WO2019198755A1

WO2019198755A1 - Silicone resin composition

Info

Publication number: WO2019198755A1
Application number: PCT/JP2019/015615
Authority: WO
Inventors: 吉仁武井; 大輔津島; 丈章齋木
Original assignee: 横浜ゴム株式会社
Priority date: 2018-04-13
Filing date: 2019-04-10
Publication date: 2019-10-17
Also published as: JP2019183049A

Abstract

The present invention provides a silicone resin composition having excellent transparency and heat resistance. This silicone resin composition contains: an organopolysiloxane having a silanol group, a condensation catalyst, and an organic metal compound having at least one metal selected from the group consisting of Fe, Mn, Co, Ni, Cu and Ce. The content of the metal is 0.1 to 200 ppm.

Description

Silicone resin composition

The present invention relates to a silicone resin composition.

An optical semiconductor device (hereinafter also referred to as an LED) has features such as long life, low power consumption, shock resistance, high-speed response, lightness, thinness, and the like. Development in various fields such as lights, in-vehicle lighting, indoor / outdoor advertising, indoor / outdoor lighting, etc. is making dramatic progress.
The LED is manufactured by encapsulating an optical semiconductor element by applying, for example, a silicone resin composition on the optical semiconductor element and curing the composition.

On the other hand, the silicone resin composition is used as, for example, a sealing material in addition to the material for sealing the optical semiconductor element.
As a silicone resin composition, for example, in Patent Document 1,
(A) 100 parts by weight of an organopolysiloxane represented by the general formula (1) HO (SiR ¹ ₂ O) _n H (1)
(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may be the same or different from each other. N is an integer of 10 or more. is there.)
(B) A silane compound having two or more hydrolyzable groups bonded to a silicon atom in one molecule or a partial hydrolyzate thereof 0.1 to 30 parts by weight (C) An organic zirconium compound 0.1 part by weight or more 0 Room temperature curable organopolysiloxane compositions containing less than 5 parts by weight are described.

Japanese Patent Laid-Open No. 2001-161

In recent years, the demand for heat resistance of LEDs has been increasing with the enhancement of functions of LEDs.
Under these circumstances, the present inventors prepared a silicone resin composition with reference to Patent Document 1 and evaluated it. When such a composition does not satisfy the high level of heat resistance required recently, It became clear that there was.
Moreover, it became clear that the above compositions may have poor transparency.
Then, an object of this invention is to provide the silicone resin composition excellent in transparency and heat resistance.

As a result of diligent research to solve the above-mentioned problems, the present inventors have obtained a desired effect by including a specific amount of an organometallic compound having a predetermined metal with respect to an organopolysiloxane having a silanol group and a condensation catalyst. As a result, the present invention was found.
The present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.

[1]
Organopolysiloxane having silanol groups,
A condensation catalyst, and
An organometallic compound having at least one metal selected from the group consisting of Fe, Mn, Co, Ni, Cu and Ce;
A silicone resin composition having a metal content of 0.1 to 200 ppm.
[2]
The silicone resin composition according to [1], wherein the condensation catalyst is a compound represented by the following formula (1).

In formula (1), R ^1-1 and R ^1-2 each independently represents a hydrocarbon group, and n is 1 to 3.
[3]
The organometallic compound is at least one selected from the group consisting of a compound represented by the following formula (2), a compound represented by the formula (3), and a compound represented by the formula (4): [1 ] Or the silicone resin composition as described in [2].

In the formula (2), M ² represents the above metal, R ² each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and m ² represents the same number as the valence of M ² .

In the formula (3), M ³ represents the above metal, R ³ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and m3 represents the same number as the valence of M ³ .

In the formula (4), M ⁴ represents the above metal, and R ⁴ represents a hydrocarbon group having 1 to 18 carbon atoms.
[4]
And a silicon compound having at least one substituent selected from the group consisting of a SiH group, a hydrolyzable group and an R—COO— group (wherein R represents a hydrocarbon group). The silicone resin composition according to any one of [3].
[5]
The silicone resin composition according to [4], wherein the hydrolyzable group is an alkoxysilyl group.
[6]
The silicone resin composition according to any one of [1] to [5], which is used for sealing a semiconductor.

