JP2017118111A - Silicone-based cured product, composition for silicone-based cured product, and semiconductor light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a silicone-based cured product enhanced in cracking resistance; a composition for a silicone-based cured product, which can provide the cured product; and a semiconductor light-emitting device including the cured product.SOLUTION: A silicone-based cured product is a cured product of (A) a bifunctional thermosetting silicone resin and (B) a multifunctional thermosetting silicone resin. According to solid Si-nuclear magnetic resonance spectra, a terminal silicon content, which is a rate of silicon atoms included in terminal silicon to all of silicon atoms included the cured product, calculated from a peak selected from a group consisting of (1) a peak of which the peak top position is in a chemical shift region of -40 to 0 ppm, and (2) a peak of which the peak top position is in a chemical shift region of -80 to -40 ppm (exclusive -40 ppm) is less than 0.1 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a silicone-based cured product, a composition for a silicone-based cured product, and a semiconductor light emitting device.

  In recent years, UV (ultraviolet) -LEDs have started to appear on the market. Quartz glass is generally used for sealing the UV-LED. However, quartz glass is expensive, and there is a problem that UV light extraction efficiency is low due to the refractive index. Therefore, it has been studied to seal the UV-LED with a resin such as an epoxy resin or an addition reaction type silicone resin. However, when the UV-LED is sealed with these resins, there is a problem that UV light transmittance is low and the resin is severely deteriorated.

  As a silicone-based sealing material composition that solves the above problems, a sealing material using a condensation type silicone resin has been proposed. For example, a silicone-based encapsulant composition comprising (A) a bifunctional thermosetting silicone resin, (B) a polyfunctional thermosetting silicone resin, and (C) a curing catalyst at 80 ° C. ( A silicone-based sealing material composition in which A) and (B) are incompatible with each other has been proposed (see Patent Document 1).

  In the silicone-based sealing material composition of Patent Document 1, (A) and (B) are incompatible with each other at 80 ° C., so that (A) and (B) are phase-separated in the melted system. Since the density of (B) is higher than the density of (A), the component (B) mainly settles in the liquefied encapsulant composition and gathers in the vicinity of the lead electrode at the bottom, where there is a high degree of crosslinking reaction. In this case, the surface of the lead electrode is covered with a layer having a high gas barrier property.

JP 2012-238636 A

  However, the sealing material obtained by curing the silicone-based sealing material composition described in Patent Document 1 may not have sufficient crack resistance.

  The present invention has been made in view of the above problems, and provides a silicone-based cured product with improved crack resistance, a composition for a silicone-based cured product that provides the cured product, and a semiconductor light emitting device including the cured product. With the goal.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention as follows. That is, one embodiment of the present invention is a cured product of (A) a bifunctional thermosetting silicone resin and (B) a polyfunctional thermosetting silicone resin, and (1) a peak in a solid Si-nuclear magnetic resonance spectrum. Calculated from a peak selected from the group consisting of a peak in the region where the top position is chemical shift −40 ppm to 0 ppm and (2) a peak in the region where the peak top position is chemical shift −80 ppm to −40 ppm. A silicone-based cured product having a terminal silicon content, which is a ratio of silicon atoms contained in terminal silicon with respect to all silicon atoms contained in the cured product, is less than 0.1% by mass.

  One embodiment of the present invention is a cured product obtained by curing a composition containing (A) a bifunctional thermosetting silicone resin, (B) a polyfunctional thermosetting silicone resin, and (C) a curing catalyst. In the solid Si-nuclear magnetic resonance spectrum, (1) the peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half width is 0.5 ppm or more and 3.0 ppm or less, and (2) The peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the half value width of the peak is calculated from a peak selected from the group consisting of peaks of 1.0 ppm or more and 5.0 ppm or less. Even if the terminal silicon content, which is the ratio of the silicon atoms contained in the terminal silicon to the total silicon atoms contained in the product, is less than 0.1% by mass There.

  In one embodiment of the present invention, (C) may be a phosphoric acid catalyst.

In one embodiment of the present invention, the ratio of (B) based on the sum of (A) and (B) (100% by mass) is 20% by mass or more and less than 80% by mass, and the functional number of (B) is It is 2.5 to 3.5, and 50% or more of the repeating units constituting (B) are trifunctional, and the sum of (A), (B) and (C) is the standard (100% by mass). The ratio of (C) may be 1.0 mass% or more and less than 3.0 mass%.
In the present specification, “functional number” refers to the number of functional groups.

  In one embodiment of the present invention, the ratio of (B) based on the sum of (A) and (B) as a reference (100% by mass) may be 30% by mass or more and less than 60% by mass.

  In one embodiment of the present invention, the ratio of (C) based on the sum of (A), (B), and (C) (100% by mass) is 1.2% by mass or more and less than 2.0% by mass. Also good.

  In one embodiment of the present invention, the total content of (A), (B), and (C) may be 90% by mass or more.

  1 aspect of this invention WHEREIN: The silicone type sealing material used for a sealing use may be sufficient as the said silicone type hardened | cured material.

  Another aspect of the present invention is a semiconductor comprising a base material, a semiconductor light emitting element disposed on the base material, and a silicone-based cured material according to the first aspect that seals at least a part of the semiconductor light emitting element. A light emitting device is provided.

  In one aspect of the present invention, the emission wavelength of the semiconductor light emitting device may be in the ultraviolet region.

  Another aspect of the present invention is a composition comprising (A) a bifunctional thermosetting silicone resin, (B) a polyfunctional thermosetting silicone resin and (C) a curing catalyst, wherein (A) and ( The ratio of (B) based on the sum of B) (100% by mass) is 20% by mass or more and less than 70% by mass and is based on the sum of (A), (B) and (C) (C ) Is 1.0 mass% or more and less than 3.0 mass%, the functional number of (B) is 2.5 to 3.5, and 50% or more of the repeating units constituting (B) are three Provided is a composition for a silicone-based cured product that is a functional type.

  In one embodiment of the present invention, (C) may be a phosphoric acid catalyst.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention as follows. That is, one embodiment of the present invention is a cured product obtained by curing a composition containing (A) a bifunctional thermosetting silicone resin, (B) a polyfunctional thermosetting silicone resin, and (C) a curing catalyst. In the solid Si-nuclear magnetic resonance spectrum, (1) the peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-value width is 0.5 ppm or more and 3.0 ppm or less, And (2) the peak top position is in the region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is calculated from a peak selected from the group consisting of peaks of 1.0 ppm or more and 5.0 ppm or less. A silicone-based cured product having a terminal silicon content of less than 0.1% by mass with respect to the total mass of the cured product is provided.

  1st aspect of this invention WHEREIN: The ratio of (B) which made the sum total of (A) and (B) the standard (100 mass%) is 20 mass% or more and less than 80 mass%, and the functional number of (B) Is 2.5 to 3.5, 50% or more of the repeating units constituting (B) are trifunctional, and based on the total of (A), (B) and (C) (100% by mass) The ratio of (C) may be 1.0 mass% or more and less than 3.0 mass%.

  In the first aspect of the present invention, the ratio of (B) based on the sum of (A) and (B) as a reference (100% by mass) may be 30% by mass or more and less than 60% by mass.

  In the first aspect of the present invention, the ratio of (C) based on the sum of (A), (B), and (C) (100 mass%) was 1.2 mass% or more and less than 2.0 mass%. May be.

  In the first aspect of the present invention, the total content of (A), (B), and (C) may be 90% by mass or more.

  1st aspect of this invention WHEREIN: The silicone type sealing material used for a sealing use may be sufficient as the said silicone type hardened | cured material.

