JP7088880B2 - Additive-curable silicone resin composition, manufacturing method of the composition, and optical semiconductor device - Google Patents

Description

The present invention relates to an addition-curable silicone resin composition, a method for producing the composition, and an optical semiconductor device.

It has been proposed to use a silicone resin as a die-bonding material for a light-emitting diode (hereinafter referred to as "LED") element (Patent Documents 1 to 3). Since the silicone resin is superior in heat resistance, weather resistance, and discoloration resistance as compared with the conventional epoxy resin, it has been proposed to mainly use blue LEDs and white LEDs.

However, the die bond material made of these conventional silicone resin materials is mainly composed of a methyl-based silicone resin composition, which does not sufficiently satisfy the optical element performance, and does not necessarily have a particularly high light transmittance at 400 nm.
On the other hand, in Patent Document 4, an addition-curable silicone composition has a low refractive index due to a silicone composition containing a perfluoroalkyl group bonded to a silicon atom, and provides an elastomer having good transparency and excellent light extraction efficiency. A material and a sealing material for an optical element made of the composition have been proposed. However, the fluorosilicone resin having a perfluoroalkyl group has a large weight loss at high temperatures, and the hardness increases accordingly. Weight reduction and hardness increase cause serious errors such as cracks in LEDs, and a solution is desired.

Patent Document 5 reports a heat-resistant silicone rubber composition containing a rare earth salt mixture of 2-ethylhexanoic acid, and reports that the transmittance of light having a wavelength of 600 nm in a sheet having a thickness of 2 mm is 90% or more. Has been done. However, this heat-resistant silicone rubber composition has a problem that the light transmission of short wavelength light having a wavelength of around 400 nm is inferior. Further, such a heat-resistant imparting agent has a problem that it is incompatible with a fluorosilicone resin having a perfluoroalkyl group and separates with time, and the heat resistance of the cured product is not exhibited or the transparency is impaired. ..

Japanese Unexamined Patent Publication No. 11-1619 Japanese Unexamined Patent Publication No. 2002-265787 Japanese Unexamined Patent Publication No. 2004-186168 Japanese Unexamined Patent Publication No. 2013-010881 Japanese Patent No. 542755

The present invention has been made to solve the above problems, and is an addition-curable silicone that has a low refractive index and provides a cured silicone product having high transparency and little change in hardness and mass loss even when used under high temperature conditions. It is an object of the present invention to provide a resin composition.

In order to achieve the above problems, in the present invention,
(A) An alkenyl group bonded to two or more silicon atoms in one molecule and a group represented by CF _3- (CF ₂ ) _a- (CH ₂ ) _b -bonded to one or more silicon atoms (however). , A is an integer greater than or equal to 3 and b is an integer greater than or equal to 1).
(B) Organic silicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule: Silicon in the component (B) for one alkenyl group bonded to the silicon atom in the component (A). The amount of hydrogen atoms bonded to an atom is 0.5 to 5.0,
(C) Platinum group metal-based catalyst: An amount of 1 to 500 ppm in terms of mass of the platinum group metal with respect to the total mass of the component (A) and the component (B), and (D) the following i), ii). And iii) Reaction product of the component: 0.01 to 20 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
i) A group represented by CF _3- (CF ₂ ) _j- (CH ₂ ) _k- , which has a viscosity at 25 ° C. of 10 to 10,000 mPa · s and is bonded to at least one silicon atom in one molecule. Organopolysiloxane, having (where j is an integer greater than or equal to 3 and k is an integer greater than or equal to 1).
ii) Carboxylate of cerium-containing rare earth element: Amount of cerium in an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass of the above i) component.
iii) (R ⁴ O) ₄ Ti (in the formula, R ⁴ is a monovalent or different monovalent hydrocarbon group) or at least one of its partially hydrolyzed condensates: titanium is the i) component. Provided is an addition-curable silicone resin composition containing an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass.

This addition-curable silicone resin composition has a low refractive index, is excellent in light transmission at a wavelength of around 400 nm even when used under high temperature conditions, and provides a silicone cured product with little change in hardness and mass loss. ..

The component (B) is a group represented by CF _3- (CF ₂ ) _f- (CH ₂ ) _g -bonded to one or more silicon atoms in one molecule (where f is an integer of 0 or more, g is an integer of 1 or more).

When the component (B) has the fluoroalkyl group, the addition-curable silicone resin composition has a low refractive index, is excellent in light transmittance in the vicinity of a wavelength of 400 nm when used under high temperature conditions, and is excellent. , Gives a cured product with less change in hardness and loss of mass.

It is preferable that a = 5 and b = 2 in the component (A) and j = 5 and k = 2 in the component (D).

If the component (A) is an organopolysiloxane having the specific fluoroalkyl group and the component (D) is produced using the organopolysiloxane having the specific fluoroalkyl group, the addition thereof. The curable silicone resin composition has a low refractive index, is superior in light transmittance near a wavelength of 400 nm when used under high temperature conditions, and gives a silicone cured product having less change in hardness and less mass loss.

The addition-curable silicone resin composition preferably has a refractive index of light having a wavelength of 589 nm at 25 ° C. of 1.37 or less.
When the addition-curable silicone resin composition exhibits a refractive index of the predetermined value or less, the addition-curable silicone resin composition gives a silicone cured product having an excellent light extraction efficiency.

Further, in the present invention, the addition-curable silicone comprising a step of reacting the components i), ii) and iii) at a temperature of 150 ° C. or higher while bubbling an oxygen-containing gas to generate the component (D). A method for producing a resin composition is provided.

