JP6400904B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition.

  Conventionally, a curable resin composition containing a silicone resin having a reactive functional group at both ends has been known (see, for example, Patent Document 1), and is used, for example, in the field of electronic materials.

JP-A-63-270762

  In recent years, the level of performance required for curable resin compositions containing silicone resins has increased. In particular, a curable resin composition having good adhesion to an adherend is demanded. Further, when such a curable resin composition is a composition for encapsulating an optical semiconductor, good transparency after curing and a higher refractive index are also required. This is because the higher the refractive index of a cured product that seals an optical semiconductor such as an LED, the light extraction efficiency is improved and the brightness becomes brighter.

  This invention is made | formed in view of the above point, and it aims at providing the curable resin composition which is excellent in adhesiveness, and has hardened | cured material with favorable transparency and high refractive index. .

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a composition containing a specific silicone resin and a specific organometallic compound has excellent adhesion and good transparency and high after curing. The inventors have found that it exhibits a refractive index and completed the present invention.
That is, the present invention provides the following (1) to (7).

  (1) A silicone resin (A) having one or more aryl groups in one molecule and having an alkenyl group and an alkoxy group at both ends, and one or more aryl groups and two or more in one molecule A curable resin composition containing a polysiloxane compound (B) having a Si—H bond, an organic zirconium compound (C), and a hydrosilylation catalyst (D).

  (2) The curable resin composition according to (1), wherein the silicone resin (A) is a silicone resin represented by the following formula (A1).

(In Formula (A1), R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, R ² represents an alkyl group, X represents an alkenyl group, r represents an integer of 0 or 1, and n represents And represents an integer greater than or equal to ^{1. A} plurality of R ¹ , R ² and X may be the same or different from each other, but at least one R ¹ in one molecule represents an aryl group.

  (3) The content of the organic zirconium compound (C) is 0.001 to 10 parts by mass with respect to 100 parts by mass in total of the silicone resin (A) and the polysiloxane compound (B) ( The curable resin composition according to 1) or (2).

  (4) The content of the catalyst for hydrosilylation reaction (D) is 0.00001 to 0.1 parts by mass with respect to 100 parts by mass in total of the silicone resin (A) and the polysiloxane compound (B). The curable resin composition according to any one of the above (1) to (3).

(5) The curable resin composition according to any one of (1) to (4), further including a silicone resin (F) represented by the following average composition formula (f):
(R ⁶ SiO _3/2 ) _a (R ⁶ ₂ SiO _2/2 ) _b (R ⁶ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (X ⁶ O _1/2 ) _e (f)
(In formula (f), R ⁶ is the same or different substituted or unsubstituted monovalent hydrocarbon group, and 10 mol% or more of all R ^{6 in} one molecule is an aryl group, and X ⁶ is a hydrogen atom. Or an alkyl group, a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, e is 0 or a positive number, and , B / a is a number from 0 to 10, c / a is a number from 0 to 0.5, d / (a + b + c + d) is a number from 0 to 0.3, and e / (a + b + c + d) is 0. A number of ~ 0.4.)

(6) The curable resin according to any one of (1) to (5), wherein a part or all of the polysiloxane compound (B) is a silicone resin represented by the following average composition formula (b2): Composition.
(R ⁵ SiO _3/2 ) _f (R ⁵ ₂ SiO _2/2 ) _g (R ⁵ ₃ SiO _1/2 ) _h (SiO _4/2 ) _i (X ⁵ O _1/2 ) _j (b2)
(In the formula (b2), R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom excluding the same or different alkenyl groups, and 0.1 to 40 mol% of all R ^{5 in} one molecule is Is a hydrogen atom, 10 mol% or more of the total R ⁵ is an aryl group, X ⁵ is a hydrogen atom or an alkyl group, h is a positive number, i is 0 or a positive number, and j is 0 or (It is a positive number, g / f is a number from 0 to 10, h / f is a number from 0 to 0.5, and j / (f + g + h + i) is a number from 0 to 0.3.)

  (7) The curable resin composition according to any one of (1) to (6), wherein the curable resin composition is an optical semiconductor element sealing composition.

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which is excellent in adhesiveness and whose cured | curing material has favorable transparency and high refractive index can be provided.

The curable resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) is a silicone having one or more aryl groups in one molecule and having an alkenyl group and an alkoxy group at both ends. Resin (A), polysiloxane compound (B) having one or more aryl groups and two or more Si-H bonds in one molecule, organic zirconium compound (C), hydrosilylation reaction catalyst (D ) And a curable resin composition.
Hereinafter, each component contained in the composition of the present invention will be described in detail.

<Silicone resin (A)>
The silicone resin (A) contained in the composition of the present invention is a silicone resin having one or more aryl groups in one molecule and having an alkenyl group and an alkoxy group at both ends.
The composition of the present invention has improved adhesion to the adherend, but it can be added by an alkenyl group and a condensation reaction by an alkoxy group by containing the silicone resin (A). It is presumed that.