  The second aspect of the present invention is a silicone-based curing obtained by curing a composition containing (A) a bifunctional thermosetting silicone resin, (B) a polyfunctional thermosetting silicone resin, and (C) a curing catalyst. It is a manufacturing method of a thing, Comprising: Before apply | coating the said composition to a base material, the manufacturing method of the silicone type hardened | cured material which goes through the process of heating the said composition in the range of 40 to 100 degreeC is provided.

  According to a third aspect of the present invention, there is provided a semiconductor light emitting device comprising: a base material; a semiconductor light emitting element disposed on the base material; and a silicone-based cured product according to the first aspect that seals at least a part of the semiconductor light emitting element. Providing equipment.

  In the third aspect of the present invention, the emission wavelength of the semiconductor light emitting device may be in an ultraviolet region.

  A fourth aspect of the present invention is a composition containing (A) a bifunctional thermosetting silicone resin and (B) a polyfunctional thermosetting silicone resin, which is based on the sum of (A) and (B). The proportion of (B) as (100% by mass) is 20% by mass or more and less than 70% by mass, the functional number of (B) is 2.5 to 3.5, and the repeating unit constituting (B) Provided is a composition for a silicone-based cured product in which 50% or more of the trifunctional type is trifunctional.

  The composition for a silicone-based cured product according to the present invention is useful because it provides a silicone-based cured product having improved crack resistance. Moreover, since the silicone type hardened | cured material with which the semiconductor light-emitting device which concerns on this invention was equipped has improved crack resistance, it is useful for the use of the sealing material of a light emitting element.

1 is a cross-sectional view of a semiconductor light emitting device according to a first embodiment. It is a ²⁹ Si-NMR spectrum of the silicone type hardened | cured material produced in the Example.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the invention.

<Silicone-based cured product>
In the first embodiment, (A) a bifunctional thermosetting silicone resin and (B) a cured product of a polyfunctional thermosetting silicone resin, and (1) the position of the peak top in the solid Si-nuclear magnetic resonance spectrum Is calculated from a peak selected from the group consisting of a peak in the region where the chemical shift is −40 ppm or more and 0 ppm or less, and (2) the peak top position is in the region where the chemical shift is −80 ppm or more and less than −40 ppm. Provided is a silicone-based cured product having a terminal silicon content, which is a ratio of silicon atoms contained in terminal silicon to total silicon atoms contained in the product, of less than 0.1% by mass.
A cured product obtained by curing a composition containing (A) a bifunctional thermosetting silicone resin, (B) a polyfunctional thermosetting silicone resin, and (C) a curing catalyst, the cured product In the solid Si-nuclear magnetic resonance spectrum of (1), the peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half width is 0.5 ppm or more and 3.0 ppm or less, and (2) The peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the half value width of the peak is calculated from a peak selected from the group consisting of peaks of 1.0 ppm or more and 5.0 ppm or less. Silico with a terminal silicon content of less than 0.1% by mass, which is the ratio of silicon atoms contained in terminal silicon to all silicon atoms contained in the product It provides a system cured product. Hereinafter, each configuration of the present embodiment will be described.

The cured product of this embodiment is obtained by curing a composition containing (A) a bifunctional thermosetting silicone resin, (B) a polyfunctional thermosetting silicone resin, and (C) a curing catalyst. As such a composition, the composition for silicone type hardened | cured material mentioned later can be used. By measuring the solid ²⁹ Si-NMR of the cured product by a known method, at least one peak satisfying the condition (1) or (2) is observed.

  In the peak satisfying the condition (1), the abundance ratio of silicon atoms, generally called D sites, in which two oxygen atoms are bonded and two atoms other than oxygen atoms (usually carbon atoms) are bonded. One or more peaks are included. Here, if the cured product contains a silanol group, the peak or peaks indicating the abundance ratio of a silanol group (Si—OH) in which a hydrogen atom is bonded to one of the two oxygen atoms is the D Observed with peaks originating from the site.

  In the peak satisfying the condition (2), the abundance ratio of silicon atoms, generally called T sites, in which three oxygen atoms are bonded and one atom other than oxygen atoms (usually carbon atoms) is bonded. One or more peaks are included. Here, if the cured product contains a silanol group, one or more peaks indicating the abundance ratio of a silanol group (Si—OH) in which a hydrogen atom is bonded to one or two of the three oxygen atoms are present. Are observed together with peaks derived from the T site.

In the present embodiment, terminal silicon means silicon in which a crosslinkable reactive group having an oxygen atom such as a hydroxyl group or an alkoxy group is bonded to a silicon atom via the oxygen atom.
In solid-state ²⁹ Si-NMR, one or more peaks indicating the abundance ratio of terminal silicon are usually observed as peaks of D1, T1, or T2.

The peak of D1 is derived from a silicon atom in which two oxygen atoms are bonded, and one of the oxygen atoms constitutes the reactive group. The remaining one oxygen atom is usually bonded to another silicon atom.
The peak of T1 is derived from a silicon atom in which three oxygen atoms are bonded and two of them constitute the reactive group. The remaining one oxygen atom is usually bonded to another silicon atom.
The peak of T2 is derived from a silicon atom in which three oxygen atoms are bonded, and one of these oxygen atoms constitutes the reactive group. The remaining two oxygen atoms are usually bonded to other silicon atoms.

Therefore, the content of terminal silicon in the cured product of the present embodiment is obtained as follows.
First, in the spectrum chart obtained by measuring solid ²⁹ Si-NMR of the cured product of this embodiment, the ratio of the signal area derived from terminal silicon to the total signal area corresponding to silicon atoms is calculated. The calculated ratio (ratio of terminal silicon) is the ratio of silicon atoms contained in terminal silicon (present as terminal silicon) to all silicon atoms contained in the cured product.

In the spectrum analysis obtained by the solid ²⁹ Si-NMR measurement, the method for obtaining the signal area corresponding to the silicon atom and the signal area corresponding to the terminal silicon is not particularly limited, and a known method can be applied. Specifically, the area of the target signal can be obtained by obtaining an integral value for the signal to be measured using an analyzer that is normally attached to the NMR measuring apparatus. In the NMR measurement described above, the structure of atoms, functional groups, and substituents bonded to silicon atoms can be determined by referring to known databases and literatures.

When the spectrum obtained by solid-state ²⁹ Si-NMR measurement includes a lot of noise, a spectrum smoothing process may be performed. For example, the obtained spectrum can be first subjected to Fourier transform, smoothing processing can be performed by a method such as inverse Fourier transform after removing a high frequency component of 100 Hz or higher.

  When signals derived from silicon atoms placed in different chemical environments are observed independently without overlapping, on the baselines on both sides of the signal corresponding to the silicon atom to be measured, The start and end points of integration are set and the signal area is obtained.

  When signals derived from each of the silicon atoms are observed to overlap each other, the overlapping signals are separated by using the waveform separation processing software that is usually attached to the NMR apparatus, thereby corresponding to each silicon atom. Obtain the area of the signal to be transmitted. For example, using a Gauss function as a fit function and separating a plurality of superimposed signals into waveforms, the integration start point and end point are set in the same manner as when the above signals are observed independently, and the signal area is Desired.