The silicone resin composition of the present invention is excellent in transparency and heat resistance.

The present invention will be described in detail below.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, unless otherwise specified, each component can be used alone or in combination of two or more of the substances corresponding to the component. When a component contains two or more types of substances, the content of the component means the total content of the two or more types of substances.
In the present specification, unless otherwise specified, each component is not particularly limited with respect to its production method. For example, a conventionally well-known thing is mentioned.

[Silicone resin composition]
The silicone resin composition of the present invention (the composition of the present invention)
Organopolysiloxane having silanol groups,
A condensation catalyst, and
An organometallic compound having at least one metal selected from the group consisting of Fe, Mn, Co, Ni, Cu and Ce;
A silicone resin composition having a metal content of 0.1 to 200 ppm.
In the present invention, the unit “ppm” of the metal content means “mass ppm”.

Since the composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason is not clear, but it is presumed that it is as follows.
The silicone resin composition generally contains an organopolysiloxane. The organopolysiloxane has a hydrocarbon group bonded to a silicon atom forming the polysiloxane.
When the composition is cured and the cured product obtained after curing is placed under a high temperature condition (for example, about 250 ° C.), the hydrocarbon group is oxidized and deteriorated, and the C—H bond in the hydrocarbon group is reduced. It is considered that they dissociate and generate radicals derived from the hydrocarbon group (for example, CH ₂ radicals), OH radicals, radicals of silicone resin, and the like.
When such oxidative deterioration occurs, the cured product becomes brittle.

On the other hand, since the said organometallic compound traps the said radical in the composition of this invention, the present inventors estimate that the composition of this invention is excellent in heat resistance.
Moreover, in the composition of this invention, when the content of the said organometallic compound is a predetermined range, it is thought that the composition of this invention is excellent in transparency.
Hereinafter, each component contained in the composition of this invention is explained in full detail.

<< organopolysiloxane >>
The organopolysiloxane contained in the composition of the present invention is a compound having a silanol group, a skeleton of polysiloxane, and a hydrocarbon group bonded to a silicon atom constituting the skeleton.

<Silanol group>
The silanol group possessed by the organopolysiloxane is a group in which a hydroxy group is bonded to a silicon atom.
1 to 3 hydroxy groups can be bonded to the silicon atom. A silanol group is mentioned as a preferred embodiment in which one hydroxy group is bonded to one silicon atom.
The group that can be bonded to the silicon atom in the silanol group (excluding the hydroxy group directly bonded to the silicon atom) is not particularly limited. Examples thereof include a hydrocarbon group, a hydrocarbon group —O—, and a hydrogen atom.

(Hydrocarbon group)
The hydrocarbon group that can be bonded to the silicon atom in the silanol group is not particularly limited. For example, an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof can be used.
The hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group.
Examples of the hydrocarbon group include a methyl group, an ethyl group, and a phenyl group.

(Hydrocarbon group -O-)
The hydrocarbon group in the group represented by the hydrocarbon group —O— that can be bonded to the silicon atom in the silanol group is the same as the hydrocarbon group.

Specific examples of the silanol group include a silanol group having two hydrocarbon groups such as a dimethylsilanol group.
The silanol group may be generated by hydrolysis of a hydrolyzable silyl group. The hydrolyzable silyl group is not particularly limited. Examples thereof include a group in which one group represented by a hydrocarbon group —O— and two hydrocarbon groups are bonded to one silicon atom.

(Skeleton)
The organopolysiloxane skeleton (polysiloxane skeleton) is not particularly limited. The polysiloxane as the skeleton is a polymer having a repeating unit represented by — (Si—O) —. For example, a linear shape, a branched shape, and a network shape can be mentioned. One preferred embodiment of the skeleton is a straight chain.
-Linear When the skeleton of the organopolysiloxane is linear, the skeleton is preferably a diorganopolysiloxane.
When the skeleton of the organopolysiloxane is linear, the silanol groups are preferably bonded to both ends of the skeleton.