By the method for producing this addition-curable silicone resin composition, an addition that has a low refractive index, is excellent in light transmission at a wavelength of around 400 nm even when used under high temperature conditions, and gives a cured product with little change in hardness and weight loss. A curable silicone resin composition can be produced.

Further, the present invention provides a silicone cured product which is a cured product of the addition-curable silicone resin composition.

This silicone cured product has a low refractive index, is excellent in light transmission at a wavelength of around 400 nm even when used under high temperature conditions, and has little hardness change and mass loss.

The silicone cured product preferably has a transmittance of light having a wavelength of 400 nm at an optical path length of 2 mm and a transmittance of 80% or more.

The cured silicone product having a light transmittance of a predetermined value or higher is superior in light transmittance in the vicinity of a wavelength of 400 nm even when used under high temperature conditions.

In addition, the present invention provides an optical semiconductor device in which an optical semiconductor element is die-bonded with the cured silicone material, and an optical semiconductor device in which the optical semiconductor element is sealed with the cured silicone material.

These optical semiconductor devices are highly reliable.

The addition-curable silicone resin composition of the present invention provides a cured product having a low refractive index, excellent light transmission at a wavelength of around 400 nm even when used under high temperature conditions, and with little change in hardness and weight loss. Therefore, the additive-curable silicone resin composition of the present invention is used for protecting / encapsulating LED elements, wavelength changing / adjusting materials, die bonding materials, lens constituent materials, and other optical devices or optics. It is especially useful as a material for parts.

As described above, there has been a demand for the development of an addition-curable silicone composition having a low refractive index, excellent light transmittance in the vicinity of a wavelength of 400 nm when used under high temperature conditions, and little change in hardness and mass loss.

As a result of diligent studies on the above problems, the present inventors can achieve the above problems if the addition-curable silicone resin composition contains the following components (A) to (D), and is suitable as a material for LEDs and the like. We found that it would be a good thing, and completed the present invention.

That is, the present invention
(A) An alkenyl group bonded to two or more silicon atoms in one molecule and a group represented by CF _3- (CF ₂ ) _a- (CH ₂ ) _b -bonded to one or more silicon atoms (however). , A is an integer greater than or equal to 3 and b is an integer greater than or equal to 1).
(B) Organic silicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule: Silicon in the component (B) for one alkenyl group bonded to the silicon atom in the component (A). The amount of hydrogen atoms bonded to an atom is 0.5 to 5.0,
(C) Platinum group metal-based catalyst: An amount of 1 to 500 ppm in terms of mass of the platinum group metal with respect to the total mass of the component (A) and the component (B), and (D) the following i), ii). And iii) Reaction product of the component: 0.01 to 20 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
i) A group represented by CF _3- (CF ₂ ) _j- (CH ₂ ) _k- , which has a viscosity at 25 ° C. of 10 to 10,000 mPa · s and is bonded to at least one silicon atom in one molecule. Organopolysiloxane, having (where j is an integer greater than or equal to 3 and k is an integer greater than or equal to 1).
ii) Carboxylate of cerium-containing rare earth element: Amount of cerium in an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass of the above i) component.
iii) (R ⁴ O) ₄ Ti (in the formula, R ⁴ is a monovalent or different monovalent hydrocarbon group) or at least one of its partially hydrolyzed condensates: titanium is the i) component. It is an addition curable silicone resin composition containing an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
[Additionally curable silicone composition]
The addition-curable silicone resin composition of the present invention contains the components (A) to (D) described later.
(A) An alkenyl group bonded to two or more silicon atoms in one molecule and a group represented by CF _3- (CF ₂ ) _a- (CH ₂ ) _b -bonded to one or more silicon atoms (however). , A is an integer greater than or equal to 3 and b is an integer greater than or equal to 1).
(B) An organosilicon compound having two or more hydrogen atoms bonded to a silicon atom in one molecule,
(C) Platinum group metal catalyst,
(D) Reaction products of the following i), ii) and iii) components,
i) A group represented by CF _3- (CF ₂ ) _j- (CH ₂ ) _k- , which has a viscosity at 25 ° C. of 10 to 10,000 mPa · s and is bonded to at least one silicon atom in one molecule. Organopolysiloxane, having (where j is an integer greater than or equal to 3 and k is an integer greater than or equal to 1).
ii) Carboxylate of cerium-containing rare earth elements,
iii) (R ⁴ O) ₄ Ti (in the formula, R ⁴ is a homovalent or heterologous monovalent hydrocarbon group) at least one of the compound or a partially hydrolyzed condensate thereof.

Hereinafter, each component will be described in detail.
<Ingredient (A)>
The component (A) is represented by an alkenyl group bonded to two or more silicon atoms in one molecule and CF _3- (CF ₂ ) _a- (CH ₂ ) _b -bonded to one or more silicon atoms. It is an organopolysiloxane having a group (where a is an integer of 3 or more and b is an integer of 1 or more), and contributes to lowering the refractive index of the addition-curable silicone resin composition and the cured silicone.
The component (A) may be linear or branched, or may be liquid, waxy or solid.

Examples of the alkenyl group bonded to the silicon atom in the component (A) include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group and the like, and an alkenyl group having 2 to 10 carbon atoms, particularly 2 to 6 carbon atoms is used. Preferably, a vinyl group is more preferred.
a is an integer of 3 or more, preferably an integer of 3 to 9, and more preferably 5. If a is less than 3, there is a possibility that a sufficiently low refractive index cannot be achieved.
b is an integer of 1 or more, preferably an integer of 1 to 5, and more preferably 2. Those in which b is 0 are not preferable in terms of manufacturing.