Moreover, the hardened | cured material shows a high refractive index because the composition of this invention contains the silicone resin (A) which has an aryl group. This is presumably because the polarizability of the aryl group is high and intermolecular interaction works. Since the cured product exhibits a high refractive index, the light extraction efficiency is improved when the composition of the present invention is a composition for encapsulating an optical semiconductor.
Furthermore, since the intermolecular interaction works in the aryl group as compared with the methyl group or the like, the gas permeability is improved, and an improvement in sulfur resistance can be expected.
In the present invention, the aryl group means a substituted or unsubstituted aryl group.

In the silicone resin (A), the content of aryl groups in all organic groups bonded to silicon atoms (hereinafter also referred to as “silicon atom bonded total organic groups”) is preferably 5 mol% or more. More preferably, it is at least mol%. If the content of the aryl group is within this range, the composition of the present invention has an appropriate viscosity and the cured product has a higher refractive index. Moreover, it is preferable that content of the aryl group in a silicon atom bond all organic group is 99 mol% or less.
The “organic group” bonded to the silicon atom is not particularly limited, and examples thereof include a substituted or unsubstituted monovalent hydrocarbon group represented by R ¹ described later (hereinafter the same).

  The silicone resin (A) contained in the composition of the present invention is particularly limited as long as it is a silicone resin having one or more aryl groups in one molecule and having an alkenyl group and an alkoxy group at both ends. However, it is preferably a silicone resin represented by the following formula (A1).

In formula (A1), R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, R ² represents an alkyl group, X represents an alkenyl group, r represents an integer of 0 or 1, and n represents 1 The above integers are shown. A plurality of R ¹ , R ² and X may be the same or different from each other, but at least one R ¹ in one molecule represents an aryl group.
Moreover, it is preferable that the integer which n shows is an integer of 3-1000, and can be made into the numerical value corresponding to the weight average molecular weight of a silicone resin (A).

Examples of the substituted or unsubstituted monovalent hydrocarbon group (excluding the aryl group) represented by R ¹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl Group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups and other alkyl groups having 1 to 18 carbon atoms; vinyl group, propenyl group, allyl group, hexenyl group Alkenyl group having 2 to 18 carbon atoms such as octenyl group, cyclopentenyl group and cyclohexenyl group; aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group;
Among these, an alkyl group having 1 to 18 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is further preferable, and a methyl group Particularly preferred is an ethyl group.

Further, the substituted or unsubstituted monovalent hydrocarbon group represented by R ¹ includes an aryl group. This aryl group is a substituted or unsubstituted aryl group. Specifically, for example, an aryl group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group; a tolyl group, a xylyl group, and an ethylphenyl group Alkyl having 7 to 18 carbon atoms such as propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group, etc. Aryl group; and the like.
Of these, an unsubstituted aryl group having 6 to 18 carbon atoms is preferable and a phenyl group is more preferable because the cured product of the composition of the present invention exhibits a higher refractive index.

Examples of the alkyl group represented by R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, and various hexyl groups. , Various octyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups, and the like.
Among these, from the viewpoints of curability and adhesion, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group and an ethyl group are preferable. Is more preferable.
When R ² represents an alkyl group, “—OR ² ” represents an alkoxy group in the formula (A1).

  Examples of the alkenyl group represented by X include a vinyl group, a propenyl group, an allyl group, a hexenyl group, an octenyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, because the curability of the composition of the present invention is excellent. , Vinyl group and allyl group are preferable.

The weight average molecular weight (Mw) of the silicone resin (A) is preferably from 500 to 1,000,000 from the viewpoints of mechanical properties, ease of viscosity operation, and ease of reaction operation.
In addition, in this invention, a weight average molecular weight shall be the weight average molecular weight of polystyrene conversion by the gel permeation chromatography (GPC) which uses chloroform as a solvent.

The viscosity at 25 ° C. of the silicone resin (A) is preferably 20 to 1,000,000 mPa · s from the viewpoints of mechanical properties, ease of viscosity operation, and ease of reaction operation. 500 to 100,000 mPa · s is more preferable.
In the present invention, the viscosity is measured at 25 ° C. in accordance with 4.1 (Brookfield rotary viscometer) of JIS K7117-1.

(Manufacturing method of silicone resin (A))
Such a silicone resin (A) includes, for example, a silicone resin having one or more aryl groups in one molecule and silanol groups at both ends, and one or more alkenyl groups in one molecule. It is obtained by reaction with the alkoxysilane it has.
More specifically, the silicone resin (A) is preferably obtained by a reaction between a silicone resin (a1) described later and an alkoxysilane (a2) described later. Hereinafter, the manufacturing method of a silicone resin (A) is demonstrated.

[Silicone resin (a1)]
The silicone resin (a1) used in the method for producing the silicone resin (A) is a silicone resin having silanol groups at both ends represented by the following formula (1). The silanol group is a group in which a hydroxy group (—OH) is directly bonded to a silicon atom (Si).