  The terminal silicon content is a useful index for improving the physical properties of the cured product of the present embodiment. When the terminal silicon is formed when the oxygen atom bonded to the silicon atom of the silicone resin is bonded to a hydrogen atom or an alkyl group without being bonded to another silicon atom, the terminal silicon is formed. The resin network structure is not formed at the locations. That is, in the network structure of the resin constituting the cured product, the peripheral region of the terminal silicon tends to be a region where the molecular motion is locally high. The present inventors have found that the temperature change durability and crack resistance of the cured product can be improved when the terminal silicon content in the cured product is less than 0.1% by mass. Although this detailed mechanism is not yet elucidated, it is presumed that the local molecular motion of the resin is remarkably restricted by suppressing the generation of local high-motion regions in the network structure inside the cured product. The

Therefore, the terminal silicon content of the cured product of the present embodiment is less than 0.1% by mass, preferably as small as possible, and more preferably 0% by mass. Here, the terminal silicon content of 0% by mass refers to a state in which the silicon atom constituting the terminal silicon is not detected in the solid ²⁹ Si-NMR spectrum, that is, the signal corresponding to the terminal silicon is less than the detection limit. .
When the terminal silicon content in the cured product of the present embodiment is less than 0.1% by mass, the temperature change durability and crack resistance of the cured product can be improved.

  By the way, if it is assumed that a cured product can be obtained using only a silicone resin that does not have a reactive group such as a hydroxyl group and an alkoxy group in the side chain before curing, a cured product having theoretically zero terminal silicon content. Is obtained. However, even when a silicone resin having no reactive group in the side chain is cured, the resins are not chemically cross-linked, so that a network structure is not formed and a cured product having desired physical properties is difficult to obtain.

  Therefore, as a raw material for obtaining the cured product of the present embodiment, as will be described later, (A) a bifunctional thermosetting silicone resin (hereinafter sometimes referred to as component (A)), and (B) a polyfunctional thermosetting. It is preferable that a reactive silicone resin (hereinafter sometimes referred to as the component (B)) is used in combination, and at least one of the component (A) and the component (B) has a hydroxyl group or an alkoxy group constituting a silanol group. By adjusting the blending amounts of the component (A) and the component (B), almost all of the terminal silicon can be cross-linked in the curing reaction to obtain a cured product substantially free of terminal silicon.

In the solid ²⁹ Si-NMR measurement of the cured product of this embodiment, it is preferable that the spectrum corresponding to (A) the bifunctional thermosetting silicone resin satisfies the above condition (1), and (B) the polyfunctional thermosetting. The spectrum corresponding to the silicone resin preferably satisfies the condition (2).

  In the conditions (1) and (2), the position of the chemical shift at the peak top is mainly determined by the number of oxygen atoms bonded to the silicon atom and the type of functional group constituted by the oxygen atom. On the other hand, the half width of the peak is influenced by the distribution of siloxane bond angles of silicon atoms and reflects the internal stress of the cured product. That is, a large peak half width indicates that various strains are added to the siloxane bond angle.

  Therefore, from the viewpoint of reducing the internal stress of the cured product of the present embodiment and improving the temperature change durability and crack resistance, the half width of the peak in the condition (1) is 0.5 ppm or more and 3.0 ppm or less. It is preferable that it is 0.5 ppm or more and 2.0 ppm or less. From the same viewpoint, the half width of the peak under the condition (2) is preferably 1.0 ppm or more and 5.0 ppm or less, and more preferably 1.0 ppm or more and 4.0 ppm or less.

<Composition for silicone-based cured product>
In 2nd embodiment, the composition containing (A) bifunctional thermosetting silicone resin and (B) polyfunctional thermosetting silicone resin is provided. Hereinafter, each structure of the composition of this embodiment is demonstrated.

[(A) Bifunctional thermosetting silicone resin]
In this specification, (A) bifunctional thermosetting silicone resin (component (A)) is an organic polymer having a siloxane bond as the main chain, and is represented by the following general composition formula (F3). The average functional number of the compound is about 2. The average functional number is usually less than 2.5, preferably 2.4 or less, more preferably 1.8 or more and 2.2 or less.

(R ¹ R ² R ³ SiO _1/2 ) _M (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ SiO _3/2 ) _T (SiO _4/2 ) _Q (F3)

In the formula (F3), R ^{1 to} R ⁶ are each independently a reactive group capable of a crosslinking reaction such as a hydroxyl group or an alkoxy group, a hydrocarbon group such as an alkyl group or a phenyl group, or a halogen atom.
The alkyl group constituting the alkyl group and the alkoxy group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and preferably a linear alkyl group having 1 to 3 carbon atoms. More preferred. When R ^{1 to} R ⁶ are halogen atoms, these halogen atoms are regarded as oxygen atoms in the above formula (F3), and the functional number is counted.

In the above formula (F3), M, D, T, and Q are 0 or more and less than 1, and M + D + T + Q = 1. The repeating unit constituting the polyorganosiloxane represented by the formula (F3) is monofunctional [R, R, R—SiO _0.5 ] (triorganosylhemioxane), bifunctional [R, R. —SiO] (diorganosiloxane), trifunctional [R—SiO _1.5 ] (organosilsesquioxane), tetrafunctional [SiO ₂ ] (silicate) (however, for simplification, R ¹ shows the R collectively to R ^6.) a and, depending on the configuration ratio of these 4 kinds of repeating units, the functional number of the polyorganosiloxane is determined.

The functional number of the polyorganosiloxane of the above formula (F3) is calculated by the following formula (F4).
Functional number = (1 × M + 2 × D + 3 × T + 4 × Q) / (M + D + T + Q) (F4)

As a typical bifunctional thermosetting silicone resin, in the above formula (F3), a bifunctional (R ⁴ R ⁵ SiO _2/2 ) repeating unit, that is, a diorganosiloxane structure (—O—Si (R ⁴⁾ ) (R ⁵ ) —O—), a polyorganosiloxane composed of only. This (A) component has a functional number of 2.0.

In this embodiment, not only the typical bifunctional thermosetting silicone resin but also a known bifunctional thermosetting silicone resin having an average functionality of about 2 can be used.
As the component (A) of this embodiment, diorganopolysiloxane containing hydroxyl groups at both ends is preferable.

  300-10000 may be sufficient as the weight average molecular weight Mw of (A) component, for example, 500-4500 may be sufficient, for example, 800-4500 may be sufficient as it. When the said weight average molecular weight is too small, the volatilization amount at the time of thermosetting becomes large, and there exists a possibility that (A) component may not fully be contained in hardened | cured material. Moreover, when the said weight average molecular weight is too large, there exists a possibility that compatibility with (B) component may deteriorate.

  As the weight average molecular weight, a value generally measured by a gel permeation chromatography (GPC) method can be used. Specifically, after the polymer sample to be measured is dissolved in a soluble solvent, the solution is passed along with the mobile phase solution through a column using a filler having a large number of pores, and the molecular weight of the sample is measured. They are separated according to size and detected using a differential refractometer, UV meter, viscometer, light scattering detector or the like as a detector. In general, the weight average molecular weight is expressed in terms of standard polystyrene. The weight average molecular weight in this specification is indicated by this standard polystyrene conversion value. The column to be used may be appropriately selected according to the assumed molecular weight.

  In the GPC measurement, the solvent used for dissolving the silicone resin or the silicone oligomer is preferably the same solvent as the mobile phase solvent used in the GPC measurement, specifically tetrahydrofuran, chloroform, toluene, xylene, dichloromethane, dichloroethane, methanol. , Ethanol, isopropyl alcohol and the like.

[(B) Multifunctional thermosetting silicone resin]
In the present specification, (B) the polyfunctional thermosetting silicone resin (component (B)) means that the component (A) in the formula (F3) exceeds 2 and is included in the composition. It means a thermosetting silicone resin having a functional number greater than the functional number. Suitable polyfunctional thermosetting silicone resins in the present embodiment include those having a functional number of 2.5 to 3.5 and having at least one of a hydroxyl group and an alkoxy group.