Such a group represented by CF _3- (CF ₂ ) _a- (CH ₂ ) _b- is preferably a group represented by CF _3- (CF ₂ ) _3- (CH ₂ ) _2- , CF. It is a group represented by _3- (CF ₂ ) _5- (CH ₂ ) _2- .

In addition to the above fluoroalkyl group, the component (A) is a group represented by CF _3- (CF ₂ ) _d- (CH ₂ ) _e -bonded to a silicon atom (where d is an integer of 0 to 2). , E may be an integer of 1 to 5), and a group represented by CF _3- (CH ₂ ) _2- is preferable from the viewpoint of raw material procurement and synthesis.

The substituent other than the alkenyl group and the fluoroalkyl group bonded to the silicon atom in the component (A) is not particularly limited, but a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms is used. preferable. The monovalent hydrocarbon group includes an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group, an aryl group such as a phenyl group, a trill group and a xylyl group, and a benzyl group. Examples thereof include an aralkyl group such as a group and a phenylethyl group, a chloroalkyl group such as a chloromethyl group, a chloropropyl group and a chlorocyclohexyl group. An alkyl group is preferable, and a methyl group is more preferable.

（式中、Ｒ_１は同一でも異なっていてもよいアルケニル基、Ｒ_２は同一でも異なっていてもよいアルケニル基以外の炭素数１～８の置換又は非置換の一価炭化水素基、Ｒ_ｆ１はそれぞれ同一又は異なっていてもよいフッ化アルキル基であり、Ｒ_ｆ１のうち少なくとも１個はＣＦ_３－（ＣＦ_２）_ａ－（ＣＨ_２）_ｂ－で表される基（ただし、ａは３以上の整数であり、ｂは１以上の整数である）である。ｗは１～３の整数であり、ｘ、ｙ、ｚは、それぞれｘ≧０、ｙ≧１、ｚ≧０の整数である。ｘ、ｙ、ｚが付された括弧内のシロキサン単位は任意の配列順であってもよい。） Examples of the component (A) include linear organopolysiloxane represented by the following formula (1).

(In the formula, R ₁ is an alkenyl group which may be the same or different, R ₂ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms other than the alkenyl group which may be the same or different, R _f1 . Are alkyl fluoride groups that may be the same or different, respectively, and at least one of R _f1 is a group represented by CF _3- (CF ₂ ) _a- (CH ₂ ) _b- (where a is 3). (B is an integer of 1 or more). W is an integer of 1 to 3, and x, y, and z are integers of x ≧ 0, y ≧ 1, and z ≧ 0, respectively. The siloxane units in parentheses with x, y, z may be in any sequence order.)

x is an integer of 0 or more, preferably an integer of 0 to 10, y is an integer of 1 or more, preferably 2 to 20, and more preferably an integer of 5 to 10. z is an integer of 0 or more, preferably an integer of 0 to 10, and more preferably an integer of 0 to 5. x + y + z is preferably 1 to 30, more preferably 2 to 20, and even more preferably 5 to 12. The value of y / (x + y + z) is preferably in the range of 1/20 to 1/1, more preferably 1/10 to 1/1, and even more preferably 1/5 to 1/1.

Further, the component (A) is a branched organopolysiloxane having at least one of a siloxane unit represented by SiO _4/2 unit (Q unit) or R ₂ SiO _3/2 unit (T unit) (R ₂ is the above. It may be the same as.).
Such branched organopolysiloxanes further include (R ₂ ) ₂ SiO _2/2 units (D units) such as methyl vinyl syroxy units and dimethyl syroxy units, dimethyl vinyl syroxy units, trimethyl syroxy units and the like (R ₂ ). ₃ SiO _1/2 unit (M unit) (R ₂ is the same as above) may be contained, and the total content of Q unit and T unit is preferably the total siloxane unit in the component (A). It is 5 mol% or more, more preferably 10 to 95 mol%, still more preferably 20 to 80 mol%, and particularly preferably 20 to 60 mol%.

The component (A) preferably has a weight average molecular weight in the range of 500 to 100,000 from the viewpoint of ease of handling.
Specific examples of the component (A) include organopolysiloxane represented by the following constituent unit ratio.
[(CH ₃ ) ₃ SiO _1/2 ] _0.10 [(CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 ] _0.17 [SiO _4/2 ] _0.29 [CF _3- (CF ₂ ) ) ₅ -CH ₂ -CH ₂ -SiO _3/2 ] _0.44
[(CH ₂ = CH) (CH ₃ ) SiO _2/2 ] _0.16 [(CF ₃ -CH ₂ -CH ₂ ) SiO _3/2 ] _0.78 [(CF _3- (CF ₂ ) ₃ -CH ₂ -CH ₂ ) (CH ₃ ) SiO _2/2 ] _0.05
[(CH ₂ = CH) (CH ₃ ) SiO _2/2 ] _0.12 [CF _3- (CF ₂ ) ₅ -CH ₂ -CH ₂ -SiO _3/2 ] _0.35 [CH ₃ SiO _3/2 ] ] _0.53
(In the above formula, the order of arrangement of siloxane units is arbitrary.)