-Reticulated When the skeleton of the organopolysiloxane is reticulated, the skeleton can be a silicone resin.

(Hydrocarbon groups bonded to silicon atoms constituting the skeleton of organopolysiloxane)
The hydrocarbon group bonded to the silicon atom constituting the skeleton (polysiloxane) is not particularly limited. For example, the hydrocarbon group similar to the above is mentioned.

The organopolysiloxane may be an oligomer.

As said organopolysiloxane, the compound represented by following formula (5) is mentioned, for example.
HO (SiR ⁵ ₂ O) _n H (5)
・ R ⁵
In formula (5), R ⁵ represents a hydrocarbon group, and R ⁵ may be the same or different. R ⁵ is preferably a saturated aliphatic hydrocarbon group, more preferably a methyl group.

・ N
In formula (5), n is preferably a positive number of 10 or more. n can be a positive number of 1,000 or less. In addition, said n can be made into the value corresponding to the weight average molecular weight of the organopolysiloxane mentioned later.

The above-mentioned organopolysiloxane is polydimethylsiloxane-α, ω-diol (having silanol groups at both ends and two methyl groups bonded to one silicon atom from the viewpoint of being superior in transparency and / or heat resistance. And polydialkylsiloxanes having silanol groups at both ends, such as linear polysiloxane.

The weight average molecular weight of the organopolysiloxane is preferably from 500 to 1,000,000, more preferably from 1,000 to 100,000, from the viewpoint of excellent transparency and / or heat resistance and excellent physical properties of the cured product. More preferably.
In the present invention, the weight average molecular weight of the organopolysiloxane is a standard polystyrene equivalent value based on a value measured by gel permeation chromatography (GPC) using chloroform as a solvent.

<< Condensation catalyst >>
The condensation catalyst contained in the composition of the present invention is not particularly limited as long as it can condense a silanol group.
The condensation catalyst can condense silanols.
The condensation catalyst is at least one selected from the group consisting of the silanol and a SiH group, a hydrolyzable group, and an R—COO— group (wherein R represents a hydrocarbon group) contained in a silicon compound described later. A group of species can be condensed.
In the present invention, the condensation includes a dehydrogenation reaction between a silanol group and a SiH group.

As the condensation catalyst, one of the preferred embodiments is a compound having zirconium.

(Compound represented by Formula (1))
Especially, the compound represented by following formula (1) is preferable from a viewpoint that the said condensation catalyst is excellent by transparency and / or heat resistance, and is excellent in sclerosis | hardenability.

In formula (1), R ^1-1 and R ^1-2 each independently represents a hydrocarbon group, and n is 1 to 3.
In addition, when n is 2 or 3, several ^R1-1 may be the same or different. When 4-n is 2 or 3, the plurality of R ^1-2 may be the same or different.

-Hydrocarbon group In formula (1), the hydrocarbon group as R ^1-1 or R ^1-2 is not particularly limited.
Examples of the hydrocarbon group include an aliphatic hydrocarbon group (straight, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof.
The hydrocarbon group is preferably an aliphatic hydrocarbon group.

・ R ^1-1
In the formula (1), the hydrocarbon group represented by R ^1-1 preferably has 3 to 8 carbon atoms.
R ^1-1 is preferably an aliphatic hydrocarbon group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, from the viewpoint of being excellent in transparency and / or heat resistance and excellent in curability.

・ R ^1-2
In the formula (1), the hydrocarbon group represented by R ^1-2 preferably has 3 to 16 carbon atoms, more preferably 4 to 16 carbon atoms.

R ^1-2 preferably has a cyclic structure. Examples of the cyclic structure include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. The cyclic structure may further have, for example, an aliphatic hydrocarbon group.
Among these, the cyclic structure is more excellent in transparency and / or heat resistance, and is excellent in curability, from the viewpoint of cyclopropane ring, cyclopentane ring, cyclohexane ring, adamantane ring, naphthene ring (naphtholate as —OOCR ^1-2 ). A benzene ring, more preferably a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a naphthene ring.