The total number of hydroxyl groups and alkoxy groups possessed by component (B) is not particularly limited, and is, for example, 1 to 75, for example, 5 to 50 per 100 silicon atoms constituting component (B). For example, 10-30 may be sufficient. The total number of hydroxyl groups and alkoxy groups is 1 or more from the viewpoint of increasing the adhesion with the substrate during curing and from the viewpoint of sufficiently increasing the reaction point to form a cross-linking reaction with the component (A). Is preferred. The total number of hydroxyl groups and alkoxy groups is preferably 75 or less from the viewpoint of controlling the condensation reaction and controlling volume shrinkage at the time of curing that causes cracks. From the viewpoint of increasing the reactivity, a hydroxyl group is preferable to the alkoxy group.
As the component (B), a polyfunctional thermosetting silicone resin in which 50% or more (molar fraction) of the repeating units is trifunctional is preferable.

As a typical trifunctional thermosetting silicone resin, in the formula (F3), a trifunctional (R ⁶ SiO _3/2 ) repeating unit, that is, an organosilsesquioxane structure (—O—Si (O— ) (R ⁶ ) —O—).
The functional number of this (B) component is 3.0.

  In the present embodiment, not only the above-described typical trifunctional thermosetting silicone resin but also a known trifunctional thermosetting silicone resin having an average functional number of about 3 can be used.

  (B) The weight average molecular weight Mw of a component may be 1000-20000, for example, and 2000-10000 may be sufficient as it. If the weight average molecular weight is too small, the amount of shrinkage at the time of thermosetting becomes large and cracks are likely to occur. Moreover, when the said weight average molecular weight is too large, there exists a possibility that compatibility with (A) component may deteriorate. The measurement of the weight average molecular weight of (B) component can be performed by the method mentioned above.

  In addition to the component (A) and the component (B), the composition for a silicone-based cured product of the present embodiment contains (C) a curing catalyst (hereinafter sometimes referred to as the component (C)). Also good. The composition for a silicone-based cured product containing the component (C) may be a one-component (single agent type) composition containing the components (A), (B) and (C), or (A). A two-component (two-agent type) composition in which the component and the component (B) constitute the first composition and the component (C) constitutes the second composition may be used. Here, each composition is preferably liquid. Usually, a two-component composition is cured in a state where the respective compositions are mixed before curing.

  An organic solvent for dilution may be added to the first composition and the second composition for the purpose of adjusting the concentration of each component, improving operability, adjusting the viscosity, and the like. What is necessary is just to determine suitably the kind and usage-amount of an organic solvent according to the objective. For example, the organic solvent can be selected so that the boiling point of the liquid composition is 40 to 250 ° C, preferably 100 to 230 ° C. The content of the organic solvent in the total amount of the composition is preferably 30% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

[(C) Curing catalyst]
The curing catalyst as component (C) is not particularly limited as long as it can accelerate the condensation reaction of the silicone resin. For example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, organic acids such as formic acid, acetic acid, succinic acid, citric acid, propionic acid, butyric acid, lactic acid and succinic acid; ammonium hydroxide, tetramethylammonium hydroxide, hydroxylated Alkaline compounds such as tetraethylammonium; tin (Sn), zinc (Zn), iron (Fe), titanium (Ti), zirconium (Zr), bismuth (Bi), hafnium (Hf), yttrium (Y) as metal components, Examples thereof include organic metal compound catalysts such as organic complexes or organic acid salts containing at least one metal selected from the group consisting of aluminum (Al), boron (B), and gallium (Ga).

  Of these, a phosphoric acid catalyst is preferred from the viewpoint of compatibility with the silicone component and curing acceleration. Examples of the phosphoric acid catalyst include compounds represented by the following formula (C-1) or (C-2). In the formula, M represents a counter cation. * Represents another atom or atomic group. n is an integer of 0-2. When there are a plurality of M, the plurality of M may be the same or different from each other. When there are a plurality of *, the plurality of * may be the same or different from each other. Examples of the counter cation include a hydrogen ion. Examples of the atom or atomic group represented by * include —OR and R. Here, R represents a monovalent organic group. Specific examples of the phosphoric acid catalyst include phosphoric acid, phosphorous acid, phosphoric acid ester, phosphorous acid ester and the like. Among these, phosphoric acid is preferable from the viewpoint of high transparency and easy to obtain a cured product having a terminal silicon content of less than 0.1% by mass.

  In order to easily dissolve the curing catalyst at a predetermined concentration in the composition, the curing catalyst may be added to the composition in a state diluted with a silicone monomer or a silicone oligomer. A curing catalyst may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Moreover, you may use together with another reaction accelerator and reaction inhibitor.

  The amount of the curing catalyst can be appropriately adjusted in consideration of the heating temperature during the curing reaction, the reaction time, the type of catalyst, and the like. From the viewpoint of making the terminal silicon content of the cured product of this embodiment less than 0.1% by mass, the amount of the curing catalyst that is the component (C) is based on the total mass of the component (A) and the component (B). (100% by mass) is preferably 0.001 to 5.0% by mass, and more preferably 1.0 to 3.0% by mass. The amount of the curing catalyst described here is an acid, a base, a metal compound, etc. that act as a catalyst when the total mass of the component (A), the component (B), and the component (C) is 100% by mass ( C) The ratio (mass%) of the total mass of a component is represented. Therefore, when the curing catalyst is diluted with a solvent, the mass of the solvent is not included in the amount of the curing catalyst.

  When an organometallic compound catalyst is used as the curing catalyst, the amount of the curing catalyst is 0.001 to 0.001 based on the total mass of the component (A), the component (B), and the component (C) (100% by mass). The content is preferably 0.5% by mass (in terms of metal atoms), more preferably 0.003 to 0.2% by mass. The content of the organometallic compound catalyst can be measured by high frequency inductively coupled plasma (ICP) analysis of the metal component.

  When a phosphoric acid catalyst is used as the curing catalyst, the amount of the curing catalyst is 0.1 or more and 3 based on the total amount (100% by mass) of the component (A), the component (B) and the component (C). It is preferably less than 0.0% by mass, more preferably 1.0 or more and less than 3.0% by mass, and even more preferably 1.2 or more and less than 2.0% by mass. When the catalyst amount is in the preferred range, a cured product having a terminal silicon content of less than 0.1% by mass is easily obtained.

  The curing catalyst may be added to the composition containing the component (A) and the component (B) immediately before performing the curing reaction, or the composition containing only one of the component (A) or the component (B). (C) A curing catalyst may be added in advance, and a composition containing all of the components (A) to (C) during curing may be prepared.

[(D) Other ingredients]
The composition for a silicone-based cured product of the present embodiment may further contain other components (hereinafter sometimes referred to as (D) component). Examples of other components include any resin component other than the components (A) and (B), silicone oligomers, inorganic particles, phosphors, silane coupling agents, modifying silicone compounds, antifoaming agents, and others. And the like.

The mixing method of (A) component, (B) component, and (D) component is not specifically limited, You may use any of the well-known methods normally performed when mixing 2 or more types of polymer | macromolecule. For example, (A) component, (B) component, and (D) component can be mixed by dissolving or dispersing in an organic solvent.