<Ingredient (B)>
The component (B) is an organosilicon compound having two or more hydrogen atoms (that is, SiH groups) bonded to silicon atoms in one molecule. The component (B) acts as a cross-linking agent that crosslinks the alkenyl group contained in the component (A) by a hydrosilylation reaction.
The component (B) is not particularly limited as long as it is an organic silicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule, and examples thereof include organohydrogensilanes and organohydrogenpolysiloxanes. , Preferably organohydrogenpolysiloxane. The molecular structure of the organohydrogenpolysiloxane is not particularly limited, and examples thereof include linear, cyclic, branched chain, and three-dimensional network structures (resin).

The number of SiH groups in the component (B) is preferably 2 to 200, more preferably 3 to 100 in one molecule. When the organosilicon compound of the component (B) has a linear structure or a branched chain structure, these SiH groups may be located only at either the end of the molecular chain or the non-terminal portion of the molecular chain. It may be located in both.
The number of silicon atoms (degree of polymerization) in one molecule of the organosilicon compound (B) is preferably 2 to 1,000, more preferably 3 to 200, and even more preferably 4 to 100.
Further, the organosilicon compound of the component (B) is preferably liquid at 25 ° C., and the kinematic viscosity at 25 ° C. measured by a Canon Fenceke viscometer is preferably 1 to 1,000 mm ² / s, more preferably. Is 10 to 300 mm ² / s.

In the component (B), the substituent bonded to the silicon atom other than the SiH group is not particularly limited, but preferably does not have an aliphatic unsaturated group, and is an unsubstituted monovalent hydrocarbon group or a halogen atom. Substituted with (eg, fluorine atom, chlorine atom, bromine atom), epoxy group-containing group (eg, epoxy group, glycidyl group, glycidoxy group), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group), etc. The above-mentioned monovalent hydrocarbon group can be exemplified. Examples of such substituted or unsubstituted monovalent hydrocarbon groups include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group or an ethyl group, or these. Can be mentioned as a group in which the group of is substituted with the above-exemplified substituent. Further, when it has an epoxy group-containing group and / or an alkoxy group as a substituent of the monovalent hydrocarbon group, it is possible to impart adhesiveness to the cured product of the addition-curable silicone resin composition of the present invention.

The substituent bonded to silicon in the component (B) is a group represented by CF _3- (CF ₂ ) f- (CH ₂ ) _g- (where _f is 0 or more) from the viewpoint of further lowering the refractive index. , G is an integer of 1 or more).
As a group represented by CF _3- (CF ₂ ) _f- (CH ₂ ) _g- , preferably CF _3- (CH ₂ ) _2- , CF _3- (CF ₂ ) _3- (CH ₂ ) _2- , It is a group represented by CF _3- (CF ₂ ) _5- (CH ₂ ) _2- .

Specific examples of the component (B) include organohydrogenpolysiloxane represented by the following formula (2).
R ³ _h Hi SiO (4-h- _{i ) / 2} (2)
(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, respectively, and h and i are 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 ≦ It is a number that satisfies 2.5.)

The substituted or unsubstituted monovalent hydrocarbon group of R ³ is not particularly limited as long as it does not have an alkenyl group, but is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Is preferable. The monovalent hydrocarbon includes an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group, an aryl group such as a phenyl group, a trill group and a xylyl group, and a benzyl group. , Aralkyl group such as phenylethyl group, chloromethyl group, chloropropyl group, chlorocyclohexyl group, CF _3- (CF ₂ ) _e- (CH ₂ ) f- (where e is an integer of 0 or more, _f is 1 or more. ) Etc. are exemplified.

Among these, R ³ is preferably an alkyl group and an alkyl halide group, more preferably a methyl group, and CF _3- (CH ₂ ) _2- , CF _3- (CF ₂ ) _3- (CH ₂ ). It is a group represented by _2- , CF _3- (CF ₂ ) _5- (CH ₂ ) _2- .

The organohydrogensiloxane represented by the average composition formula (2) includes a monoorganosiloxane unit (M unit), a diorganosiloxane unit (D unit), a triorganosiloxane unit (T unit) and / or a SiH group-free monoorganosiloxane unit. Alternatively, it may contain _4/2 units of SiO (Q units), but it is preferable that 30 to 70 mol% of the total organosiloxane units are methylhydrogensiloxane units.

Specific examples of the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, and tris (hydrogen). Dimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain, trimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecular chain Methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked diphenylsiloxane / methylhydrogensiloxane copolymer at both ends of the molecular chain, trimethylsiloxy group-blocked methylphenylsiloxane / methylhydrogensiloxane copolymer at both ends of the molecular chain, both molecular chains Terminal trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer, molecular chain both-terminal trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / diphenylsiloxane copolymer, molecular chain both-terminal dimethylhydrogensiloxy Group-blocked methylhydrogenpolysiloxane, molecular chain double-ended dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, molecular chain double-ended dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain double-ended dimethylhydrogen Syloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain double-ended dimethylhydrogen Syloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer, molecular chain double-ended dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane, molecular chain both In each of these exemplary compounds, a part or all of the methyl group is an ethyl group, Examples thereof include organohydrogenpolysiloxanes substituted with other alkyl groups such as propyl groups.

As a preferable specific example of the component (B), the constituent unit ratio [CF _3- (CF ₂ ) _5- (CH ₂ ) ₂ SiO _3/2 ] _0.25 [H (CH ₃ ) ₂ SiO _1/2 ] ₀ . Examples thereof include polysiloxane represented by _.75 (in the above formula, the order of arrangement of siloxane units is arbitrary).
The component (B) may be used alone or in combination of two or more.