R ^1-2 may further have a linear or branched hydrocarbon group in addition to the cyclic structure.
As said linear or branched hydrocarbon group, an aliphatic hydrocarbon group is mentioned, for example.
The bond between the cyclic structure and the linear or branched hydrocarbon group is not particularly limited.
It is not particularly limited to which carbon atom of R ^{1-2 the} ester bond in the above formula (1) is bonded.

・ N
In the formula (1), n is preferably 2 or 3.

The compound represented by the above formula (1) is preferably a zirconium alkoxy ester and more preferably a zirconium trialkoxy monoester from the viewpoint that it is excellent in transparency and / or heat resistance and excellent in curability.
Examples of zirconium trialkoxy monoesters include:
Zirconium tributoxy mononaphthate (zirconium tributoxynaphthenate),
Zirconium tributoxy monoisobutyrate,
Zirconium tributoxy mono-2-ethylhexanoate,
Zirconium tributoxy monocyclopropanecarboxylate,
Zirconium tributoxy monocyclopentanecarboxylate,
Zirconium tributoxy monocyclohexanecarboxylate,
Zirconium tributoxy monoadamantane carboxylate.

(Condensation catalyst content)
The content of the condensation catalyst is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the organopolysiloxane, from the viewpoint of better transparency and / or heat resistance and excellent storage stability. More preferably, the content is 0.01 to 0.5 parts by mass.

<< Organic metal compound >>
The organometallic compound contained in the composition of the present invention is a compound having at least one metal selected from the group consisting of Fe, Mn, Co, Ni, Cu and Ce and an organic group.
In the present invention, it is considered that the organometallic compound can trap radicals generated from the cured product of the composition of the present invention under high temperature conditions.

<Metal>
The organometallic compound has at least one metal selected from the group consisting of Fe, Mn, Co, Ni, Cu, and Ce.
The metal is excellent in transparency and / or heat resistance, and is compatible with a silicone resin (the silicone resin contains the organopolysiloxane and a polysiloxane as a silicon compound described later. The same applies to the compatibility). From the viewpoint, Cu, Fe, Mn, and Ce are preferable, and Cu is more preferable.

-Organic group The organic group which the said organometallic compound has is not specifically limited. Examples of the organic group include a group derived from an organic carboxylic acid or a phosphate ester; and a ligand such as acetylacetonate (acac).

Examples of the organometallic compound include organic carboxylates, phosphates, and complexes.
The organic metal compound is preferably an organic carboxylate from the viewpoint of being excellent in transparency and / or heat resistance and excellent in compatibility with a silicone resin.

The organometallic compound is superior in transparency and / or heat resistance, and is excellent in compatibility with the silicone resin. The compound represented by the following formula (2), the compound represented by the formula (3), and the formula It is preferably at least one selected from the group consisting of compounds represented by (4).

In the formula (4), M ⁴ represents the above metal, and R ⁴ represents a hydrocarbon group having 1 to 18 carbon atoms.
The valence of M ⁴ is bivalent.

・ M ² to M ⁴
The metal as M ² in the formula (2) is the same as described above. The same applies to M ³ in Formula (3) and M ⁴ in Formula (4).
M ² in formula (2) can be Fe, Mn, Co, Ni, Cu, or Ce. The same applies to M ³ in Formula (3) and M ⁴ in Formula (4).
In the present invention, M ² in the formula (2) represents the metal as described above. "2" in the right shoulder of the M ² is located for convenience assigned a number to distinguish the M ² in the formula (2) and M ³ and M ⁴ in the formula (4) in the formula (3) It does not represent the valence of the metal. The same applies to M ³ in formula (3) and M ⁴ in formula (4).

・ R ² to R ⁴
Examples of the hydrocarbon group having 1 to 18 carbon atoms as R ² in the formula (2) include an aliphatic hydrocarbon group (linear, branched or cyclic), an aromatic hydrocarbon group, or a combination thereof. Is mentioned.
The carbon number is preferably from 1 to 18, and more preferably from 7 to 10, from the viewpoints of excellent transparency and / or heat resistance and excellent compatibility with the silicone resin.