  From the viewpoint of improving the stability of the obtained mixed solution by uniformly mixing, after dissolving the component (A), the component (B) and the component (D) in an organic solvent having high volatility and solubility It is preferable to substitute another solvent. Specifically, first, the component (A) is put into a highly volatile organic solvent (hereinafter referred to as organic solvent P), and dissolved by heating to a temperature near the boiling point of the organic solvent P and stirring. Next, the component (B) is added, mixed and dissolved in the same manner. Next, the component (D) is added, mixed and dissolved in the same manner. Thereafter, a solvent having a lower volatility than the organic solvent P (hereinafter, solvent Q) is added and heated to remove the organic solvent P until the concentration of the organic solvent P becomes 1% or less. Solvent replacement with solvent Q can be performed. At that time, as a means for performing solvent replacement more efficiently, the inside of the container containing the mixed solution may be heated in a reduced pressure state.

  By performing the above solvent substitution treatment, the residual solvent used when synthesizing the component (A), the component (B), and the component (D), water remaining unreacted, etc. can be removed and mixed. It is effective for improving the stability of the solution.

  As the organic solvent P, an organic solvent having a boiling point of less than 100 ° C. is preferable. Specifically, ketone solvents such as acetone and methyl ethyl ketone; alcohol solvents such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol; hydrocarbon solvents such as hexane, cyclohexane, heptane, and benzene; methyl acetate, ethyl acetate, and the like And acetate solvents such as dimethyl ether and tetrahydrofuran.

  As the solvent Q, an organic solvent having a boiling point of 100 ° C. or higher is preferable. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethyl hexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monoethylhexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol monoethyl hexyl ether, propylene glycol monophenyl ether, propylene glycol monobenzyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol monoethyl hexyl ether, dipropylene glycol monophenyl ether, dip Glycol ether solvents such as pyrene glycol monobenzyl ether; ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monohexyl ether acetate, ethylene glycol monoethylhexyl ether acetate, ethylene glycol monophenyl Examples include glycol ester solvents obtained by adding an acetic acid group to the above-described glycol ether solvents such as ether acetate and ethylene glycol monobenzyl ether acetate.

(Inorganic particles, phosphors)
The composition for a silicone-based cured product of the present embodiment may contain various inorganic particles and a phosphor that emits fluorescence by receiving light depending on the use of the cured product. For example, when the cured product of the present embodiment contains inorganic particles and a phosphor, light incident on the cured product is scattered by the inorganic particles, and the phosphor can be excited effectively. Moreover, by adding inorganic particles to the composition before curing, it is possible to suppress the precipitation of the phosphor in the composition or to adjust the viscosity of the composition. Further, the addition of inorganic particles can improve the light scattering property, refractive index, dimensional stability, and mechanical strength of the cured product.

  When a phosphor is blended in the silicone-based cured product composition of the present embodiment, it is preferable to blend inorganic particles in the composition in advance in order to suppress the precipitation of the phosphor. In addition, it is preferable that the composition containing the phosphor is rapidly cured before the phosphor is precipitated.

  The material of the inorganic particles is not particularly limited, and preferable examples include oxides such as silicon, titanium, zirconium, aluminum, iron, and zinc, carbon black, barium titanate, calcium silicate, and calcium carbonate. Among these, silicon oxide, titanium oxide, and aluminum oxide are preferable from the viewpoint of increasing the light transmittance of the cured product. Furthermore, oxides of silicon and aluminum are preferable from the viewpoint of low absorption of UV light.

  The shape of the inorganic particles is not particularly limited, and examples thereof include a substantially spherical shape, a plate shape, a column shape, a needle shape, a whisker shape, and a fiber shape.

  One type or two or more types may be sufficient as the material and shape of the inorganic particle which the composition for silicone type hardened | cured materials of this embodiment contains, respectively. Moreover, it is preferable that the inorganic particle of 2 or more types of particle sizes is included. Specifically, it is more preferable to include at least two kinds of inorganic particles A whose primary particles have an average particle diameter of 100 to 500 nm and inorganic particles B whose primary particles have an average particle diameter of less than 100 nm. By including two or more types of inorganic particles having different average particle sizes of primary particles, the excitation efficiency of the phosphor due to light scattering is further improved, and a further effect can be exhibited in preventing the precipitation of the phosphor.

  The average particle diameter of the primary particles is determined by an image imaging method or the like in which inorganic particles are observed using an electron microscope or the like. Specifically, first, the inorganic particles to be measured are put into an arbitrary solvent, and if necessary, a dispersion liquid sufficiently dispersed by irradiating ultrasonic waves or the like is dropped onto a slide glass or the like and further dried. A sample obtained by sprinkling inorganic particles on the adhesive surface of the adhesive tape and attaching the inorganic particles to the adhesive surface is prepared. Next, the sample is observed with a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like, and the dimensions of the inorganic particles are obtained from the observed image. As a method for obtaining the dimensions, for example, the projected area of the inorganic particles may be obtained, the diameter of a circle corresponding to this area may be obtained, and the particle diameter of the inorganic particles may be obtained. In this case, for example, the arithmetic average of the particle diameters obtained for 100 or more inorganic particles can be used as the average particle diameter of the inorganic particles.

  There is no restriction | limiting in particular in content of an inorganic particle, For example, 0.01-10 mass% may be sufficient on the basis (100 mass%) of the sum total of (A) component and (B) component, 0.1 It may be ˜5% by mass.

  Moreover, there is no restriction | limiting in particular in the composition and kind of fluorescent substance, For example, the red fluorescent substance which emits fluorescence in the range of wavelength 570-700 nm, the green fluorescent substance which emits fluorescence in the range of 490-570 nm, in the range of 420-480 nm Examples thereof include blue phosphors that emit fluorescence. Also, a plurality of phosphors can be mixed depending on the brightness and chromaticity. There is no restriction | limiting in particular in content of a fluorescent substance, It can adjust suitably with the light quantity of a light emitting element, chromaticity and brightness required as a semiconductor light-emitting device.

(Silane coupling agent)
When the silicone-based cured product of the present embodiment is cured in a state where it is in contact with the substrate to obtain a silicone-based cured product, it is preferable to add a silane coupling agent to the composition. The addition of the silane coupling agent has the effect of improving the adhesion of the cured product of the present embodiment to a substrate such as a semiconductor light emitting device or a substrate. Suitable silane coupling agents include, for example, at least one selected from the group consisting of vinyl group, epoxy group, styryl group, methacryl group, acrylic group, amino group, ureido group, mercapto group, sulfide group and isocyanate group. A silane coupling agent having Among these, a coupling agent containing an epoxy group or a mercapto group is more preferable. Specifically, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldi Examples of particularly preferred silane coupling agents include ethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  The content of the silane coupling agent in the silicone-based cured product composition of the present embodiment is, for example, 0.0001 to 1.0 part by mass (solid content) with respect to 100 parts by mass of the solid content of the composition. For example, 0.001-0.5 mass part may be sufficient.

  The silane coupling agent may be blended in advance in the silicone-based cured product composition of the present embodiment. In addition, the silane coupling agent may be attached in advance to the surface to which the composition of the present embodiment is applied, for example, the surface of a semiconductor light emitting device or a substrate. In the latter case, the composition is cured while being in contact with the surface to which the silane coupling agent is attached, so that the cured product with respect to the surface can be obtained even when no silane coupling agent is added to the composition in advance. Adhesion can be improved.

(Modifying silicone compound)
The silicone-based cured product composition of the present embodiment may contain a modifying silicone compound that is a silicone compound different from the component (A) and the component (B) as the component (D).

  Examples of the modifying silicone compound include general silicone compounds commercially available on the market. By adding the modifying silicone compound, for example, flexibility can be imparted to the silicone-based cured product.