In formula (1), R ¹ has the same meaning as R ¹ described above, and a plurality of R ¹ may be the same or different, but at least one R ¹ is aryl in one molecule. Indicates a group. m represents an integer of 1 or more.
The integer represented by m is preferably an integer of 3 to 1000, and can be a numerical value corresponding to the weight average molecular weight of the silicone resin (a1).

The weight average molecular weight (Mw) of the silicone resin (a1) is 500 to 1,000,000 from the viewpoints of mechanical properties, ease of viscosity operation of the resulting silicone resin (A), and ease of reaction operation. 000 is preferred.
Moreover, as a viscosity at 25 degrees C of a silicone resin (a1), it is preferable that it is 20-1,000,000 mPa * s from the same viewpoint, and it is more preferable that it is 500-100,000 mPa * s.

[Alkoxysilane (a2)]
The alkoxysilane (a2) used in the method for producing the silicone resin (A) is an alkoxysilane having at least two alkoxy groups in one molecule represented by the following formula (2).

In the formula (2), R ² , X and r are synonymous with R ² , X and r described above. A plurality of R ² may be the same or different.

  The weight average molecular weight (Mw) of the alkoxysilane (a2) is 100 to 2 from the viewpoints of reactivity, mechanical properties, ease of viscosity operation of the resulting silicone resin (A), and ease of reaction operation. Is preferably 1,000, more preferably 140 to 1,000.

[Carboxylic acid compound (a3)]
The reaction between the silicone resin (a1) and the alkoxysilane (a2) is performed in the presence of a carboxylic acid compound (a1) having at least one carboxy group in one molecule represented by the following formula (3). Is preferred. Thereby, the target silicone resin (A) can be obtained under mild conditions (low temperature and short time).

In the formula (3), R ³ represents a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom. Examples of the substituted or unsubstituted monovalent hydrocarbon group represented by R ³ include those described as the substituted or unsubstituted monovalent hydrocarbon group represented by R ¹ , among others, the ease of removal after the reaction, From the viewpoint of compatibility with the silicone resin and availability, it is preferably a monovalent aliphatic hydrocarbon group, more preferably an alkyl group, a methyl group, an ethyl group, or n-propyl. More preferably, it is a group.

[Reaction process]
The method for producing the silicone resin (A) comprises a step of reacting the silicone resin (a1) and the alkoxysilane (a2) in the presence of the carboxylic acid compound (a3) to obtain a reaction product (hereinafter referred to as “reaction step”). ").
In the reaction step, the content ratio of each component is not particularly limited, but from the viewpoint of ease of reaction operation and reaction reproducibility, alkoxysilane (a2) 5 to 100 parts by mass of silicone resin (a1). It is preferable that they are 100 mass parts and carboxylic acid compound (a3) 0.001-10 mass parts.

The reaction between the silicone resin (a1) and the alkoxysilane (a2) is preferably performed by stirring. In stirring, from the viewpoint of milder reaction conditions, heating is preferably performed in a temperature range of 60 to 120 ° C., and stirring time (reaction time) is preferably 3 to 12 hours.
In the reaction step, the method of stirring and heating is not particularly limited, and can be performed by a conventionally known method.

Through such a reaction step, the carboxylic acid compound (a3) functions as a catalyst, and the reaction between the silicone resin (a1) and the alkoxysilane (a2) proceeds. That is, “—OH” possessed by the silicone resin (a1) and “—OR ² ” possessed by the alkoxysilane (a2) react to give “R ² OH” as a by-product, whereby the silicone resin ( A) is formed as the main product.
This reaction process will be described more specifically. For example, a carboxylic acid compound (a3) represented by the following formula (3 ′) is used as a catalyst, and a silicone resin (a1 represented by the following formula (1 ′) is used. ) Reacts with “—OMe” of the alkoxysilane (a2) represented by the following formula (2 ′) to give “MeOH” as a by-product to give the following formula (A1) The silicone resin (A) represented by ′) is produced as the main product.
In the following formulae, “Me” represents a methyl group, “Ph” represents a phenyl group, and “Vi” represents a vinyl group (hereinafter the same). In the following formulae, k and l each represent an integer of 1 or more.

In the reaction step, the reaction is traced by ¹ H-NMR to confirm the disappearance of the peak derived from the silanol group of the silicone resin (a1) or the appearance of a peak derived from a component other than the component used in the reaction. Thus, the reaction can be completed as a reaction product containing the silicone resin (A) as a main product and a by-product.

[Removal process]
Furthermore, the method for producing the silicone resin (A) in the present invention is a step of removing a by-product from the reaction product to obtain a silicone resin (A) as a main product (hereinafter also referred to as “removing step”). May be provided.
The method for removing the by-product is not particularly limited, and examples thereof include a method of stirring the reaction product under reduced pressure while heating.
At this time, conditions such as heating temperature, pressure, stirring time and the like are not particularly limited and can be appropriately set according to the by-product to be generated, but together with the by-product, unreacted alkoxysilane (a2) In addition, it is preferable that the conditions are such that the carboxylic acid compound (a3) as a catalyst can be removed at the same time.
For example, when “MeOH” (methanol) is produced as a by-product, the heating temperature is preferably 120 to 160 ° C., the pressure is preferably 1 to 30 mmHg, and the stirring time is 2 to 5 hours. Is preferred.
In the removal step, the viscosity of the reaction product was measured, and the by-product, unreacted alkoxysilane (a2) and carboxylic acid compound (a3) were removed when the viscosity increased from the beginning and remained unchanged. As an end, it can be terminated.