The hydrocarbon group having 1 to 18 carbon atoms is preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group, from the viewpoints of excellent transparency and / or heat resistance and excellent curability. Specific examples of the hydrocarbon group having 1 to 18 carbon atoms include a residue obtained by removing a carboxy group from octanoic acid (C7) and a residue obtained by removing a carboxy group from neodecanoic acid (C9).
R ³ in formula (3), R ⁴ in formula (4) is the same as R ² in formula (2).

・ M2, m3
M2 in Formula (2) represents the same number as the valence of M ^2.
As for the above “m2 represents the same number as the valence of M ² ”, for example, when M ² is a divalent metal ((M ² ) ²⁺ ), the valence of M ² is divalent. , M2 represents the same number (2) as the valence (divalent) of M ² , so m2 is 2. The same applies to m3 in formula (3).
It is mentioned as a preferable aspect that m2 is 2 or 3.
M3 in the formula (3) is the same as m2.

-The compound represented by Formula (2) Especially, the compound represented by the said Formula (2) from the viewpoint that the said organometallic compound is excellent by transparency and / or heat resistance is preferable.
Examples of the compound represented by the formula (2) include a salt of the above metal of 2-ethylhexanoic acid and a salt of the above metal of neodecanoic acid.
The compound represented by the above formula (2) is preferably a salt of the above metal of 2-ethylhexanoic acid or neodecanoic acid, from the viewpoint of being excellent in transparency and / or heat resistance, Mn salt of 2-ethylhexanoic acid, Co salt, Cu salt or Ce salt, or neodecanoic acid Cu salt or Ce salt is more preferable, and 2-ethylhexanoic acid Ce salt or Cu salt is more preferable.

<< Metal content >>
In the present invention, the content of the metal contained in the organometallic compound is 0.1 to 200 ppm with respect to the composition of the present invention. In addition, content of the said metal is mass conversion.
In this invention, when content of the said metal is the said range, it is excellent in transparency and heat resistance.

The metal content is superior in transparency and / or heat resistance, excellent in heat-resistant yellowing (the property of the resulting cured product does not change to yellow or hardly changes in color under high temperature conditions), and balance between transparency and heat resistance. From the viewpoint of superiority, it is preferably 0.1 to 100 ppm, more preferably 5 to 50 ppm, and even more preferably more than 30 ppm and 50 ppm or less with respect to the composition of the present invention.

(Silicon compound)
The composition of the present invention is further selected from the group consisting of a SiH group, a hydrolyzable group, and an R—COO— group (wherein R represents a hydrocarbon group) from the viewpoint of being excellent in transparency and / or heat resistance. It is preferable to contain a silicon compound having at least one selected substituent.
The silicon compound has a silicon atom. The silicon compound may have one or more silicon per molecule.
The silicon compound does not contain the organopolysiloxane.

Substituent The silicon compound has at least one substituent selected from the group consisting of a SiH group, a hydrolyzable group, and an R—COO— group (wherein R represents a hydrocarbon group).
The substituent is preferably a SiH group or a hydrolyzable group from the viewpoint that it is excellent in transparency and / or heat resistance and excellent in storage stability.

SiH group The SiH group is a group represented by —Si—H. The group capable of bonding to a silicon atom in —Si—H (a group other than the above H) is not particularly limited. Examples of the group capable of bonding to the silicon atom in —Si—H include a group capable of bonding to the silicon atom in the silanol group. Of these, a hydrocarbon group is mentioned as one of preferred embodiments. In addition, it is mentioned as one of the preferable aspects that the said hydrocarbon group does not have an unsaturated bond.