  The content of the modifying silicone compound in the silicone-based cured product composition of the present embodiment is, for example, 0.1 to 20 parts by mass (solid content) with respect to 100 parts by mass of the solid content of the composition. For example, 0.5-10 mass parts may be sufficient.

(Defoamer)
You may add an antifoamer to the composition for silicone type hardened | cured materials of this embodiment. By adding an antifoaming agent, it is possible to suppress the generation of bubbles when the composition is mixed. The content of the antifoaming agent in the composition may be, for example, 0.01 to 3 parts by mass (solid content) with respect to 100 parts by mass of the solid content of the composition, for example 0.01 to 1 mass. Part.

[Mixing ratio of each component in the composition for silicone-based cured product]
As a suitable blending ratio in the composition for a silicone-based cured product of the present embodiment, the ratio of the component (B) based on the total mass of the component (A) and the component (B) (100% by mass) is 20% by mass. Is less than 80% by mass, the average functionality of the component (B) is 2.5 to 3.5, and 50% or more (molar fraction) of the repeating units constituting the component (B) is trifunctional. The proportion of the component (C) based on the total mass of the components (A), (B) and (C) (100% by mass) is 1.0% by mass or more and less than 3.0% by mass. The ratio can be exemplified.

  Since the composition of the above-mentioned suitable blending ratio has good efficiency of the crosslinking reaction at the time of curing, the terminal silicon content of the obtained cured product tends to be less than 0.1% by mass. Furthermore, when the ratio of the component (A) to the component (B) is as described above, the temperature change durability and crack resistance of the cured product are further improved.

  From the viewpoint of easily making the terminal silicon content of the cured product obtained by curing the silicone-based cured product composition of the present embodiment less than 0.1% by mass, and the temperature change durability of the cured product, From the viewpoint of further improving the crack resistance, the proportion of the component (B) in the composition based on the total mass of the component (A) and the component (B) (100% by mass) is 20% by mass or more and 80%. The content is preferably less than mass%, more preferably from 20 mass% to less than 70 mass%, and even more preferably from 30 mass% to 60 mass%.

  From the viewpoint of easily making the terminal silicon content of the cured product obtained by curing the silicone-based cured product composition of the present embodiment less than 0.1% by mass, and the temperature change durability of the cured product, From the viewpoint of further improving the crack resistance, the ratio of the component (C) based on the total mass of the component (A), the component (B), and the component (C) in the composition (100% by mass) It is preferable that it is 1.0 mass% or more and less than 3.0 mass%, and it is more preferable that it is 1.2 mass% or more and less than 2.0 mass%.

  From the viewpoint of easily making the terminal silicon content of the cured product obtained by curing the silicone-based cured product composition of the present embodiment less than 0.1% by mass, and the temperature change durability of the cured product, From the viewpoint of further improving crack resistance, the total content of the component (A), the component (B), and the component (C) with respect to the total mass of the composition is preferably 90% by mass or more.

  The silicone-based cured product obtained by curing the composition for a silicone-based cured product of the present embodiment has a very low terminal silicon content, so there is little deterioration due to UV light, and excellent temperature change durability and crack resistance. . Moreover, when the component (C) and the component (D) are difficult to absorb UV light, the cured product has high UV light transmittance. Therefore, the cured product of the present embodiment is suitable as a silicone-based sealing material used for sealing a light source in a light source device. In addition, since the UV light extraction efficiency is high and inexpensive compared to the UV-LED sealed with quartz glass, the cured product of this embodiment is suitable as a sealing material for the UV-LED.

  When the cured product of the present embodiment is used as a silicone-based sealing material, in the silicone-based cured product composition of the present embodiment, the content of the component (B) is relative to the total amount of the composition at the time of curing. It is preferable that it is 0.5 mass% or more and less than 100 mass%. When the content of the component (B) is less than 0.5% by mass, the gas barrier property of the silicone-based sealing material becomes insufficient, and the gloss retention of the lead electrode tends to decrease. Moreover, there is a possibility that good hardness cannot be obtained due to insufficient crosslinking. On the other hand, when the component (B) is 100% by mass, the curing rate is remarkably increased, so that it becomes difficult to control the curing reaction, the hardness after curing becomes too high, and the silicone-based sealing material has a resistance to resistance. There exists a tendency for crack property to fall.

[Method for producing silicone-based cured product]
In the third embodiment, the method for producing a silicone-based cured product by curing the silicone-based cured product composition includes, for example, (A) a bifunctional thermosetting silicone resin and (B) a polyfunctional thermosetting. Before applying a composition containing a silicone resin and (C) a curing catalyst to a substrate, a method for producing a silicone-based cured product through a step of heating the composition in the range of 40 ° C. to 100 ° C. I will provide a.

  The heating treatment time may be short if the temperature is high, and requires a long time if the temperature is low. For example, it is preferably about 1 minute to 2 hours, and more preferably about 10 minutes to 1 hour. It is preferable to gently stir the composition during the heating. Moreover, since hardening progresses by the said heating, following the said heating, it is preferable to apply | coat the said composition to a base material rapidly and to make this harden | cure.

  The heating improves the applicability of the composition to the substrate, and the terminal silicon content after curing tends to be less than 0.1% by mass. Although this mechanism has not been elucidated, it is presumed as a cause that the silicone resins in the composition are easily placed in a cross-linking reaction by performing the heating before the main curing.

  As conditions for carrying out the main curing of the composition for a silicone-based cured product of this embodiment, for example, a method of heating at room temperature to 250 ° C. for 5 minutes to 6 hours can be mentioned. For example, after adding the (C) curing catalyst to the composition, it is applied to the substrate through the heating step, and further in an atmosphere at a temperature of 250 ° C. or lower, for example, in an atmosphere at 40 to 200 ° C. The method of making it harden | cure by leaving to stand is mentioned.

  Moreover, as a method of this hardening, in order to remove the solvent and water which may exist in the said composition, and control the condensation reaction rate of a silicone resin, for example, it is 5-30 minutes at 40-60 degreeC, and then 60- You may make it harden | cure in steps, such as 10 to 60 minutes at 100 degreeC, and 30 minutes to 5 hours after that at 140-200 degreeC.

[Semiconductor light emitting device]
In 4th embodiment, the semiconductor light-emitting device which has a base material, the semiconductor light-emitting device arrange | positioned at the said base material, and the said silicone type hardened | cured material which seals at least one part of the said semiconductor light-emitting device is provided. Hereinafter, description will be given with reference to the drawings.

  FIG. 1 is a cross-sectional view of the semiconductor light emitting device 100 of this embodiment. The semiconductor light emitting device 100 includes a substrate 110, a semiconductor light emitting element 120 disposed on the substrate, and a sealing portion 130 that seals the semiconductor light emitting element 120. The sealing part 130 is a silicone-based sealing material constituted by a silicone-based cured product obtained by curing the composition for a silicone-based cured product. The semiconductor light emitting device 120 is covered and sealed by the substrate 110 and the sealing portion 130 and is isolated from the outside air.

  The sealing unit 130 does not have a discontinuous surface in a direction perpendicular to the substrate 110. The presence or absence of a discontinuous surface can be determined, for example, by performing X-ray CT measurement. In X-ray CT, since the scattering intensity varies depending on the electron density, if there is a discontinuous surface of the material, it appears in the density of the CT image.

