogen atoms (that is, SiH groups) bonded to silicon atoms in one molecule (usually 2 to 200), preferably 3 It is an organohydrogenpolysiloxane having at least one (for example, about 3 to 100).

R ⁶ _a H _b SiO _{(4-ab) / 2} (3)
(In the formula, R ⁶ independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, provided that at least 50 mol% of all R ⁶ is a methyl group; (7 ≦ a ≦ 2.1, b is a number satisfying 0.001 ≦ b ≦ 1.0, where a + b is a number satisfying 0.8 ≦ a + b ≦ 3.0.)

In the average composition formula (3), the unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond represented by R ⁶ is represented by R ² in the formula (1) of the component (A). Are the same as those exemplified as the organic group bonded to the silicon atom other than the aliphatic unsaturated bond, but at least 50 mol% (50 to 100 mol%), preferably 60 to 100 mol% of the total R ⁶ Particularly preferably, 90 to 100 mol% is a methyl group. When the proportion of methyl groups is less than 50 mol% of the total R ⁶ , the compatibility with the component (A) and the component (B) is inferior, and there arises a problem that the composition becomes cloudy or phase separates.

  It is preferable that a is 1.0 to 2.0, b is 0.01 to 1.0, and a + b is 1.1 to 2.6.

  In the component (C), the content of hydrogen atoms bonded to the silicon atom is preferably in the range of 0.001 to 0.02 mol, and in the range of 0.002 to 0.017 mol, per gram of the component (C). It is more preferable that If the content of silicon-bonded hydrogen atoms is too small, sufficient hardness may not be obtained, and if it is too high, curability and heat resistance may be reduced.

  Hydrogen atoms bonded to silicon atoms contained in two or more, preferably three or more in one molecule (that is, SiH groups) may be located either at the end of the molecular chain or in the middle of the molecular chain. It may be located in both. The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or the degree of polymerization) is usually 2 to 400, preferably 3 to 200, and more preferably about 4 to 100.

  The organohydrogenpolysiloxane of component (C) has a viscosity at 25 ° C. of preferably 1,000 mPa · s or less (usually 1 to 1,000 mPa · s), more preferably 5 to 200 mPa · s.

Specific examples of the organohydrogenpolysiloxane of component (C) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydro Gendimethylsiloxy) methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, trimethyl at both ends Siloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group-blocked dimethylsiloxy Methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both-end trimethyl Siloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydro Gensiloxane / dimethylsiloxane / methylphenylsiloxane copolymer, (CH ₃ ) ₂ HSiO _1/2 unit and (CH ₃ ) ₃ SiO _1/2 Copolymer consisting of units and SiO _4/2 units, copolymer consisting of (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units, (CH ₃ ) ₂ HSiO _1/2 units and SiO _{4 / 2} units and a copolymer composed of (C ₆ H ₅ ) ₃ SiO _1/2 units, and the following general formulas (9) and (10):
R ⁶ ₃ SiO (R ⁶ HSiO) _t SiR ⁶ ₃ (9)
Annular (R ⁶ HSiO) _u (10)
(Wherein R ⁶ is as described above, t is an integer of 2 to 30, preferably 2 to 25, and u is an integer of 4 to 8)
Represented by the following general formula:

（式中、Ｒ⁶は前記の通りであり、ｈは５〜４０の整数、ｉは５〜２０の整数、ｊは２〜３０の整数である。）
で表されるもの等が例示される。

(Wherein, R ⁶ are as defined above, h is an integer of 5 to 40, i is 5-20 integer, j is an integer of 2 to 30.)
What is represented by etc. is illustrated.

Specific examples of the component (C) include the following general formula (11):
Me ₃ SiO (MeHSiO) _t SiMe ₃ (11)
(Wherein t is as described above.)
Represented by the following structural formula:

で表されるもの等が挙げられる。
（Ｃ）成分は、一種単独で用いても二種以上を併用してもよい。

The thing etc. which are represented by are mentioned.
(C) A component may be used individually by 1 type, or may use 2 or more types together.