Hydrolyzable group The hydrolyzable group is preferably a hydrolyzable silyl group, more preferably an alkoxysilyl group, from the viewpoint that it is excellent in transparency and / or heat resistance and excellent in storage stability. preferable.
The alkoxysilyl group is a group in which 1 to 3 alkoxy groups are bonded to a silicon atom. In the alkoxysilyl group, 2 to 3 alkoxy groups can be bonded to the silicon atom.
The alkoxy group is not particularly limited. For example, a methoxy group, an ethoxy group, and a propoxy group are mentioned.
When there are one or two alkoxy groups bonded to a silicon atom, the organic group that can bond to the silicon atom is not particularly limited. For example, an alkyl group such as a methyl group; and a hydrocarbon group such as an aromatic hydrocarbon group.

-R-COO- group In the R-COO- group, the above R represents a hydrocarbon group. The hydrocarbon group as R is not particularly limited.
The R—COO— group can be bonded to the silicon atom of the silicon compound directly or through an organic group. The organic group is not particularly limited.

The above-mentioned SiH group, hydrolyzable silyl group, and R—COO— group bonded to a silicon atom can further have another functional group to constitute a silane coupling agent. As said another functional group, an amino group and a hydroxy group are mentioned, for example. The SiH group, hydrolyzable silyl group, or R—COO— group bonded to a silicon atom and the other functional group can be bonded directly or via an organic group.

Silane compound A silicon compound having one silicon per molecule may be hereinafter referred to as a silane compound.
Examples of the silane compound include tetraalkoxysilanes such as tetramethoxysilane, alkyltrialkoxysilanes such as methyltrimethoxysilane, and silane coupling agents having the above substituents.

-Polysiloxane (as a silicon compound) When the said silicon compound has multiple silicon atoms per molecule, it is mentioned as one of the preferable aspects that the said silicon compound is polysiloxane. Examples of the polysiloxane include organopolysiloxane. The organopolysiloxane may be linear, branched, or network.
The polysiloxane may have one or a plurality of the substituents in one molecule.

Examples of the polysiloxane include a hydrolysis condensate of the silane compound (hydrolysis condensation may be partial) and an organopolysiloxane having the substituent.
The hydrolysis condensate of the silane compound is preferably an alkyltrialkoxysilane hydrolysis condensate such as methyltrimethoxysilane.
Examples of the hydrolysis condensate include hydrolysis condensates of 3 to 10 alkyltrialkoxysilanes.
The organopolysiloxane having a substituent is preferably a hydrolyzable silyl group, and more preferably a linear polydialkylsiloxane having a trialkoxysilyl group at both ends.

-Content of silicon compound The content of the silicon compound is from 1 to 1,000 parts by mass with respect to 100 parts by mass of the organopolysiloxane from the viewpoint of being excellent in transparency and / or heat resistance and excellent in curability. It is preferably 5 to 500 parts by mass, more preferably 10 to 500 parts by mass.

(Additive)
The composition of this invention can contain an additive further as needed in the range which does not impair the objective and effect of this invention other than said component.
Examples of the additive include a compound containing silicon other than the organopolysiloxane and the silicon compound (for example, a compound having a vinyl group and a silicon atom), a catalyst other than the condensation catalyst (for example, a hydrosilylation catalyst), and packing. Agents, antioxidants, lubricants, ultraviolet absorbers, solvents, fluorescent substances (including inorganic and organic substances), and antioxidants. The content of the additive is not particularly limited.

The composition of the present invention is not particularly limited with respect to its production method. For example, it can be produced by mixing the organopolysiloxane, the condensation catalyst, the organometallic compound, and the silicon compound and additives that can be used as necessary.

The composition of the present invention can be cured, for example, under conditions of 100 to 200 ° C.

Examples of adherends to which the composition of the present invention can be applied include metals, glass, plastics, rubbers, and semiconductors (for example, optical semiconductor elements).
The composition of the present invention can be used, for example, as a semiconductor sealant.
The composition of this invention is mentioned as one of the aspects with preferable using for sealing a semiconductor.
The semiconductor to which the composition of the present invention can be applied is not particularly limited. For example, a conventionally well-known thing is mentioned.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.
<Production of composition>
Each component of the following Table 1 was used in the composition (part by mass) shown in the same table, and these were mixed with a stirrer to produce a composition.
However, in Table 1, the value described in the column of each organometallic compound is the metal content (unit: ppm) of each organometallic compound relative to the total mass of the silicone resin composition.