As for the blending amount of the component (B), the hydrogen atom (SiH group) bonded to the silicon atom in the component (B) is 0.5 to 5 for one alkenyl group bonded to the silicon atom in the component (A). The number of hydrogen atoms (SiH groups) bonded to the silicon atom in the component (B) is 0 with respect to the amount of 0.0, that is, the total number of alkenyl groups bonded to all the silicon atoms in the component (A). The amount is 5.5 to 5.0 times. From the viewpoint of the balance of cross-linking, the amount is preferably 0.7 to 3.0 times. If it is less than 0.5 times, the cross-linking becomes insufficient, and if it exceeds 5.0 times, the cross-linking proceeds insufficiently or excessively, and a cured silicone product having excellent hardness cannot be obtained.

<Ingredient (C)>
The platinum group metal-based catalyst of the component (C) is a component for advancing and promoting the hydrosilylation reaction between the component (A) and the component (B).
The platinum group metal-based catalyst is not particularly limited, and for example, platinum group metals such as platinum, palladium, and rhodium; a combination of platinum chloride acid, alcohol-modified platinum chloride acid, platinum chloride acid and olefins, vinylsiloxane, or acetylene compound. Platinum compounds such as position compounds; platinum group metal compounds such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium can be mentioned, and the compatibility with the components (A) and (B) is good. It is preferably a platinum chloride acid modified with silicone because it contains almost no chlor impurities.
The component (C) may be used alone or in combination of two or more.

The blending amount of the component (C) is 1 to 500 ppm, preferably 3 to 100 ppm, more preferably 5 to 40 ppm in terms of the mass of the platinum group metal element with respect to the total mass of the components (A) and (B). be. If the blending amount of the component (C) is less than 1 ppm, the obtained additive-curable silicone resin composition is not sufficiently cured, while if the blending amount is more than 500 ppm, the additive-curable silicone resin composition is not sufficiently cured. The curing rate does not improve any more and is uneconomical.

<(D) component>
The component (D) is a reaction product of the following components i), ii) and iii), exhibits high compatibility with the components (A) to (C), and provides heat resistance to the additive-curable silicone resin composition. It is an additive for imparting.

i) A group represented by CF _3- (CF ₂ ) _j- (CH ₂ ) _k- , which has a viscosity at 25 ° C. of 10 to 10,000 mPa · s and is bonded to at least one silicon atom in one molecule. Organopolysiloxane, having (where j is an integer greater than or equal to 3 and k is an integer greater than or equal to 1).
ii) Carboxylate of cerium-containing rare earth element: cerium is 0.05 to 5 parts by mass with respect to 100 parts by mass of the component,
iii) (R ⁴ O) ₄ At least one of the compound represented by Ti (in the formula, R ⁴ is a monovalent or different monovalent hydrocarbon group) or a partially hydrolyzed condensate thereof: titanium is i) component 100. Amount of 0.05 to 5 parts by mass with respect to parts by mass

The organopolysiloxane component (i) has a viscosity at 25 ° C. of 10 to 10,000 mPa · s, preferably 100 to 7000 mPa · s. If the viscosity is less than 10 mPa · s, it will volatilize during the reaction, and if the viscosity is higher than 10,000 mPa · s, it will be difficult to handle.

(I) In the group represented by CF _3- (CF ₂ ) _j- (CH ₂ ) _k -in the component, j is an integer of 3 or more, preferably an integer of 3 to 9, and more preferably. It is 5. When j is less than 3, the compatibility with the component (A) is insufficient, and the transparency of the addition-curable silicone resin composition and the cured silicone resin is impaired.
k is an integer of 1 or more, preferably an integer of 1 to 5, and more preferably 2. Those in which k is 0 are not preferable in terms of manufacturing.

Such a group represented by CF _3- (CF ₂ ) _j- (CH ₂ ) _k -preferably a group represented by CF _3- (CF ₂ ) _3- (CH ₂ ) _2- , CF. It is a group represented by _3- (CF ₂ ) _5- (CH ₂ ) _2- .

i) Specific examples of the components include the constituent unit ratio [(CH ₃ ) ₃ SiO _1/2 ] _0.2 [(CH ₃ ) SiO _3/2 ] _0.4 [CF _3- (CF ₂ ) _5- ( CH ₂ ) ₂ SiO _3/2 ] Polysiloxane represented by _0.4 can be mentioned.

Examples of the carboxylic acid salt of the rare earth element of the ii) component include salts of cerium and 2-ethylhexanoic acid, naphthenic acid, oleic acid, lauric acid, stearic acid and the like.

In the iii) component, examples of the monovalent hydrocarbon group of ^R4 include those similar to those exemplified as _R2 in the above formula (1), preferably a methyl group, an ethyl group, a propyl group, and a butyl group. It is an alkyl group having 1 to 4 carbon atoms such as.
Examples of the titanium compound of the iii) component include tetraalkoxytitanium such as tetra-n-butyl titanate and a hydrolyzed condensate thereof.

The component (D) is a reaction product obtained by reacting the components i), ii) and iii) at a temperature of 150 ° C. or higher while bubbling an oxygen-containing gas.
As the oxygen-containing gas, a gas containing 5% by volume or more of oxygen with respect to the total gas supplied by bubbling is preferable, and a mixed gas of an inert gas such as nitrogen or argon and oxygen, air or the like can be used. ..