  Component (C) is blended in an amount of 0.5 to 5 hydrogen atoms bonded to silicon atoms in component (C) relative to alkenyl groups bonded to all silicon atoms in components (A) and (B). It is necessary that the amount be 0.0 mol, and preferably 0.7 to 3.0 mol. When the blending amount does not satisfy the amount of 0.5 to 5.0 moles, the balance of crosslinking becomes inappropriate.

<(D) component>
The platinum group metal catalyst as component (D) is a component for proceeding and promoting the hydrosilylation reaction of the components (A) to (C). The platinum group metal catalyst is not particularly limited, and examples thereof include platinum group metals such as platinum, palladium, rhodium; chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, vinyl siloxane, or acetylene compounds. Examples include platinum compounds such as coordination compounds, platinum group metal compounds such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, etc., and good compatibility with the components (A) to (C). Since chloro impurities are hardly contained, chloroplatinic acid is preferably silicone-modified.
(D) A component may be used individually by 1 type, or may use 2 or more types together.

  (D) The compounding quantity of a component should just be an effective amount as a catalyst, However, Usually, it is 1-500 ppm in conversion of the mass of a platinum group metal element with respect to the sum total of (A)-(C) component, Preferably 3 to 100 ppm, particularly preferably 5 to 40 ppm. If this blending amount is appropriate, the hydrosilylation reaction can be promoted more effectively.

<(E) component>
The fumed silica as component (E) is a component for imparting thixotropy to the composition and improving workability, forming fillets, and improving die shear strength. The composition must be thinned for use in die bonding, and fumed silica with a small particle size is preferred.

The specific surface area of the fumed silica by the BET method is preferably 50 to 500 m ² / g, particularly preferably 100 to 400 m ² / g.

  The fumed silica is preferably surface-treated with silanes, silazanes or siloxanes in order to increase dispersibility in the composition.

  (E) The compounding quantity of a component is 1-20 mass parts normally with respect to a total of 100 mass parts of (A)-(C) component, Preferably it is 3-10 mass parts. When the blending amount is too small, the effect of imparting thixotropy is poor, and when it is too large, workability is deteriorated and the die shear strength is reduced.

<Other ingredients>
The composition of this invention may mix | blend the other component illustrated below other than the said (A)-(E) component, unless the objective of this invention is impaired.

Other components include, for example, light scattering agents or reinforcing materials such as crystalline silica; phosphors; petroleum solvents, viscosity modifiers such as non-reactive silicone oils that do not have reactive functional groups; carbon functional silanes Silicone compounds other than components (A) to (C) having at least one of alkenyl groups such as epoxy groups, alkoxy groups, hydrogen atoms bonded to silicon atoms (ie, SiH groups) and vinyl groups bonded to silicon atoms, etc. Adhesion improvers; conductivity imparting agents such as metal powders such as silver and gold; pigments and dyes for coloring; reaction inhibitors such as tetramethyltetravinyltetracyclosiloxane;
These other components may be used alone or in combination of two or more.

<About the composition>
In the components (A) to (C) in the composition of the present invention, 80 mol% or more (80 to 100 mol%) of all monovalent hydrocarbon groups bonded to silicon atoms other than aliphatic unsaturated bonds, particularly 90 It is excellent in heat resistance and light resistance (ultraviolet light resistance), and in resistance to deterioration including discoloration due to stress such as heat and ultraviolet rays, when the mol% or more (90 to 100 mol%) is a methyl group. Is preferable.

-Preparation method The composition of the present invention can be prepared by mixing the components (A) to (E) and optionally other components. For example, in order to ensure sufficient storage stability (C) The part containing the component and the part containing the component (D) can be prepared separately, and these two parts can be mixed and used at the time of use.

Curing conditions The composition may be cured under known conditions, for example, by heating at 60 to 180 ° C. for 10 minutes to 5 hours. Moreover, it is preferable that the Shore D hardness of the hardened | cured material obtained by hardening a composition is 30 or more, especially 50-90.

Application The composition of the present invention is particularly useful as a die bond material used for die bonding of LED elements and the like.