  Next, the polysiloxane compound (B), the organic zirconium compound (C), and the hydrosilylation reaction catalyst (D) will be described as components that contribute to the curing of the silicone resin (A) described above.

<Polysiloxane compound (B)>
The polysiloxane compound (B) contained in the composition of the present invention is a polysiloxane compound having one or more aryl groups and two or more Si—H bonds in one molecule. Here, the “Si—H bond” means a hydrogen atom (H) bonded to a silicon atom (Si) in a main skeleton formed by a siloxane bond (... Si—O—Si...).

  The polysiloxane compound (B) undergoes an addition reaction (hydrosilylation reaction) with respect to the alkenyl group of the silicone resin (A). At this time, since the polysiloxane compound (B) has at least two Si—H bonds in one molecule, it functions as a crosslinking agent between the silicone resins (A).

  In the polysiloxane compound (B), from the viewpoint of ensuring curability, the amount of the Si—H bond (hereinafter referred to as “Si—H / Si for convenience” with respect to 1 mol of the alkenyl group of the silicone resin (A) described above. -Vi molar ratio ") preferably satisfies 0.5 to 5.0 mol, more preferably 0.5 to 1.5 mol.

In addition, the polysiloxane compound (B) has an aryl group, which makes the composition of the present invention excellent in compatibility with the above-described silicone resin (A) having an aryl group and suppresses turbidity. Excellent in transparency of cured product.
At this time, in the polysiloxane compound (B), the content of the aryl group in the silicon atom-bonded total organic group is preferably 5 mol% or more, and more preferably 10 mol% or more. If the content of the aryl group is within this range, the composition of the present invention is more excellent in transparency and has a higher refractive index after curing. Moreover, it is preferable that content of the aryl group in a silicon atom bond all organic group is 99 mol% or less.

  The polysiloxane compound (B) is not particularly limited as long as it is a polysiloxane compound having one or more aryl groups and two or more Si-H bonds in one molecule. For example, the polysiloxane compound (B) is represented by the following formula (b1). What is done.

In formula (b1), R ⁴ represents a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom excluding an alkenyl group, and t represents an integer of 1 or more. Several R < ⁴ > may be the same or different, However, In 1 molecule, at least 1 R < ⁴ > shows an aryl group and at least 2 R < ⁴ > shows a hydrogen atom.
Examples of the substituted or unsubstituted monovalent hydrocarbon group represented by R ⁴ include those described as the substituted or unsubstituted monovalent hydrocarbon group represented by R ¹ .
The integer represented by t can be a numerical value corresponding to the weight average molecular weight of the polysiloxane compound (B).

The weight average molecular weight (Mw) of the polysiloxane compound (B) is 100 to 10,000 because the adhesiveness of the composition of the present invention is more excellent and the physical properties after curing are also improved. Is preferable, and it is more preferable that it is 120-5,000.
Further, the viscosity of the polysiloxane compound (B) at 25 ° C. is preferably 0.1 to 10,000 mPa · s, more preferably 1 to 100 mPa · s, from the viewpoint of compatibility and workability. preferable.

  As the polysiloxane compound (B) represented by the formula (b1), a commercially available product can be used. Specifically, for example, both terminal dimethylhydrogensiloxy groups represented by the following formula (b1 ′) Blocked methylhydrogensiloxane-methylphenylsiloxane copolymer (HPM-502, manufactured by Gelest, Mw: 4,300, p: q = 1: 1, phenyl group content in silicon-bonded all organic groups: 33 Mol%).

The polysiloxane compound (B) may be partly or wholly a silicone resin represented by the following average composition formula (b2).
(R ⁵ SiO _3/2 ) _f (R ⁵ ₂ SiO _2/2 ) _g (R ⁵ ₃ SiO _1/2 ) _h (SiO _4/2 ) _i (X ⁵ O _1/2 ) _j (b2)
(In the formula (b2), R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom excluding the same or different alkenyl groups, and 0.1 to 40 mol% of all R ^{5 in} one molecule is Is a hydrogen atom, 10 mol% or more of the total R ⁵ is an aryl group, X ⁵ is a hydrogen atom or an alkyl group, h is a positive number, i is 0 or a positive number, and j is 0 or (It is a positive number, g / f is a number from 0 to 10, h / f is a number from 0 to 0.5, and j / (f + g + h + i) is a number from 0 to 0.3.)