<Sample preparation>
-Initial sample Each composition manufactured as mentioned above was hardened on 150 degreeC conditions for 5 hours, and the initial sample (thickness 2mm) was obtained.
Sample after heat test A heat test was performed by placing each of the initial samples prepared as described above at 250 ° C. for 48 hours to obtain a sample after the heat test.

<Evaluation>
The following evaluation was performed using the initial sample and the sample after the heat resistance test prepared as described above. The results are shown in Table 1.
(hardness)
・ Measurement of hardness The hardness of each of the above initial samples was determined in accordance with JIS K 6253-3: 2012 (vulcanized rubber and thermoplastic rubber-Determination of hardness-Part 3: Durometer hardness). And measured. The obtained value is taken as the initial hardness.
Moreover, the hardness of the sample after each said heat test was measured similarly to the above. Let the obtained value be the hardness after the heat resistance test.

-Evaluation standard of heat resistance The hardness increase rate (%) was calculated by applying the initial hardness and the hardness after the heat test to the following formula.
Hardness increase rate (%) = [(BA) / A] × 100
A: Initial hardness B: Hardness after heat test

In the present invention, when the hardness after the heat test is measured, if the sample after the heat test is not broken and the hardness can be measured, the heat resistance is excellent. Table 1 shows the initial hardness and the hardness after the heat resistance test.
On the other hand, when measuring the hardness after the heat test, if the sample after the heat test breaks and the hardness cannot be measured, it is evaluated that the heat resistance is inferior, and this is indicated as “x” in the hardness column after the heat test. Is displayed.
As described above, when the sample after the heat test is destroyed, it is considered that the sample contains at least a large amount of radicals derived from the organopolysiloxane having a silanol group.

Also, the hardness can be measured, and the lower the increase rate of the hardness, the better the heat resistance.

Total light transmittance Using the initial sample prepared as described above, the total light transmittance of the initial sample (in accordance with JIS K 7375: 2008 (Plastics-Determination of total light transmittance and total light reflectance)) ( %).
The higher the total light transmittance, the better the transparency.

-Transmittance at a wavelength of 450 nm Using the initial sample prepared as described above, the transmittance (%) at a wavelength of 450 nm was measured using an ultraviolet / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation) according to JIS K0115: 2004. It was measured.
The higher the transmittance, the better the transmittance of light having the specific wavelength (the emission color is blue).

Details of each component shown in Table 1 are as follows.
(Organopolysiloxane)
PRX-413: Product name PRX-413 manufactured by Toray Dow Corning. Polydimethylsiloxane-α, ω-diol (weight average molecular weight 4,000)
Ss10: trade name ss10 manufactured by Shin-Etsu Chemical Co., Ltd. Polydimethylsiloxane-α, ω-diol (weight average molecular weight 49,000)

(Silicon compound)
KC-89S: Product name KC-89S manufactured by Shin-Etsu Chemical Co., Ltd. Condensate of 3 to 5 methyltrimethoxysilane. Methoxy group 45% by mass. Viscosity 5mPa · s
TMS-ss70: 10 parts by mass of tetramethoxysilane and 100 parts by mass of acetic acid with respect to 100 parts by mass of polydimethylsiloxane having a silanol group at both ends (weight average molecular weight 28,000, trade name ss70, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 part by mass was added, and these were reacted under conditions of 100 ° C. for 6 hours under a nitrogen atmosphere. The reaction product was analyzed by ¹ H-NMR, and it was confirmed that the silanol group of the ss70 had disappeared in the reaction product. The resulting reaction product (organopolysiloxane) is designated TMS-ss70. The weight average molecular weight of TMS-ss70 was 35,000. The main structure of TMS-ss70 is shown by the following formula. N in the formula can be a value corresponding to the weight average molecular weight.