The blending amount of the component (D) is 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0 with respect to 100 parts by mass of the total of the components (A) and (B). .5 to 5 parts by mass. If the blending amount of the component (D) exceeds the above range, the obtained additive-curable silicone resin composition may be colored or the hardness of the cured silicone resin may decrease. Further, if the blending amount of the component (C) is less than the above range, sufficient heat-resistant discoloration cannot be obtained.

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

(Reaction inhibitor)
In the addition-curable silicone resin composition of the present invention, a conventionally known reaction inhibitor (reaction control agent), which is a compound having a curing inhibitory effect on the addition reaction catalyst of the component (C), is applied as needed. Can be used. Examples of this reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; sulfur-containing compounds; acetylene-based compounds; hydroperoxy compounds; maleic acid derivatives and the like. Will be done.
Since the degree of the curing inhibitory effect of the reaction inhibitor varies greatly depending on the chemical structure of the reaction inhibitor, it is preferable to adjust the blending amount of the reaction inhibitor to an optimum amount for each reaction inhibitor to be used. Usually, 0.001 to 5 parts by mass is preferable with respect to a total of 100 parts by mass of the component (A), the component (B), the component (C) and the component (D).

(Adhesive imparting agent)
The addition-curable silicone resin composition of the present invention may contain an adhesive-imparting agent for improving the adhesiveness thereof. Examples of this adhesiveness-imparting agent include a silane coupling agent and a hydrolyzed condensate thereof. Examples of the silane coupling agent include an epoxy group-containing silane coupling agent, a (meth) acrylic group-containing silane coupling agent, an isocyanate group-containing silane coupling agent, an isocyanurate group-containing silane coupling agent, and an amino group-containing silane coupling agent. , A known substance such as a mercapto group-containing silane coupling agent is exemplified, and is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 3 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). 10 parts by mass can be used. Further, the adhesiveness-imparting agent may contain an alkenyl group or a hydrogen atom bonded to a silicon atom while having the above-mentioned adhesive functional group. In this case, it undergoes a hydrosilylation reaction with the components (A) and (B) and is incorporated into the reaction system.

(filler)
In the addition-curable silicone resin composition of the present invention, an inorganic filler such as crystalline silica, a hollow filler, and silsesquioxane, and these fillers are used as an organoalkoxysilane compound, an organochlorosilane compound, an organosilazane compound, and a low amount. It is possible to fill a filler, silicone rubber powder, silicone resin powder or the like which has been surface-hydrophobicized with an organosilicon compound such as a molecular weight siloxane compound. As this component, it is particularly preferable to use a filler capable of imparting tinxability, and by imparting tinxability, a cured silicone product having excellent workability and mechanical properties can be obtained.

The addition-curable silicone resin composition of the present invention can be prepared by mixing the above-mentioned components (A) to (D) and other components used as necessary by a known method using a planetary mixer or the like. can.
The addition-curable silicone resin composition of the present invention comprises a first agent composed of the component (A), the component (C), the component (D) and, if necessary, other components, and the component (A) and (B). ), (D) and, if necessary, other components, a second agent may be prepared separately, and the first agent and the second agent may be mixed before use to form a two-component composition. In addition, there may be a component commonly used in the first agent and the second agent. By using such a two-part type for the addition-curable silicone resin composition, storage stability can be further ensured.

The addition-curable silicone resin composition of the present invention preferably has a refractive index (nD25) of light having a wavelength of 589 nm at 25 ° C. of 1.40 or less.
When the addition-curable silicone resin composition exhibits a refractive index of the predetermined value or less, the addition-curable silicone resin composition gives a silicone cured product having an excellent light extraction efficiency.

[Cursed product]
Furthermore, the present invention provides a cured product (silicone cured product) of an addition-curable silicone resin composition.
This cured silicone product is highly transparent even when used under high temperature conditions, has a small change in hardness and a small decrease in mass, and is particularly useful as a sealing material for LED elements and the like. In particular, since the addition-curable silicone composition of the present invention has a fluoroalkyl group in the component (A), the component (D), and in some cases, the component (B), the light transmittance is increased with a low refractive index. It is possible to obtain a cured silicone product having excellent light extraction efficiency.

The cured silicone product of the present invention preferably has a transmittance of light having a wavelength of 400 nm at an optical path length of 2 mm of 80% or more.
The addition-curable silicone resin composition of the present invention may be cured under known conditions, and as an example, it can be cured at 100 to 180 ° C. for 10 minutes to 5 hours.

The addition-curable silicone resin composition of the present invention can be used as a coating material, a sealing material, a die bonding material, and a protective coating material for electricity and electronics of semiconductor elements, particularly semiconductor elements for optical applications such as LED elements. can.

[Optical semiconductor device]
Further, the present invention provides an optical semiconductor device in which an optical semiconductor element is die-bonded or sealed with the cured silicone product.
The addition-curable silicone resin composition of the present invention is highly transparent even when used under high temperature conditions, and can provide a cured silicone product having a small change in hardness and a small decrease in mass. Therefore, the optical semiconductor device using this cured silicone product has high reliability.