The substituted or unsubstituted monovalent hydrocarbon group represented by R ⁵ in the formula (b2) is described as a substituted or unsubstituted monovalent hydrocarbon group represented by R ¹ and excludes an alkenyl group Is mentioned.

<Organic zirconium compound (C)>
The organozirconium compound (C) contained in the composition of the present invention functions as a condensation catalyst that accelerates the condensation reaction of the alkoxy group of the silicone resin (A).
The composition of the present invention is excellent in adhesion by containing the organic zirconium compound (C) in combination with the silicone resin (A).

  For example, when an organic titanium compound is used as the condensation catalyst, the resulting cured product is colored and inferior in transparency, but the cured product of the composition of the present invention using the organic zirconium compound (C) is colored. Suppressed and excellent in transparency. This is presumably because the transition of d electrons in zirconium is less likely to occur than in titanium.

  Although it does not specifically limit as an organic zirconium compound (C), For example, a zirconium alkoxide, a zirconium chelate, etc. are used suitably.

  The zirconium alkoxide is not particularly limited, and examples thereof include tetraethoxyzirconium, tetra-n-propoxyzirconium, tetra-i-propoxyzirconium, tetra-n-butoxyzirconium, tetra-i-butoxyzirconium, tetra-sec-butoxyzirconium. , Tetra-t-butoxyzirconium, tetra-2-ethylhexylzirconium, and the like. Among them, tetra-n-butoxyzirconium and tetra-2-ethylhexylzirconium are preferable.

  The zirconium chelate is not particularly limited, and examples thereof include triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxymono (acetylacetonato) zirconium, Tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxymono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) Zirconium, di-n-propoxy bis (acetylacetonato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, -Sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxy tris (acetylacetonate) Zirconium, mono-i-propoxy-tris (acetylacetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy Tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) Zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy Mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n- Butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy Lith (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, Mono-sec-butoxy-tris (ethylacetoacetate) zirconium, mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, Bis (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium, etc. But, di -i- propoxy bis (ethylacetoacetate) zirconium, di -i- propoxy bis (acetylacetonate) zirconium, tetrakis (acetylacetonato) zirconium are preferred.

Further, the organic zirconium compound (C) used in the present invention may be a zirconium metal salt containing zirconyl [(Zr = O) ²⁺ ] as a constituent element. Examples of such zirconium metal salts include aliphatic carboxylates such as zirconyl dioctylate and zirconyl dineodecanoate; alicyclic carboxylates such as zirconyl naphthenate and zirconyl cyclohexane; aromatic carboxylates such as zirconyl benzoate; Acid salt; and the like.

As the organic zirconium compound (C), those described above may be used alone or in combination of two or more.
The content of the organic zirconium compound (C) is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass in total of the silicone resin (A) and the polysiloxane compound (B), and 0.01 to 5 It is preferable that it is a mass part.
If content of an organozirconium compound (C) is this range, while the composition of this invention is excellent in sclerosis | hardenability, adhesiveness is more excellent and transparency of hardened | cured material is also more excellent.

<Hydrosilylation catalyst (D)>
The catalyst for hydrosilylation reaction (D) contained in the composition of the present invention is used in combination with the polysiloxane compound (B) to promote the addition reaction (hydrosilylation reaction) to the alkenyl group of the silicone resin (A). Function as.
As the hydrosilylation catalyst (D), a conventionally known catalyst can be used, and examples thereof include a platinum-based catalyst, a rhodium-based catalyst, a palladium-based catalyst, and the like, and a platinum-based catalyst is preferable. Specific examples of platinum-based catalysts include chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-divinyltetramethyldisiloxane complexes, chloroplatinic acid-alcohol coordination compounds, platinum diketone complexes, and the like. May be used alone or in combination of two or more.
The content of the hydrosilylation reaction catalyst (D) is a catalytic amount, but because the curability of the composition of the present invention is excellent, a total of 100 of the above-described silicone resin (A) and polysiloxane compound (B). It is preferable that it is 0.00001-0.1 mass part with respect to a mass part, and it is more preferable that it is 0.0001-0.01 mass part.

<Curing retarder (E)>
The composition of the present invention may further contain a curing retarder (E). The curing retarder (E) is a component for adjusting the curing rate and working life of the composition of the present invention. For example, 3-methyl-1-butyn-3-ol, 3,5-dimethyl- Alcohol derivatives having a carbon-carbon triple bond such as 1-hexyn-3-ol, phenylbutynol, 1-ethynyl-1-cyclohexanol; 3-methyl-3-penten-1-yne, 3,5-dimethyl- Enyne compounds such as 3-hexen-1-yne; alkenyl group-containing low molecular weight siloxanes such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; methyl-tris (3-methyl-1-butyne-3- Alkyne-containing silanes such as oxy) silane, vinyl-tris (3-methyl-1-butyne-3-oxy) silane; Gerare, may be used those either alone, or in combination of two or more.
Although content of a hardening retarder (E) is suitably selected according to the usage method etc. of the composition of this invention, for example, a total of 100 mass parts of silicone resin (A) mentioned above and a polysiloxane compound (B). On the other hand, it is preferably 0.00001 to 0.1 parts by mass, and more preferably 0.0001 to 0.01 parts by mass.