  The silicone-based encapsulant constituting the encapsulating part 130 has high UV light permeability, little deterioration due to UV light, and excellent temperature change durability and crack resistance. Moreover, compared with the sealing part comprised with quartz glass, the transmittance | permeability of UV light is equivalent, and the extraction efficiency of light is high and cheap. Therefore, it is preferable that the semiconductor light emitting device of the present embodiment is a UV-LED because the above characteristics of the silicone-based sealing material constituting the sealing portion 130 can be utilized.

  Known light-emitting elements and substrates constituting the semiconductor light-emitting device of this embodiment can be applied. The emission wavelength of the light emitting element may be in the ultraviolet region (for example, 10 to 400 nm), in the visible light region (for example, more than 400 nm and less than 830 nm), or in the infrared region (for example, 830 nm to 1000 μm). May be.

  Hereinafter, although an experiment example is shown and this invention is demonstrated concretely, this invention is not limited to the following experiment example.

  The measurement conditions for each measurement shown in the experimental examples described later are shown below.

^<29 Si-NMR measurement conditions>
Device name: 400-MR manufactured by Agilent
Observation nucleus: ²⁹ Si
Observation frequency: 79.42 MHz
Measurement temperature: room temperature Measurement solvent: CDCl ₃
Pulse width: 8.40 μsec (45 °)
Pulse repetition time: 15.0 sec
Integration count: 4000 times Sample concentration (sample / measuring solvent): 300 mg / 0.6 ml

<GPC measurement conditions>
Device name: HLC-8120 GPC manufactured by Tosoh Corporation
Column: TSKgel Multipore HXL-M × 3 Flow rate: 1.0 ml / min Detection condition: RI
Concentration: 100 mg + 5 ml (THF)
Injection volume: 100 μl
Column temperature: 40 ° C
Eluent: THF

<Heat shock test>
Device name: Small spec thermal shock device TSE-11-A manufactured by Espec
Cold temperature: -30 ° C ⇔ 90 ° C
Holding time: 30 minutes Temperature increase / decrease rate: 140/2 (° C / min)
Number of cycles: 100 cycles

<UV irradiation test>
Device name: Spot cure SP9-250DB manufactured by Ushio Electric Co., Ltd. With uniform irradiation optical unit Measurement temperature: Room temperature Irradiation intensity: 30 μW / cm ²
Irradiation time: 100 hours

<Measurement of storage modulus>
Device name: DMA Q800, manufactured by TA Instruments
Measurement frequency: 10Hz
Measurement temperature: -50 ° C to 250 ° C
Temperature increase rate: 5 ° C./min Measurement atmosphere: Nitrogen Sample size: 4.8 mm × 20 mm × 0.3 mm

[Example 1]
A silicone-based cured product was prepared by thermally curing a composition for a silicone-based cured product in which resin A (functional number 2) and resin B (functional number 3) were blended at a mass ratio of 60:40.
Specifically, 40.0 g of the following resin B (weight average molecular weight = 3500) and 22.2 g of isopropyl alcohol are put into a flask with a return apparatus installed in an oil bath, and the liquid temperature is 80 to 85. The mixture was stirred while refluxing isopropyl alcohol at a temperature to sufficiently dissolve the resin.

  Next, 60.0 g of the resin A represented by the following formula (A-1) (weight average molecular weight = 2100, high molecular weight side 5% fractional molecular weight = 4609) is added to the resin B solution for 1 hour or more. The composition containing resin A and resin B was obtained by stirring and dissolving.

［式中、Ｍｅはメチル基であり、ｎは１以上の整数を表す。］

[In the formula, Me represents a methyl group, and n represents an integer of 1 or more. ]

  After adding 0.026 g of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent to the obtained composition, it was set in an evaporator, and the temperature of the composition was 80 ° C. and the pressure was 4 kPa. The isopropyl alcohol was distilled off until the isopropyl alcohol concentration in the composition was 1% by mass or less.

  The additive which consists of a silicone oligomer (n represents the integer of 3-7) represented by a following formula (D-1) containing 15 mass% phosphoric acid as a curing catalyst was prepared.

  The above-mentioned additive was added to the above composition obtained by distilling off isopropyl alcohol so as to be 10% by mass, and the mixture was sufficiently stirred and mixed to obtain the desired composition for a silicone-based cured product. Here, the concentration of the curing catalyst with respect to the total mass (100 mass%) of the resin A, the resin B and the curing catalyst in the composition was 1.5 mass%.

(Production of silicone-based cured product)
1.2 g of the obtained composition for a silicone-based cured product is put into an aluminum cup, heated in an oven for 10 minutes to 40 ° C. and then left for 10 minutes, and then heated to 150 ° C. for 0.5 hour. After the temperature rise, the composition was allowed to stand for 5 hours, and the composition for a silicone-based cured product was cured by heat (main curing) to obtain a desired silicone-based cured product.

When the obtained silicone-based cured product was measured by ²⁹ Si-NMR, a terminal silicon peak was not observed. That is, even if terminal silicon was contained in the obtained silicone-based cured product, the content was less than 0.1% by mass, and the content was less than the detection limit (quantitative lower limit). ^{The 29} Si-NMR spectrum is shown in FIG. The arrow “SSB” in FIG. 2 indicates the spinning sideband.

  On the other hand, a plurality of peaks (peak group A) in which the peak top position is in the region where the chemical shift is −40 ppm to 0 ppm and the half width of the peak is 0.5 ppm to 3.0 ppm are observed. Further, a plurality of peaks (peak group B) in which the peak top position was in the region where the chemical shift was −80 ppm or more and less than −40 ppm and the half width of the peak was 1.0 ppm or more and 5.0 ppm or less were observed. In the NMR chart obtained by the measurement, the ratio of the signal areas of the peak group A and the peak group B was approximately 6: 4.

(Production of semiconductor light emitting device)
A predetermined amount of the composition for a silicone-based cured product prepared above was heated to 40 ° C. in an oven for 10 minutes and then allowed to stand for 10 minutes, and then quickly applied onto a substrate equipped with a semiconductor light emitting device. The semiconductor element was sealed. At this time, since the coating property of the composition was excellent, sealing was easy. Subsequently, the temperature was raised to 150 ° C. over 0.5 hours, and then left for 5 hours to be fully cured, thereby obtaining a target semiconductor light emitting device.
Here, as the substrate, a substrate of 3.5 mm × 3.5 mm size (manufactured by LTCC) in which an electrode substrate was gold-plated was used.

(Heat shock test)
About the produced semiconductor light-emitting device, the temperature cycle which hold | maintains at -30 degreeC for 30 minutes, heats up to 90 degreeC over 2 minutes, hold | maintains at 90 degreeC for 30 minutes, and falls to -30 degreeC over 2 minutes. A heat shock test repeated 100 times was performed, and the occurrence of cracks in the sealing portion immediately above the chip was evaluated by microscopic observation. As a result, no crack was generated.

[Example 2]
Except having changed the compounding of resin A and resin B into 50:50 (mass ratio), the composition for silicone type hardened | cured materials was prepared similarly to Example 1, and the silicone type hardened | cured material and the semiconductor light-emitting device were produced. .
The solid ²⁹ Si-NMR of the silicone-based cured product obtained in Example 2 was measured, and the NMR measurement of Example 1 was performed except that the ratio of the signal area of peak group A and peak group B was approximately 5: 5. The same result as in the above was obtained. The terminal silicon content was less than 0.1% by mass.
When the heat shock test of the semiconductor device obtained in Example 2 was performed in the same manner as in Example 1, no cracks occurred in the sealing portion.