<Die bonding method>
As an example of a method for die-bonding an LED element using the composition of the present invention, a syringe is filled with the composition of the present invention, and a thickness of, for example, 5 to 100 μm is dried on a substrate such as a package using a dispenser. After the application, the LED element is placed on the applied composition, and the composition is cured, whereby the LED element is die-bonded on the substrate. The curing conditions for the composition may be as described above.

EXAMPLES Hereinafter, although this invention is demonstrated concretely using a preparation example, an Example, and a comparative example, these Examples do not restrict | limit this invention at all. In addition, in the following example, the symbol which shows the average composition of a silicone oil or a silicone resin shows the following units. The number of moles of each silicone oil or each silicone resin indicates the number of moles of vinyl groups or SiH groups contained in each component.
M ^H : (CH ₃ ) ₂ HSiO _1/2
M: (CH ₃ ) ₃ SiO _1/2
M ^Vi : (CH ₂ ═CH) (CH ₃ ) ₂ SiO _1/2
D ^H : (CH ₃ ) HSiO _2/2
D: (CH ₃ ) ₂ SiO _2/2
D ^Vi : (CH ₂ ═CH) (CH ₃ ) SiO _2/2
Q: SiO _4/2

[Preparation Example 1] Preparation of platinum catalyst The platinum catalyst used in this example is a reaction product of hexachloroplatinic acid and sym-tetramethyldivinyldisiloxane, and this reaction product has a platinum content of 1.0. This is a catalyst diluted with liquid dimethylvinylsiloxy-terminated polydimethylsiloxane having a viscosity of 0.6 Pa · s so as to have a mass% (catalyst A).

The component (E) in the present example used fumed silica (silica B) having an average particle diameter of 10 nm and a specific surface area of 300 m ² / g, and the surface treated with dimethylsiloxy units.

<Example 1>
Is composed of a M units and M ^Vi units and Q units, is 6.25 molar ratio of M units to M ^Vi units, in a molar ratio of the sum of M units and M ^Vi units to Q units is 0.8 80 g (65.6 mmol) of a silicone resin and 20 g (13.2 mmol, D ^Vi / D = 0) of silicone oil having a viscosity of 6,000 mPa · s and an average composition of M ₂ D ₄₁₆ D ^Vi ₂₂ .05), and 11 g (16.0 mmol) of methylhydrogensiloxane represented by the average structural formula: M ₂ ^DH ₈ . By removing toluene from the obtained liquid mixture at 120 ° C. under reduced pressure of 10 mmHg or less, a viscous liquid was obtained at room temperature.

で示されるエポキシ基含有シロキサン化合物５ｇ（４２．５ミリモル）を混合し、透明の液状混合物を得た。更に、この混合物１００質量部に対し、シリカＢを５質量部混合し、ダイボンディング用組成物を得た。この組成物を用いて、１ｍｍ×１ｍｍ、厚み０．３５ｍｍのシリコンチップを銀めっき上にダイボンディングした。加熱硬化条件は１００℃，１時間＋１５０℃，５時間とした。これを用いてダイシェア強度をダイボンディングテスタＰＴＲ−１０００（（株）レスカ製）により測定した。更に、同様の硬化条件で厚さ２ｍｍの板状成型物を作製し、ショアＤ硬度計によりショアＤ硬度を測定した。このときのダイシェア強度と硬度を表１に示す。 For 100 g of this viscous liquid, 0.1 g of ethynylcyclohexanol, 3 g (34.8 mmol) of tetramethyltetravinyltetracyclosiloxane, 0.30 g of catalyst A as a reaction control agent, and the following structural formula (12):

Was mixed with 5 g (42.5 mmol) of an epoxy group-containing siloxane compound represented by formula (II) to obtain a transparent liquid mixture. Furthermore, 5 parts by mass of silica B was mixed with 100 parts by mass of this mixture to obtain a composition for die bonding. Using this composition, a silicon chip having a size of 1 mm × 1 mm and a thickness of 0.35 mm was die-bonded on the silver plating. The heat curing conditions were 100 ° C., 1 hour + 150 ° C., 5 hours. Using this, the die shear strength was measured with a die bonding tester PTR-1000 (manufactured by Resuka Co., Ltd.). Furthermore, a plate-like molded product having a thickness of 2 mm was produced under the same curing conditions, and the Shore D hardness was measured with a Shore D hardness meter. Table 1 shows the die shear strength and hardness at this time.