As an example of a method of die-bonding an optical semiconductor device using the addition-curable silicone resin composition of the present invention, the addition-curable silicone resin composition of the present invention is filled in a syringe, and a substrate such as a package is used using the dispenser. After applying the coating to a thickness of 5 to 100 μm in a dry state, an optical semiconductor element (for example, a light emitting diode) is arranged on the applied curable addition-curable silicone resin composition, and the composition is cured. , A method of die-bonding an optical semiconductor element onto a substrate can be mentioned. Further, the addition-curable silicone resin composition is placed on a squeegee dish, and while squeezing, it is applied onto the substrate in a dry state to a thickness of 5 to 100 μm by a stamping method, and then on the applied cure-type silicone resin composition. A method of die-bonding the optical semiconductor element onto the substrate by arranging the optical semiconductor element in the substrate and curing the composition may also be used. The curing conditions of the addition-curing silicone resin composition may be as described above. In this way, it is possible to obtain a highly reliable optical semiconductor device in which an optical semiconductor element is die-bonded with the cured silicone product of the present invention.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following, the viscosity is a value at 25 ° C. measured using a rotational viscometer, and the kinematic viscosity is a value at 25 ° C. measured using a Canon Fenceke viscometer. The meaning of the abbreviations for each siloxane unit is as follows.

M: (CH ₃ ) ₃ SiO _1/2
^MH : H (CH ₃ ) ₂ SiO _1/2
D ^Vi : (CH = CH ₂ ) (CH ₃ ) SiO _2/2
^DF3 : CF _3- (CH ₂ ) ₂ (CH ₃ ) SiO _2/2
^DF13 : CF _3- (CF ₂ ) _5- (CH ₂ ) ₂ (CH ₃ ) SiO _2/2
T: (CH ₃ ) SiO _3/2
^TF13 : CF _3- (CF ₂ ) _5- (CH ₂ ) ₂ SiO _3/2

[Synthesis Example 1]
In a 3L 4-neck flask equipped with a stirrer, cooling tube, dropping funnel and thermometer (3,3,4,4,5,5,6,6,7,7,8,8,8-trideca) Fluorooctyl) Trimethoxysilane 2340.0 g, hexamethyldisiloxane 202.5 g, methyltrimethoxysilane 680 g, and methanol 52 g were added, 6.6 g of methanesulfonic acid was added dropwise with stirring, and 80.3 g of water was further added dropwise. .. After adding 500 g of hexafluoromethoxylen and reacting at 65 ° C. for 5 hours, 10.7 g of a 50% potassium hydroxide aqueous solution was added dropwise. Methanol was distilled off by heating, and the reaction was carried out at 120 ° C. for 5 hours. Further, 3.4 g of methanesulfonic acid was added and a neutralization reaction was carried out at 110 ° C. for 2 hours, then 6.9 g of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and the mixture was stirred at 25 ° C. The obtained solution was filtered and then concentrated under reduced pressure at 120 ° C. to remove the solvent to obtain an organopolysiloxane having a viscosity of 5,300 mPa · s and a refractive index of 1.35. The constituent unit ratio of the obtained organopolysiloxane by NMR spectrum analysis was M _0.2 T _0.4 T ^F13 _0.4 .

[Synthesis Example 2]
To 130 parts by mass of the organopolysiloxane obtained in Synthesis Example 1, 13 parts by mass (0.55% by mass as the amount of cerium) of a turpen solution of 2-ethylhexanoate of a cerium-containing rare earth element mixture (rare earth element content 6% by mass). Part) and 2.7 parts by mass of tetra n-butyl titanate (titanium mass is 0.85 times the mass of cerium in the 2-ethylhexanate) are added with stirring, and a yellowish white dispersion is added. Obtained. Air was bubbled in this dispersion at a pressure of 0.1 MPa (flow rate: 0.3 L / min), and nitrogen gas was heated while flowing through the reaction vessel to remove the turpentine. Then, it was heated at 300 ° C. for 1 hour to obtain a reddish brown transparent composition (D-1).

[Comparative synthesis example 1]
A terpenate solution of 2-ethylhexanate of a cerium-containing rare earth element mixture (rare earth element content) in 130 parts by mass of an organopolysiloxane (refractive index 1.38, viscosity 450 mPa · s) represented by the average formula M ₂ D ^F3 . 6 parts by mass) 13 parts by mass (0.55 parts as cerium amount) and 2.7 parts by mass of tetra n-butyl titanate (titanium mass is 0.85 times the mass of cerium in the 2-ethylhexanate) in advance. The mixture was added with sufficient stirring to obtain a yellowish white dispersion. Air was bubbled in this dispersion at a pressure of 0.1 MPa (flow rate: 0.3 L / min), and nitrogen gas was heated while flowing through the reaction vessel to remove the turpentine. Then, it was heated at 300 ° C. for 1 hour to obtain a reddish brown transparent composition (D-2).

[Synthesis Example 3]
The reaction product of hexamethyldichloride and 1,3-divinyltetramethyldisiloxane was diluted with an ethanol solution so that the platinum content was 3% by mass to prepare a platinum catalyst (C-1).

[Examples 1 and 2, Comparative Examples 1 and 2]
The following components were mixed in the blending amount (part by mass) shown in Table 1 to prepare an addition-curable silicone composition.
(A) Ingredient:
(A-1) Organopolysiloxane represented by the constituent unit ratio T ^F13 _0.35 T _0.53 D ^Vi _0.12 (refractive index 1.36, viscosity 49 Pa · s)

(B) Ingredient:
(B-1) Organohydrogenpolysiloxane (kinematic viscosity 2.5 mm ² / s) represented by the constituent unit ratio ^TF13 _0.25 ^MH _0.75 ,
(B-2) Organohydrogenpolysiloxane represented by the constituent unit ratio D ^F13 _0.17 D ^F3 _0.5 ^MH _0.33 (kinematic viscosity 230 mm ² / s)

(C) Ingredient:
(C-1) Platinum catalyst (D) component obtained in Synthesis Example 3:
(D-1) The composition obtained in Synthesis Example 2,
(D-2) Composition obtained in Comparative Synthesis Example 1

Other ingredients:
(E-1) Compound represented by the following structural formula

［ＳｉＨ基］／［アルケニル基］：（Ａ）成分及中のケイ素原子に結合したアルケニル基１個に対する（Ｂ）成分中のＳｉＨ基の個数

[SiH group] / [alkenyl group]: Number of SiH groups in the component (B) with respect to one alkenyl group bonded to the silicon atom in the component (A).