<Silicone resin (F)>
The composition of the present invention may further contain a silicone resin (F) represented by the following average composition formula (f). Thereby, the composition of the present invention has high hardness and suppresses surface tack.

(R ⁶ SiO _3/2 ) _a (R ⁶ ₂ SiO _2/2 ) _b (R ⁶ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (X ⁶ O _1/2 ) _e (f)
(In formula (f), R ⁶ is the same or different substituted or unsubstituted monovalent hydrocarbon group, and 10 mol% or more of all R ^{6 in} one molecule is an aryl group, and X ⁶ is a hydrogen atom. Or an alkyl group, a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, e is 0 or a positive number, and , B / a is a number from 0 to 10, c / a is a number from 0 to 0.5, d / (a + b + c + d) is a number from 0 to 0.3, and e / (a + b + c + d) is 0. A number of ~ 0.4.)

Examples of the substituted or unsubstituted monovalent hydrocarbon group represented by R ⁶ in the formula (f) include those described as the substituted or unsubstituted monovalent hydrocarbon group represented by R ¹ .

  In the silicone resin (F), the content of aryl groups in the silicon-bonded all organic groups is preferably 5 to 95 mol%, more preferably 20 to 80 mol%.

  Although content of a silicone resin (F) is not specifically limited, For example, it is preferable that it is 10-1000 mass parts with respect to a total of 100 mass parts of silicone resin (A) and polysiloxane compound (B) mentioned above, More preferably, it is 50-500 mass parts.

<Adhesion imparting agent (G)>
The composition of the present invention may further contain an adhesion promoter (G).
Examples of the adhesion-imparting agent (G) include a silane coupling agent. Specific examples of the silane coupling agent include aminosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, imino silane, reaction products thereof, and the like. The compound etc. which are obtained by reaction with polyisocyanate are mentioned, It is preferable that it is an epoxy silane.
The epoxy silane is not particularly limited as long as it is a compound having an epoxy group and an alkoxysilyl group. For example, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycid Dialkoxyepoxysilanes such as xylpropylmethyldiethoxysilane, β- (3,4 epoxycyclohexyl) ethylmethyldimethoxysilane; γ-glycidoxypropyltrimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane And the like, and the like.
The content of the adhesion-imparting agent (G) is not particularly limited, but it is 0.5 with respect to a total of 100 parts by mass of the above-described silicone resin (A), polysiloxane compound (B), and organic zirconium compound (C). It is preferable that it is -10 mass parts, and it is more preferable that it is 1-5 mass parts.

The manufacturing method of the composition of this invention is not specifically limited, For example, the method of manufacturing by mixing the essential component mentioned above and an arbitrary component is mentioned.
Moreover, the method of hardening the composition of this invention and obtaining hardened | cured material is not specifically limited, For example, the method of heating the composition of this invention for 80-200 degreeC and 10 minutes-720 minutes is mentioned.

  The composition of the present invention is, for example, in the field of display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, semiconductor integrated circuit peripheral materials, etc. It can be used as a primer, a sealing material and the like.

In particular, the composition of the present invention can be suitably used as a composition for encapsulating an optical semiconductor because it has excellent adhesion and its cured product exhibits good transparency and high refractive index.
The optical semiconductor to which the composition of the present invention can be applied is not particularly limited, and examples thereof include a light emitting diode (LED), an organic electroluminescent element (organic EL), a laser diode, and an LED array.
As a method for using the composition of the present invention as an optical semiconductor sealing composition, for example, the composition of the present invention is applied to an optical semiconductor, and the optical semiconductor to which the composition of the present invention is applied is heated. The method of hardening the composition of invention is mentioned.
At this time, the method for applying and curing the composition of the present invention is not particularly limited, and examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Examples 1 to 3, Comparative Examples 1 to 5]
<Manufacture of curable resin composition>
The components shown in Table 1 below were used in the amounts shown in the table (unit: parts by mass), and these were uniformly mixed with a vacuum stirrer to give a curable resin composition (hereinafter also simply referred to as “composition”). Manufactured. In the table, “Si—H / Si—Vi molar ratio” is as described above.

<Transmissivity>
The produced composition was cured by heating at 150 ° C. for 2 hours to obtain a cured product (thickness = 2.0 mm). About the obtained hardened | cured material, according to JISK0115: 2004, the transmittance | permeability (unit:%) in wavelength 400nm was measured using the ultraviolet-visible (UV-Vis) absorption-spectrum measuring apparatus (made by Shimadzu Corp.). The measurement results are shown in Table 1 below. If the transmittance value is 80% T or more, it can be evaluated as being excellent in “transparency”.