<Example 2>
Is composed of a M units and M ^Vi units and Q units, is 6.25 molar ratio of M units to M ^Vi units, in a molar ratio of the sum of M units and M ^Vi units to Q units is 0.8 80 g (65.6 mmol) of a silicone resin in toluene solution and ₂₀ g (26.0 mmol, D ^Vi /D=0.11) of silicone oil having a viscosity of 700 mPa · s and an average composition formula: M ₂ D ₁₇₈ D ^Vi ₂₀ ), And 13 g (18.9 mmol) of methylhydrogensiloxane represented by the average structural formula: M ₂ ^DH ₈ . By removing toluene from the obtained liquid mixture at 120 ° C. under reduced pressure of 10 mmHg or less, a viscous liquid was obtained at room temperature.
With respect to 100 g of this viscous liquid, 0.1 g of ethynylcyclohexanol, 3 g (34.8 mmol) of tetramethyltetravinyltetracyclosiloxane, 0.30 g of catalyst A, and the above structural formula (12) are used as reaction control agents. 5 g (42.5 mmol) of an epoxy group-containing siloxane compound was mixed to obtain a transparent liquid mixture. Furthermore, 5 parts by mass of silica B was mixed with 100 parts by mass of this mixture to obtain a composition for die bonding. Using this composition, a silicon chip having a size of 1 mm × 1 mm and a thickness of 0.35 mm was die-bonded on the silver plating. The heat curing conditions were 100 ° C., 1 hour + 150 ° C., 5 hours. Using this, the die shear strength was measured in the same manner as in Example 1. Further, a plate-like molded product having a thickness of 2 mm was produced under the same curing conditions, and the hardness was measured in the same manner as in Example 1. Table 1 shows the die shear strength and hardness at this time.

<Comparative Example 1>
Is composed of a M units and M ^Vi units and Q units, is 6.25 molar ratio of M units to M ^Vi units, in a molar ratio of the sum of M units and M ^Vi units to Q units is 0.8 80 g (65.6 mmol) of a silicone resin and ₂₀ g (118.8 mmol, D ^Vi /D=1.0) of a silicone oil having a viscosity of 100 mPa · s and an average composition formula of M ₂ D ₂₀ D ^Vi ₂₀ And 24 g (348.0 mmol) of methylhydrogensiloxane represented by the average structural formula: M ₂ ^DH ₈ . By removing toluene from the obtained liquid mixture at 120 ° C. under reduced pressure of 10 mmHg or less, a viscous liquid was obtained at room temperature.
With respect to 100 g of this viscous liquid, 0.1 g of ethynylcyclohexanol, 3 g (34.8 mmol) of tetramethyltetravinyltetracyclosiloxane, 0.30 g of catalyst A, and the above structural formula (12) are used as reaction control agents. 5 g (42.5 mmol) of an epoxy group-containing siloxane compound was mixed to obtain a transparent liquid mixture. Furthermore, 5 parts by mass of silica B was mixed with 100 parts by mass of this mixture to obtain a composition for die bonding. Using this composition, a silicon chip having a size of 1 mm × 1 mm and a thickness of 0.35 mm was die-bonded on the silver plating. The heat curing conditions were 100 ° C., 1 hour + 150 ° C., 5 hours. Using this, the die shear strength was measured in the same manner as in Example 1. Further, a plate-like molded product having a thickness of 2 mm was produced under the same curing conditions, and the hardness was measured in the same manner as in Example 1. Table 1 shows the die shear strength and hardness at this time.