The addition-curable silicone resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated as follows, and the results are shown in Table 2.
[exterior]
The appearance of each composition was visually observed.

[Refractive index]
For each composition, the refractive index (nD25) of light having a wavelength of 589 nm at 25 ° C. was measured using a refractometer (RX-5000, manufactured by Atago).

[Light transmittance]
For the silicone cured product obtained by pouring the addition-curable silicone resin composition into a mold so as to have a thickness of 2 mm and heating and curing it at 150 ° C. for 2 hours, immediately after the production of the silicone cured product and the environment of the silicone cured product at 250 ° C. After storing underneath for 250 hours, the light transmission rate of straight light having a wavelength of 400 nm at 25 ° C. was measured using a spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.).

[Hardness]
For the silicone cured product obtained by heating and curing the addition-curable silicone resin composition at 150 ° C. for 2 hours, immediately after producing the silicone cured product and after storing the silicone cured product in an environment of 250 ° C. for 250 hours, 25 ° C. The Type A hardness of the cured silicone product was measured. The rate of change in hardness was calculated according to the following formula.
(Rate of change%) = ((250 ° C, hardness after 250 hours) ÷ (hardness immediately after production) x 100) -100)

[Mass residual ratio after heat resistance test]
When the initial mass of the cured silicone product used for measuring the light transmittance was 100, the mass after storage for 250 hours in an environment of 250 ° C. was measured.

As shown in Table 2, it can be seen that the cured products obtained from the addition-curable silicone compositions of Examples 1 and 2 have excellent transparency and little change in physical properties in the heat resistance test.
On the other hand, in Comparative Example 1, since the component (D) was not contained, the hardness change and the mass change in the heat resistance test were large, and the heat resistance was inferior. Further, the composition (D-2) of Comparative Example 2 using an organopolysiloxane having a CF ₃ -CH ₂ -CH _2- group as a fluoroalkyl group as a reaction component is a component (A) to (C). The compatibility was poor, and the addition-curable silicone composition was inferior in transparency, and the cured silicone composition was also inferior in transparency, and the changes in hardness and mass were slightly large.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.

Claims (8)

(A) An alkenyl group bonded to two or more silicon atoms in one molecule and a group represented by CF _3- (CF ₂ ) _a- (CH ₂ ) _b -bonded to one or more silicon atoms (however). , A is an integer of 3 to 9 and b is an integer of 1 or more).
(B) Organic silicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule: Silicon in the component (B) for one alkenyl group bonded to the silicon atom in the component (A). The amount of hydrogen atoms bonded to an atom is 0.5 to 5.0,
(C) Platinum group metal catalyst: An amount of 1 to 500 ppm in terms of mass of the platinum group metal with respect to the total mass of the component (A) and the component (B), and (D) the following i), ii). And iii) Reaction product of the component: 0.01 to 20 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
i) A group represented by CF _3- (CF ₂ ) _j- (CH ₂ ) _k- , which has a viscosity at 25 ° C. of 10 to 10,000 mPa · s and is bonded to at least one silicon atom in one molecule. Organopolysiloxane, having (where j is an integer of 3-9 and k is an integer of 1 or greater).
ii) Carboxylate of cerium-containing rare earth element: Amount of cerium in an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass of the above i) component.
iii) (R ⁴ O) ₄ Ti (in the formula, R ⁴ is a monovalent or different monovalent hydrocarbon group) or at least one of its partially hydrolyzed condensates: titanium is the i) component. It contains an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass .
The group (B) represented by CF _3- (CF ₂ ) _f- (CH ₂ ) _g -in which the component (B) is bonded to one or more silicon atoms in one molecule (where f is an integer of 0 to 5). , G is an integer greater than or equal to 1)
An addition-curable silicone resin composition characterized by being. The addition-curable silicone resin composition according to claim 1 , wherein the component (A) has a = 5 and b = 2, and the component (D) has j = 5 and k = 2. thing. The addition-curable silicone resin composition according to claim 1 or 2 , wherein the refractive index of light having a wavelength of 589 nm at 25 ° C. is 1.37 or less. Claims 1 to 3 include the steps of reacting the components i), ii) and iii) at a temperature of 150 ° C. or higher while bubbling an oxygen-containing gas to generate the component (D). The method for producing an addition-curable silicone resin composition according to any one of the following items. A silicone cured product, which is a cured product of the addition-curable silicone resin composition according to any one of claims 1 to 3 . The cured silicone product according to claim 5 , wherein the transmittance of light having a wavelength of 400 nm at an optical path length of 2 mm is 80% or more. An optical semiconductor device according to claim 5 or 6 , wherein the optical semiconductor element is die-bonded with the cured silicone product. An optical semiconductor device in which an optical semiconductor device is sealed with the cured silicone product according to claim 5 or 6 .