(Condensation catalyst)
・ Tributoxynaphthenic acid Zr
Tributoxynaphthenic acid Zr was produced as follows.
Zirconium tetrabutoxide (manufactured by Kanto Chemical Co., Ltd., 0.026 mol) and naphthenic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Hydrocarbon group having a carboxy group and a cyclic structure (cyclopentane ring) (the average number of carbon atoms of the hydrocarbon group is 15) ), And a neutralization value of 220 mg.) 6.6 g (0.026 mol) was stirred and reacted at room temperature for about 2 hours in a nitrogen atmosphere to obtain a target compound. The neutralization value of naphthenic acid is the amount of KOH required to neutralize 1 g of naphthenic acid.

The obtained compound was analyzed using a Fourier transform infrared spectrophotometer (FT-IR), and it was confirmed that the compound was tributoxynaphthenic acid Zr. The average number of carbons derived from naphthenic acid in the tributoxynaphthenic acid Zr is 15.

(Organic metal compound)
-2-ethylhexanoic acid Fe: Tris (2-ethylhexanoic acid) iron (III), manufactured by Nippon Chemical Industry Co., Ltd.

-2-ethylhexanoic acid Mn: manufactured by Nippon Chemical Industry Co., Ltd. The following structure.

-2-ethylhexanoic acid Co: manufactured by Nippon Chemical Industry Co., Ltd. The following structure.

・ 2-ethylhexanoic acid Ni: manufactured by Nippon Chemical Industry Co., Ltd. The following structure.

・ Neodecanoic acid Cu: manufactured by Nippon Chemical Industry Co., Ltd. Cu (OC (= O) C ₁₀ H ₁₉ ) ₂
-2-ethylhexanoic acid Cu: manufactured by Nippon Chemical Industry Co., Ltd. Cu [OC (= O) CH (C 2 H 5) C 4 H 9] 2

-2-ethylhexanoic acid Ce: manufactured by Wako Pure Chemical Industries, Ltd. The following structure.

Ni compound: Ni complex, Ni (acac) ₃ manufactured by Gelest Co. Cu compound: Cu complex, Cu (acac) ₃ manufactured by Gelest

As is apparent from the results shown in Table 1, Comparative Example 1 not containing a predetermined organometallic compound had poor heat resistance.
In Comparative Examples 2, 4 to 8 in which the content of the predetermined organometallic compound was less than the predetermined range, the heat resistance was poor.
Comparative Example 3 in which the content of the predetermined organometallic compound is larger than the predetermined range has poor transparency.

In contrast, the composition of the present invention was excellent in transparency and heat resistance.

Claims

Organopolysiloxane having silanol groups,
A condensation catalyst, and
An organometallic compound having at least one metal selected from the group consisting of Fe, Mn, Co, Ni, Cu and Ce;
A silicone resin composition, wherein the metal content is 0.1 to 200 ppm.
The silicone resin composition according to claim 1, wherein the condensation catalyst is a compound represented by the following formula (1).

In formula (1), R 1-1 and R 1-2 each independently represents a hydrocarbon group, and n is 1 to 3.
The organometallic compound is at least one selected from the group consisting of a compound represented by the following formula (2), a compound represented by the formula (3), and a compound represented by the formula (4). 3. The silicone resin composition according to 1 or 2.

In formula (2), M 2 represents the metal, R 2 independently represents a hydrocarbon group having 1 to 18 carbon atoms, and m2 represents the same number as the valence of M 2 .

In Formula (3), M 3 represents the metal, R 3 independently represents a hydrocarbon group having 1 to 18 carbon atoms, and m3 represents the same number as the valence of M 3 .

In the formula (4), M 4 represents the metal, and R 4 represents a hydrocarbon group having 1 to 18 carbon atoms.
Furthermore, it contains a silicon compound having at least one substituent selected from the group consisting of a SiH group, a hydrolyzable group, and an R—COO— group (wherein R represents a hydrocarbon group). 4. The silicone resin composition according to any one of 3 above.
The silicone resin composition according to claim 4, wherein the hydrolyzable group is an alkoxysilyl group.
The silicone resin composition according to any one of claims 1 to 5, which is used for sealing a semiconductor.