<Refractive index>
The produced composition was cured by heating at 150 ° C. for 2 hours to obtain a cured product (thickness = 2.0 mm). About the obtained hardened | cured material, the refractive index in D line | wire 589.6nm of the spectrum of sodium was measured by the measuring method based on JISK7105: 1981 using the Abbereflectometer (made by ATAGO). The measurement results are shown in Table 1 below. If the value of the refractive index is 1.43 or more, it can be evaluated as a high refractive index, and if it is 1.5 or more, it can be evaluated as a higher refractive index.

<Tensile shear bond strength, CF>
The prepared composition was bonded to an adherend (aluminum alloy plate, A1050P, manufactured by Partec Co., Ltd.) with an adhesion area of 12.5 mm × 25 mm, and then cured by heating at 150 ° C. for 2 hours, and tested. Got the body. Using the obtained specimen, a tensile test was performed in accordance with JIS K6850: 1999, and the tensile shear bond strength (unit: MPa) was measured. Further, the ratio (unit:%) of the cohesive failure (CF) area to the adhesion area was also measured. The results are shown in Table 1 below. It can be evaluated that the higher the value of tensile shear adhesive strength and the closer the value of CF is to 100, the better the adhesion.

<Reflow test, wet heat test>
The manufactured composition was applied to an LED package (manufactured by Enomoto) and cured by heating at 150 ° C. for 2 hours to prepare a test specimen. In addition, eight test bodies were produced for each example. The eight test specimens thus produced were subjected to the following two types of tests, and the number of test specimens for which peeling of the cured product was not confirmed was counted. The larger the number, the better the adhesion.

(Reflow test)
After leaving the test body on a hot plate heated to 280 ° C. for 40 seconds, the presence or absence of peeling of the cured product was visually confirmed.
(Moist heat test)
The specimen was left for 1000 hours in an environment at a temperature of 85 ° C. and a humidity of 85%, and then the presence or absence of peeling of the cured product was visually confirmed.

The following were used for each component in Table 1.
Silicone resin A1: Silicone resin having a phenyl group and having a vinyl group and a methoxy group at both ends, produced as described later (Mw: 2,000, viscosity: 250 mPa · s, containing vinyl group) Amount: 3.10% by mass, content of phenyl group in all silicon-bonded organic groups: 50 mol%). It is represented by the following formula (A1-1), and n ′ in the formula is a numerical value corresponding to the weight average molecular weight of the silicone resin A1.
Silicone resin A2: A silicone resin having a phenyl group and having a vinyl group and a methoxy group at both ends, produced as described later (Mw: 1,500, viscosity: 100 mPa · s, containing vinyl group) Amount: 4.51 mass%, content of phenyl group in silicon atom-bonded all organic groups: 50 mol%). It is represented by the following formula (A2-1), and k ′ and l ′ in the formula are numerical values corresponding to the weight average molecular weight of the silicone resin A2, and k ′: l ′ = 1: 1.

Silicone resin X1: A methylphenyl silicone resin having a phenyl group and having a methyl group and a vinyl group at both ends (PMV-9925, Gelest, Mw: 2,500, viscosity: 500 mPa · s, vinyl group Content: 2.2% by mass, content of phenyl group in all silicon atom-bonded organic groups: 50 mol%)
Silicone resin X2: A silicone resin represented by the following formula (X2), produced as described later, having no phenyl group and having a vinyl group and a methoxy group at both ends (Mw: 20,000) , Viscosity: 1,000 mPa · s, vinyl group content: 0.30% by mass)

Polysiloxane compound B1: dimethylhydrogensiloxy group-blocked methylhydrogensiloxane-methylphenylsiloxane copolymer (HPM-502, manufactured by Gelest, Mw: 4,300, phenyl group in silicon atom-bonded all organic groups) Content: 33 mol%)
Polysiloxane compound Z1: Organopolysiloxane represented by the following formula (Z1) (HMS-991, manufactured by Gelest, Mw: 1,600)

・ Organic zirconium compound C1: tetra-n-butoxyzirconium (Orgachix ZA-65, manufactured by Matsumoto Trading Co., Ltd.)
Organic titanium compound Y1: tetra-i-propoxy titanium (TA-10, manufactured by Matsumoto Fine Chemical Co., Ltd.)

Catalyst for hydrosilylation reaction D1: Chloroplatinic acid-divinyltetramethyldisiloxane complex (Gelest, Mw: 474.68)
Curing retarder E1: 3-methyl-1-butyn-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd., Mw: 100)
Silicone resin F1: Phenyl silicone resin represented by an average composition formula “(PhSiO _3/2 ) _0.9 (ViMe ₂ SiO _1/2 ) _0.1 ” (vinyl group content: 5.6 mass%, all silicon atoms bonded) (Phyl group content in organic group: 75 mol%)
Adhesion imparting agent G1: γ-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

About silicone resin A1, A2, X2, it manufactured as follows.
First, a 2 L 3-neck flask was equipped with a Dimroth condenser and a mechanical stirrer, and the components shown in Table 2 below (unit: parts by mass) were enclosed. Next, the mechanical stirrer was rotated while the flask was immersed in an oil bath and heated to 100 ° C., and the components enclosed in the flask were stirred and reacted for 6 hours.
At this time, the silicone resin a1-1, which will be described later, a1-2, disappearance of a peak derived from a silanol group of the a1-3, or the appearance of a peak derived from a component other than the component enclosed in a flask, ¹ H By confirming by -NMR, the reaction was terminated as a reaction product containing the main product (silicone resins A1, A2, X2) was obtained.
Next, using a vacuum pump, the reaction product was stirred for 3 hours under conditions of 140 ° C. and 10 mmHg. When the viscosity became unchanged, by-products, unreacted alkoxysilane a2-1 and carboxylic acid As the removal of compound a3-1, silicone resins A1, A2, and X2 were obtained.