[Comparative Example 1]
A silicone-based cured product and a semiconductor light emitting device were prepared by thermally curing a composition for a silicone-based cured product using the resin A and the resin B in a mass ratio of 25:75.
Specifically, 75.0 g of the resin B (weight average molecular weight = 3500) and 22.2 g of isopropyl alcohol are put into a flask with a return apparatus installed in an oil bath, and the liquid temperature is 80 to 80%. The resin was sufficiently dissolved by stirring while refluxing isopropyl alcohol at 85 ° C.

  Next, 25.0 g of the resin A was added to the solution of the resin B, and the mixture was stirred and dissolved for 1 hour or longer to obtain a composition containing the resin A and the resin B. After adding 11.1 g of 2-butoxyethyl acetate as a solvent and 0.033 g of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent, the resulting composition was set in an evaporator, The composition was allowed to stand at a temperature of 80 ° C. and a pressure of 4 kPa, and isopropyl alcohol was distilled off until the isopropyl alcohol concentration in the composition became 1% by mass or less.

  The additive which consists of a silicone oligomer (n represents the integer of 3-7) represented by the said Formula (D-1) containing 15 mass% phosphoric acid as a curing catalyst was prepared. This additive was added to the composition obtained by distilling off the isopropyl alcohol so as to be 2% by mass and sufficiently stirred and mixed to obtain a composition for a silicone-based cured product. Here, the concentration of the curing catalyst with respect to the total mass (100 mass%) of the resin A, the resin B and the curing catalyst in the composition was 0.3 mass%.

(Production of silicone-based cured product)
1.2 g of the above composition for a silicone-based cured product is placed in an aluminum cup, heated to 40 ° C. over 10 minutes in an oven and left for 10 minutes, and then heated to 150 ° C. over 0.5 hours. The composition was allowed to stand for 5 hours after warming, and the silicone-based cured product composition was thermally cured to obtain a silicone-based cured product.

When the obtained silicone sealing material was measured by ²⁹ Si-NMR, a peak indicating the presence of terminal silicon was observed. When the terminal silicon content was calculated by the method described above, it was about 5% by mass.

(Production of semiconductor light emitting device)
A predetermined amount of the composition for a silicone-based cured product of Comparative Example 1 prepared above was heated to 40 ° C. in an oven for 10 minutes and then allowed to stand for 10 minutes. The semiconductor element was sealed by coating on the top. Subsequently, the semiconductor light emitting device of Comparative Example 1 was obtained by raising the temperature to 150 ° C. over 0.5 hours and allowing it to stand for 5 hours, followed by main curing.

(Heat shock test)
For the semiconductor light emitting device of Comparative Example 1, a heat shock test was performed in the same manner as in Example 1. As a result, generation of cracks was observed.

<Comparison evaluation of crack resistance>
From the result of the above heat shock test, the silicone-based cured products of Examples 1 and 2 having a terminal silicon content of less than 0.1% by mass are cured in Comparative Example 1 in which the terminal silicon content is about 5% by mass. It was found that the crack resistance and the temperature change durability were improved as compared with the product.

  About each silicone type hardened | cured material of Examples 1-2, when storage elastic modulus (MPa) was measured, respectively, Example 1 (bifunctional resin A: polyfunctional resin B = 60: 40 (mass ratio)). The cured product was lower than the cured product of Example 2 (bifunctional resin A: polyfunctional resin B = 50: 50 (mass ratio)). From this result, it can be said that the cured product of Example 1 is more excellent in crack resistance.

  About each silicone type hardened | cured material of Examples 1-2 and the comparative example 1, when the test which irradiates an ultraviolet-ray (UV) continuously for 100 hours was performed, many cracks generate | occur | produce in the silicone type hardened | cured material of the comparative example 1 did. On the other hand, no crack occurred in each silicone-based cured product of Examples 1-2. Therefore, it turned out that UV durability is improving the silicone type hardened | cured material of Examples 1-2 compared with the comparative example 1. FIG.

  The composition for a silicone-based cured product according to the present invention is useful because it provides a silicone-based cured product having improved crack resistance. Moreover, since the silicone-based cured product according to the present invention has improved crack resistance, it is useful for sealing material applications in semiconductor light-emitting devices.

DESCRIPTION OF SYMBOLS 100 ... Semiconductor light-emitting device, 110 ... Board | substrate, 120 ... Semiconductor light-emitting device, 130 ... Sealing part,
130a ... Semiconductor light emitting element vicinity, 130b ... Seal surface surface vicinity

Claims (12)

A cured product of (A) a bifunctional thermosetting silicone resin and (B) a polyfunctional thermosetting silicone resin,
In the solid Si-nuclear magnetic resonance spectrum,
(1) The peak where the peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and
(2) The peak top position is calculated from a peak selected from the group consisting of peaks in the region where the chemical shift is −80 ppm or more and less than −40 ppm, and the silicon atoms contained in the terminal silicon with respect to all silicon atoms contained in the cured product A silicone-based cured product having a terminal silicon content ratio of less than 0.1% by mass. A cured product obtained by curing a composition containing (A) a bifunctional thermosetting silicone resin, (B) a polyfunctional thermosetting silicone resin, and (C) a curing catalyst,
In the solid Si-nuclear magnetic resonance spectrum,
(1) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half width of the peak is 0.5 ppm or more and 3.0 ppm or less, and
(2) The peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the half value width of the peak is calculated from a peak selected from the group consisting of peaks of 1.0 ppm or more and 5.0 ppm or less. The silicone-based cured product according to claim 1, wherein a terminal silicon content, which is a ratio of silicon atoms contained in terminal silicon to total silicon atoms contained in the product, is less than 0.1% by mass.   The silicone-based cured product according to claim 2, wherein (C) is a phosphoric acid-based catalyst. In the composition,
The ratio of (B) based on the sum of (A) and (B) is 20% by mass or more and less than 80% by mass,
The functional number of (B) is 2.5 to 3.5,
50% or more of the repeating units constituting (B) are trifunctional,
The silicone-based cured product according to claim 3, wherein the ratio of (C) based on the sum of (A), (B), and (C) is 1.0% by mass or more and less than 3.0% by mass. In the composition,
The silicone-based cured product according to any one of claims 2 to 4, wherein a ratio of (B) based on the sum of (A) and (B) is 30% by mass or more and less than 60% by mass. In the composition,
The ratio of (C) based on the sum of (A), (B) and (C) is 1.2% by mass or more and less than 2.0% by mass, according to any one of claims 2 to 5. Silicone-based cured product. With respect to the total mass of the composition,
The silicone-based cured product according to any one of claims 2 to 6, wherein the total content ratio of (A), (B), and (C) is 90% by mass or more.   The silicone-based cured product according to any one of claims 2 to 7, which is a silicone-based sealing material used in a sealing application.   The semiconductor light-emitting device which has a base material, the semiconductor light-emitting device arrange | positioned at the said base material, and the silicone type hardened | cured material of Claim 8 which seals at least one part of the said semiconductor light-emitting device.   The semiconductor light emitting device according to claim 9, wherein an emission wavelength of the semiconductor light emitting element is in an ultraviolet region. A composition containing (A) a bifunctional thermosetting silicone resin, (B) a polyfunctional thermosetting silicone resin and (C) a curing catalyst,
The ratio of (B) based on the sum of (A) and (B) is 20% by mass or more and less than 70% by mass,
The ratio of (C) based on the sum of (A), (B) and (C) is 1.0 mass% or more and less than 3.0 mass%,
The functional number of (B) is 2.5 to 3.5,
50% or more of the repeating units constituting (B) are trifunctional.
Composition for silicone-based cured product.   The composition for a silicone-based cured product according to claim 11, wherein (C) is a phosphoric acid-based catalyst.

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