<Comparative example 2>
80 g (65.6 mmol) of a toluene solution of a silicone resin composed of M units, M ^Vi units, and Q units, and having a total molar ratio of M units and M ^Vi units to Q units of 0.8; 20 g (12.6 mmol, D ^Vi / D = 0) of silicone oil having an average composition formula of M ^Vi ₂ D ₅₀ and methyl structure siloxane represented by M ₂ ^DH ₈ 11 g (16.0 mmol) were mixed. By removing toluene from the obtained liquid mixture at 120 ° C. under reduced pressure of 10 mmHg or less, a viscous liquid was obtained at room temperature.
With respect to 100 g of this viscous liquid, 0.1 g of ethynylcyclohexanol, 3 g (34.8 mmol) of tetramethyltetravinyltetracyclosiloxane, 0.30 g of catalyst A, and the above structural formula (12) are used as reaction control agents. 5 g (42.5 mmol) of an epoxy group-containing siloxane compound was mixed to obtain a transparent liquid mixture. Furthermore, 5 parts by mass of silica B was mixed with 100 parts by mass of this mixture to obtain a composition for die bonding. Using this composition, a silicon chip having a size of 1 mm × 1 mm and a thickness of 0.35 mm was die-bonded on the silver plating. The heat curing conditions were 100 ° C., 1 hour + 150 ° C., 5 hours. Using this, the die shear strength was measured in the same manner as in Example 1. Further, a plate-like molded product having a thickness of 2 mm was produced under the same curing conditions, and the hardness was measured in the same manner as in Example 1. Table 1 shows the die shear strength and hardness at this time.

＊１ 割れてしまうため、測定不可能
＊２ 加熱後シリコーン硬化物にクラックが発生

* 1 Measurement is impossible because it breaks. * 2 Cracks occur in the cured silicone after heating.

Claims (3)

(A) The following average composition formula (1):
(R ³ ₃ SiO _1/2 ) ₂ (R ¹ R ² SiO) _x (R ² ₂ SiO) _y (1)
(Wherein R ¹ independently represents an alkenyl group, R ² independently represents a monovalent hydrocarbon group containing no aliphatic unsaturated bond, and at least 80 mol% of all R ² is a methyl group; ³ is R ¹ or R ^2. x is an integer of 1 or more, y is an integer of 3 or more, and is a number satisfying 0.01 ≦ x / y ≦ 0.30.
Linear organopolysiloxane represented by: 40 to 10 parts by mass,
(B) The following average composition formula (2):
(R ⁵ ₃ SiO _1/2 ) _k (R ⁴ R ⁵ ₂ SiO _1/2 ) _m (R ⁴ R ⁵ SiO) _n (R ⁵ ₂ SiO) _p
(R ⁴ SiO _3/2 ) _q (R ⁵ SiO _3/2 ) _r (SiO ₂ ) _s (2)
(In the formula, R ⁴ independently represents an alkenyl group, R ⁵ independently represents a monovalent hydrocarbon group containing no aliphatic unsaturated bond, and at least 80 mol% of all R ⁵ is a methyl group; > K ≧ 0, 1> m ≧ 0, 1> n ≧ 0, 1> p ≧ 0, 1> q ≧ 0, 1> r ≧ 0 and 1> s ≧ 0, and m + n + q> 0, q + r + s> 0. And a number satisfying k + m + n + p + q + r + s = 1.)
And a waxy or solid three-dimensional network organopolysiloxane resin at 23 ° C .: 60 to 90 parts by mass (provided that the total of component (A) and component (B) is 100 parts by mass).
(C) The following average composition formula (3):
R ⁶ _a H _b SiO _{(4-ab) / 2} (3)
(In the formula, R ⁶ independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, provided that at least 50 mol% of all R ⁶ is a methyl group; (7 ≦ a ≦ 2.1, b is a number satisfying 0.001 ≦ b ≦ 1.0, where a + b is a number satisfying 0.8 ≦ a + b ≦ 3.0.)
And an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule: (C) component with respect to all silicon atom-bonded alkenyl groups in component (A) and component (B) An amount in which hydrogen atoms bonded to silicon atoms are 0.5 to 5.0 times mol,
(D) Platinum group metal catalyst: effective amount, and (E) fumed silica: silicone resin composition for die bonding containing 1 to 20 parts by mass with respect to 100 parts by mass in total of components (A) to (C). object.   2. The composition according to claim 1, wherein in the components (A) to (C) in the composition, 90 mol% or more of all monovalent hydrocarbon groups bonded to silicon atoms other than alkenyl groups are methyl groups.   The composition according to claim 1 or 2, wherein a Shore D hardness of a cured product obtained by curing the composition is 30 or more.