The following were used for each component in Table 2.
Silicone resin a1-1: Silanol group polymethylphenylsiloxane at both ends (Mw: 1,500)
Silicone resin a1-2: Silanol group diphenylsiloxane-dimethylsiloxane copolymer (PDS-1615, manufactured by Gelest, Mw: 1,000)
Silicone resin a1-3: Silanol polydimethylsiloxane at both ends (DMS-S27, manufactured by Gelest, Mw: 18,000, viscosity: 800 mPa · s)
Alkoxysilane a2-1: Trimethoxyvinylsilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd., Mw: 148.2)
Carboxylic acid compound a3-1: Acetic acid (Deer grade 1, manufactured by Kanto Chemical Co., Inc.)

Looking at the results shown in Table 1, all of Examples 1 to 3 had high transmittance values and excellent transparency, and also had a high refractive index. Furthermore, the adhesiveness was also excellent.
On the other hand, it was found that Comparative Examples 1 to 3 using the silicone resin X1 having a methyl group and a vinyl group at both ends (no alkoxy group) are inferior in adhesion.
Moreover, the comparative example 4 using the organic titanium compound Y1 had a low transmittance value and was inferior in transparency.
Further, Comparative Example 5 using the silicone resin X2 having no phenyl group had a low refractive index.

Claims (6)

A silicone resin (A) having one or more aryl groups in one molecule and having an alkenyl group and an alkoxy group at both ends;
A polysiloxane compound (B) having one or more aryl groups and two or more Si-H bonds in one molecule;
An organic zirconium compound (C);
A hydrosilylation catalyst (D);
Containing
The silicone resin (A) is a silicone resin represented by the following formula (A1),
A curable resin composition, wherein the organic zirconium compound (C) is a zirconium alkoxide.
(In Formula (A1), R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, R ² represents an alkyl group, X represents an alkenyl group, r represents an integer of 0 or 1, and n represents And represents an integer greater than or equal to ^{1. A} plurality of R ¹ , R ² and X may be the same or different from each other, but at least one R ¹ in one molecule represents an aryl group. The content of the organic zirconium compound (C), per 100 parts by weight of the silicone resin (A) and the polysiloxane compound (B), is 0.001 to 10 parts by weight, according to claim 1 Curable resin composition. Content of the said catalyst for hydrosilylation reaction (D) is 0.00001-0.1 mass part with respect to a total of 100 mass parts of the said silicone resin (A) and the said polysiloxane compound (B), Item 3. The curable resin composition according to Item 1 or 2 . Furthermore, the curable resin composition in any one of Claims 1-3 containing the silicone resin (F) represented by the following average compositional formula (f).
(R ⁶ SiO _3/2 ) _a (R ⁶ ₂ SiO _2/2 ) _b (R ⁶ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (X ⁶ O _1/2 ) _e (f)
(In formula (f), R ⁶ is the same or different substituted or unsubstituted monovalent hydrocarbon group, and 10 mol% or more of all R ^{6 in} one molecule is an aryl group, and X ⁶ is a hydrogen atom. Or an alkyl group, a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, e is 0 or a positive number, and , B / a is a number from 0 to 10, c / a is a number from 0 to 0.5, d / (a + b + c + d) is a number from 0 to 0.3, and e / (a + b + c + d) is 0. A number of ~ 0.4.) The curable resin composition according to any one of claims 1 to 4 , wherein a part or all of the polysiloxane compound (B) is a silicone resin represented by the following average composition formula (b2).
(R ⁵ SiO _3/2 ) _f (R ⁵ ₂ SiO _2/2 ) _g (R ⁵ ₃ SiO _1/2 ) _h (SiO _4/2 ) _i (X ⁵ O _1/2 ) _j (b2)
(In the formula (b2), R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom excluding the same or different alkenyl groups, and 0.1 to 40 mol% of all R ^{5 in} one molecule is Is a hydrogen atom, 10 mol% or more of the total R ⁵ is an aryl group, X ⁵ is a hydrogen atom or an alkyl group, h is a positive number, i is 0 or a positive number, and j is 0 or (It is a positive number, g / f is a number from 0 to 10, h / f is a number from 0 to 0.5, and j / (f + g + h + i) is a number from 0 to 0.3.) An optical semiconductor element encapsulation composition, the curable resin composition according to any one of claims 1-5.